JP2002293839A - Hardenable composition and its hardened product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hardenable composition giving a hardened product excellent in antistatic properties, mar resistance and transparency or the like and to provide the hardened product. SOLUTION: An organic solvent hardenable composition is characterized by containing the following compounds (A-1) to (D) in the total solid content of which the concentration is 0.5-75%. (A-1) a tin-oxide containing a needle- shaped antimon of 40-80 wt.%, (B) a reactant of a hydroxyl group-containing multifunctional (meth)acrylate and a diisocyanate of 5-40 wt.%, (C) a multifunctional (meth)acrylate of 5-30 wt.%, (D) a photopolymerization initiator of 0.5-10 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition suitable as a material for an antireflection film and the like, and a cured product thereof.

[0002]

2. Description of the Related Art As a material for an antireflection film, for example, a thermosetting polysiloxane composition is known.
-247743, JP-A-6-25599,
JP-A-7-331115 and JP-A-10-23
No. 2301, for example. However, an antireflection film obtained by using such a thermosetting polysiloxane composition has poor antistatic properties and abrasion resistance, and as a result, has poor durability. Further, in producing such an antireflection film, it is necessary to perform a heat treatment at a high temperature for a long time, and thus the productivity is low, or the types of applicable base materials are limited.

Therefore, as disclosed in JP-A-8-94806, a high-refractive-index film in which fine particles are poled in a high-refractive-index binder resin on a substrate, and a fluorine-based copolymer A material for an antireflection film in which a low refractive index film made of the following is sequentially laminated. More specifically, in order to form a high-refractive-index film, a fine particle layer of metal oxide particles or the like is previously formed on process paper, and is pressed against a high-refractive-index binder resin on a base material. Thereby, the fine particle layer is buried in the high refractive index binder resin to make it polar. Further, for the low refractive index film, a fluorine-containing copolymer consisting of vinylidene fluoride and hexafluoropropylene, a polymerizable compound having an ethylenically unsaturated group,
The resin composition comprising the polymerization initiator is cured to form a thin film. On the other hand, JP-A-8-231222 and JP-A-9-12314 disclose fine powders of acicular metal oxides. However, materials for antireflection films using such fine powders are disclosed. Absent.

[0004]

Conventionally, as disclosed in Japanese Patent Application Laid-Open No. Hei 8-94806, the shape of metal oxide particles contained in a high refractive index film is spherical. No consideration was given, and there was a problem that the antistatic property, abrasion resistance and transparency of the high refractive index film were insufficient.

Accordingly, the present inventors have conducted intensive studies and as a result,
By forming a curable composition containing acicular antimony-containing tin oxide as metal oxide particles, when cured, a cured product having excellent antistatic properties, abrasion resistance, transparency and the like is obtained. Was found to be. Accordingly, the present invention is, for example, a curable composition which is suitable as a material for an anti-reflection film, and which when cured, gives a cured product having excellent antistatic properties, scratch resistance and transparency. And a cured product comprising such a curable composition.

[0006]

According to the present invention, the following compounds (A-1) to (D) are contained in the total solid content, and the total solid content is 0.5 to 75%. The present invention can provide an organic solvent-based curable composition characterized by the above, and can solve the above-mentioned problems. (A-1) 40 to 80% by weight of acicular antimony-containing tin oxide (B) 5 to 40% by weight of a hydroxyl-containing polyfunctional (meth) acrylate and a diisocyanate (C) 5 to 30% by weight of a polyisocyanate Functional (meth) acrylate (D) 0.5 to 10% by weight of a photopolymerization initiator Here, “total solid content” is a residue obtained by drying the curable composition on a hot plate at 120 ° C. for 1 hour. is there. With this configuration, it is possible to easily obtain a curable composition capable of obtaining a cured product having excellent antistatic properties, scratch resistance, transparency, and the like when cured.

Further, according to another aspect of the present invention, the total solid content contains the following compounds (A-2) to (D), and the content of acicular antimony-containing tin oxide in the total solid content Is 40-8
0% by weight, and an organic solvent-based curable composition characterized by having a total solid content of 0.5 to 75%,
The above-mentioned problem can be solved. (A-2) 40 to 89.5% by weight of surface-treated acicular antimony-containing tin oxide (B) 5 to 40% by weight of a hydroxyl-containing polyfunctional (meth) acrylate and a diisocyanate reactant (C) 5 Up to 30% by weight of a polyfunctional (meth) acrylate (D) 0.5 to 10% by weight of a photopolymerization initiator Improving the scratch resistance of a cured product by subjecting acicular antimony-containing tin oxide to surface treatment. Can be. Also,
By defining the content of the acicular antimony-containing tin oxide in the acicular antimony-containing tin oxide surface-treated in this way, when cured, the cured composition has excellent antistatic properties, abrasion resistance and transparency. The curable composition from which the product is obtained can be reliably obtained.

In constituting the curable composition of the present invention, it is preferable that the surface treatment is to bond the acicular antimony-containing tin oxide with an organic compound having a polymerizable unsaturated group. By using the acicular antimony-containing tin oxide bonded to the organic compound having such a polymerizable unsaturated group, not only can improve the dispersibility of the acicular antimony-containing tin oxide in the curable composition, When cured, a polymerizable unsaturated group derived from an organic compound bonded on the surface of the acicular antimony-containing tin oxide is used to improve the bonding force between the curable composition and other components. It can be strong.

In constituting the curable composition of the present invention, the compound (D) preferably contains at least 1-hydroxycyclohexylphenyl ketone. By using a curable composition containing such a photopolymerization initiator, the curable composition can be more reliably cured.

[0010] Still another embodiment of the present invention is a cured product obtained by curing the curable composition described above. By curing such a curable composition, antistatic properties,
A cured product having excellent scratch resistance and transparency can be easily obtained.

The cured product cured from the composition of the present invention is:
Excellent antistatic effect. That is, the cured product of the present invention has low surface resistance. The lower the surface resistance, the better the antistatic properties. If the surface resistance is lower than the order of 10 ¹² , the antistatic property is particularly enhanced, and adhesion of dust and the like is remarkably prevented.
From the viewpoint of antistatic properties, the surface resistance is more preferably lower than 10 ¹⁰ order. Further, a cured product cured from the composition of the present invention has excellent scratch resistance and adhesion.
Further, the cured product cured from the composition of the present invention is, as compared with a cured product and the like cured from a conventional composition containing spherical antimony-containing tin oxide, a desired addition only by adding a small amount of antimony-containing tin oxide. An antistatic effect is obtained. This is because the antimony-containing tin oxide has a needle-like shape,
This is because a conductive path can be effectively formed in the cured product even with a small amount of addition. Therefore, the content of antimony-containing tin oxide in the cured product is reduced, and the transparency can be increased without impairing the antistatic effect.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the curable composition and the cured product will be described in more detail. 1. Compound (A-1), acicular antimony-containing tin oxide Acicular antimony-containing tin oxide (hereinafter sometimes referred to as acicular ATO) is an antistatic property of a cured product obtained by curing a curable composition. Used to enhance

(1) Shape The shape of the needle-like ATO is not particularly limited as long as it is a fine powder or an elongated shape, and includes a fibrous, columnar, rod-like and other similar shapes. The aspect ratio is preferably 5 or more, more preferably 10 or more. For example, as the needle-like ATO, the short axis average particle diameter is 0.005 to 0.05 μm, and the long axis average particle diameter is 0.1 to
Those having a value of 3 μm and an average aspect ratio of 5 or more are mentioned. The shape of the acicular ATO can be appropriately selected depending on the desired effect, dispersibility in the curable composition, and the like.

(2) Production Method The production method of the needle-like ATO is not particularly limited. For example, a material to be fired containing a tin component, an antimony component, a silicon component and a halide of an alkali metal is fired. Thereafter, a method of removing soluble salts of the obtained calcined product, a method of depositing antimony hydroxide containing particles on the surface of the fine particles of the acicular tin oxide fine powder, separating and collecting the same, and a method of calcining the same can be mentioned. .

(3) Addition amount In the curable composition of the present invention, the addition amount of acicular ATO is 40
It needs to be in the range of ８０80% by weight. The reason for this is that if the addition amount is less than 40% by weight, when cured, excellent antistatic properties, scratch resistance, etc. may not be obtained. If the amount exceeds the above range, the film forming property may be insufficient during application and drying of the curable composition, or the transparency of the cured product may be reduced. Further, for the above reason, the addition amount is 45 to 80.
%, Preferably within a range of 50 to 80% by weight.
It is more preferable to set the value in the range of% by weight.

2. Compound (B), a reaction product of hydroxyl group-containing polyfunctional (meth) acrylate and diisocyanate A reaction product of hydroxyl group-containing polyfunctional (meth) acrylate and diisocyanate (hereinafter sometimes simply referred to as compound (B)) is curable. It is used to increase the scratch resistance and hardness of a cured product obtained by curing the composition.

(1) Polyfunctional (meth) acrylate having a hydroxyl group The polyfunctional (meth) acrylate having a hydroxyl group is not particularly limited. For example, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate Acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid E
O-modified di (meth) acrylate and the like can be suitably used. Examples of commercially available hydroxyl group-containing polyfunctional (meth) acrylates include, for example, KA, manufactured by Nippon Kayaku Co., Ltd.
YARAD DPHA, PET-30, Toagosei Co., Ltd.
Product name Aronix M-215, M-233,
It can be obtained as M-305, M-400, or the like. In addition, the hydroxyl group-containing polyfunctional (meth) acrylate is
One type may be used alone, or two or more types may be used in combination.

(2) Diisocyanate The diisocyanate is not particularly limited as long as it has an isocyanate group capable of reacting with the above-mentioned hydroxyl group-containing polyfunctional (meth) acrylate.
Such examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate. 1,5-naphthalenediisocyanate, m-
Phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate 4,4'-biphenylene diisocyanate
1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl -1,3-phenyldiisocyanate, 4-diphenylpropanediisocyanate, lysine diisocyanate, hydrogenated diphenylmethanediisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetra Methyl xylylene diisocyanate, 2,5 (or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and the like can be mentioned. Of these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate) and 1,3-bis (isocyanatomethyl) cyclohexane are more preferred. In addition, diisocyanate can be used individually by 1 type or in combination of 2 or more types.

(3) Aspect of Compound (B) The compound is not particularly limited as long as it is a compound obtained by reacting the above-mentioned hydroxyl group-containing polyfunctional (meth) acrylate with diisocyanate. The compound (B) has at least two or more (meth) acryloyl groups in the molecule, has a molecular weight of 400 or less per (meth) acryloyl group, and has two or more urethane bonds (-O-
Those having C (＝ O) —NH—) are preferred. The following general formula (1) obtained by reacting 2 mol of hydroxyl-containing polyfunctional (meth) acrylate with 1 mol of diisocyanate
More preferably, the urethane (meth) acrylate represented by

R ¹ —OC (＝ O) NH—R ² —NHCOO—R ³ (1) [In the general formula (1), the substituents R ¹ and R ³ are derived from a hydroxyl group-containing polyfunctional (meth) acrylate. It is a monovalent organic group containing a (meth) acryloyl group, and the substituent R ² is a divalent organic group derived from diisocyanate. ]

Examples of such a compound (B) include a reaction product of dipentaerythritol penta (meth) acrylate with 1,6-hexamethylene diisocyanate,
Reaction product of dipentaerythritol penta (meth) acrylate with isophorone diisocyanate, reaction product of dipentaerythritol penta (meth) acrylate with 2,4-tolylene diisocyanate, pentaerythritol tri (meth) acrylate with 1,6-hexa One or more of a reactant with methylene diisocyanate, a reactant of pentaerythritol tri (meth) acrylate with isophorone diisocyanate, and a reactant of pentaerythritol tri (meth) acrylate with 2,4-tolylene diisocyanate Combinations are included.

Examples of the synthesizing method include a method in which diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate are charged together and react, a method in which a hydroxyl group-containing polyfunctional (meth) acrylate is dropped into diisocyanate and reacted, a method in which diisocyanate and hydroxyl group are reacted. Containing polyfunctional (meta)
A method in which acrylate is charged in an equimolar amount and reacted, and then a hydroxyl group-containing polyfunctional (meth) acrylate is reacted again can be exemplified.

(4) Addition amount In the curable composition of the present invention, the addition amount of the compound (B) is 5
It needs to be in the range of 40% by weight. The reason for this is that when the addition amount is less than 5% by weight, when the curable composition is cured, the resulting cured product may have insufficient scratch resistance. weight%
This is because, if the ratio exceeds, the hardness of the cured product may be insufficient. Further, for the above reason, the amount of the compound (B) to be added is preferably in the range of 10 to 30% by weight, more preferably in the range of 10 to 25% by weight.

3. Compound (C), polyfunctional (meth) acrylate Polyfunctional (meth) acrylate is used to increase the scratch resistance and hardness of a cured product obtained by curing the curable composition.

(1) Polyfunctional (meth) acrylate Polyfunctional (meth) acrylate is a compound containing at least two (meth) acryloyl groups in a molecule.
Examples thereof include hydroxyl-containing polyfunctional (meth) acrylates such as the above-mentioned pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, trimethylolpropanetriene. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, etc. Singly or in combination of two or more.

(2) Amount of Addition The curable composition of the present invention requires that the amount of the polyfunctional (meth) acrylate be in the range of 5 to 30% by weight. The reason for this is that if the addition amount is less than 5% by weight, when the curable composition is cured, the resulting cured product may have insufficient scratch resistance,
When the addition amount exceeds 30% by weight, application of the curable composition,
This is because film-forming properties may be insufficient during drying.
For the above-mentioned reason, the addition amount of the polyfunctional (meth) acrylate is more preferably set to a value in the range of 5 to 30% by weight, and more preferably to a value in the range of 8 to 28% by weight. .

The compound (B) and the compound (C)
Are both used to increase the scratch resistance and hardness of the cured product obtained by curing the curable composition, but both need to be used in combination. The reason for adding the compound (B) and the compound (C) is to impart appropriate elasticity to the cured film and increase scratch resistance and hardness, and to impart an elastic modulus and increase hardness, respectively. In order to maximize the properties, the compound (B) described in the claims,
The addition amount of the compound (C) is preferred.

4. Compound (D), photopolymerization initiator The photopolymerization initiator is used for curing the composition. (1) Photopolymerization initiator Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl 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-methylpropan-1-one, 2-hydroxy-2-methyl-
1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide And the like, alone or in combination of two or more.

Among these photopolymerization initiators, 1
-Hydroxycyclohexyl phenyl ketone, 2,2-
Dimethoxy-2-phenylacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2.6 −
(Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide is preferred. However, it is particularly preferable that the photopolymerization initiator contains at least 1-hydroxycyclohexylphenyl ketone, since the curable composition of the present invention can be more reliably cured. Further, the content of 1-hydroxycyclohexyl phenyl ketone is preferably 1 to 5% by weight.

(2) Amount of Addition The curable composition of the present invention requires that the amount of the photopolymerization initiator be in the range of 0.5 to 10% by weight. The reason for this is that if the addition amount is less than 0.5% by weight,
This is because the curing of the cured composition may be insufficient. On the other hand, if the addition amount exceeds 10% by weight, the photopolymerization initiator itself acts as a plasticizer, and the hardness of the cured product may decrease. For the above reason, the amount of the photopolymerization initiator is preferably set to a value within the range of 0.5 to 8% by weight, more preferably to a value within the range of 0.5 to 5% by weight. preferable.

5. Compound (A-2), surface-treated needle-like ATO Surface-treated needle-like ATO is obtained by subjecting the above-mentioned needle-like ATO to a surface treatment using a surface treatment agent such as a coupling agent. By performing the surface treatment, the dispersibility is further improved. Here, the surface treatment refers to an operation of modifying the surface by mixing acicular antimony tin oxide and a surface treatment agent, and the method includes a physical adsorption and a reaction for forming a chemical bond. May be used, but from the viewpoint of the effect of the surface treatment, a reaction for forming a chemical bond is more preferable. The content of needle-like ATO in the surface-treated needle-like ATO is 40 to 80% by weight based on the total solid content.

(1) Surface treatment agent When the surface treatment is carried out using a coupling agent, the following treatment agents may be mentioned as examples of the coupling agent. (I) Organic Compound Having a Polymerizable Unsaturated Group As the organic compound having a polymerizable unsaturated group to be bonded to the acicular ATO, a urethane bond [-OC (=
O) NH-] or thiourethane bond [-SC (= O) N
H-] and an alkoxysilane compound having an unsaturated double bond are preferred. Specific examples include, for example, compounds represented by the following formula (2).

[0033]

Embedded image

In the formula (2), R⁴, R⁵Are the same but different
Hydrogen atom or C ₁~ C₈The alkyl of
Group or aryl group, for example, methyl, ethyl
, Propyl, butyl, octyl, phenyl, xylyl
And the like. Here, p is an integer of 1 to 3.
Is a number.

Examples of the group represented by [(R ⁴ O) _p R ⁵ _3-p Si—] include, for example, trimethoxysilyl, triethoxysilyl, triphenoxysilyl, methyldimethoxysilyl, and dimethylmethoxysilyl. And the like. Among these groups, a trimethoxysilyl group or a triethoxysilyl group is preferred. R
⁶ is a divalent organic group having a C ₁ to C ₁₂ aliphatic or aromatic structure, and may have a chain, branched or cyclic structure. R ⁷ is a divalent organic group;
Usually, it is selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably 76 to 500. R ⁸ is
It is a (q + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and an unsaturated hydrocarbon group. Z represents a monovalent organic group having in its molecule a polymerizable unsaturated group that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. Further, q 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.

The synthesis of the organic compound having a polymerizable unsaturated group used in the present invention is described, for example, in JP-A-9-100111.
No. 1 can be used. More specifically, it is obtained by reacting a hydroxyl group-containing (meth) acrylate, an alkoxysilane, and a diisocyanate.

As the hydroxyl group-containing (meth) acrylate used here, for example, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid EO-modified di (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth)
Acrylate and the like can be suitably used. Examples of commercially available hydroxyl group-containing polyfunctional (meth) acrylates include, for example, KAYARAD D manufactured by Nippon Kayaku Co., Ltd.
PHA, PET-30, manufactured by Toagosei Co., Ltd. Aronix M-215, M-233, M-305, M
-400 or the like.

The alkoxysilane is not particularly limited as long as it has a functional group which reacts with diisocyanate. For example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriethoxysilane, Thiol group-containing alkoxysilanes such as mercaptopropyldimethoxyethoxysilane, γ-mercaptopropyldiethoxymethoxysilane, γ-mercaptopropyldimethoxymethylsilane, and γ-mercaptopropyldiethoxymethylsilane can be suitably used.

The diisocyanate is not particularly limited as long as it has an isocyanate group capable of reacting with the polyfunctional (meth) acrylate and alkoxysilane. Such examples include 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate,
1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate
4,4'-biphenylene diisocyanate, 1,6
-Hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3- Phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate −
2,5 (or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and the like can be mentioned. Among these, 2,4-tolylene diisocyanate
G, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate) and 1,3-bis (isocyanatomethyl) cyclohexane are more preferred. The alkoxysilane and diisocyanate can be used alone or in combination of two or more.

(Ii) Other Coupling Agents Other preferable coupling agents suitable for surface treatment include γ-methacryloxypropyltrimethoxysilane,
Compounds having an unsaturated double bond in the molecule such as γ-acryloxypropyltrimethoxysilane and vinyltrimethoxysilane, molecules such as γ-glycidoxypropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane Compounds having an epoxy group in the compound, γ-aminopropyltriethoxysilane, compounds having an amino group in the molecule such as γ-aminopropyltrimethoxysilane,
γ-mercaptopropyltriethoxysilane, a compound group having a mercapto group in a molecule such as γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane,
Examples thereof include alkylsilanes such as methyltriethoxysilane and phenyltrimethoxysilane, and one or a combination of two or more of tetrabutoxycytitanium, tetrabutoxyzirconium, and tetraisopropoxyaluminum. Further, among these coupling agents, those having a functional group capable of copolymerizing or crosslinking with the organic resin are preferable.

(Iii) Amount of Addition In the surface treatment of the acicular ATO, the addition ratio of the surface treating agent is set to 0.1 to 100 parts by weight of the acicular ATO.
It is preferred that the value be in the range of 1 to 125 parts by weight,
The value is more preferably in the range of 1 to 100 parts by weight, and more preferably in the range of 5 to 50 parts by weight. The reason is that if the addition ratio of the surface treatment agent is less than 0.1 part by weight, the scratch resistance of the cured product may be insufficient, while the addition ratio exceeds 125 parts by weight. In this case, the hardness of the cured product may be insufficient.

(2) Amount of Addition The curable composition of the present invention has a surface-treated acicular ATO.
Is in the range of 40 to 89.5% by weight of the total solid content, and the content of needle-like ATO in the total solid content is 40 to 8%.
Preferably, the value is in the range of 0% by weight. It is preferable to adjust the addition amount of the surface-treated needle-like ATO so as to be in the preferable range described above.

6. Organic Solvent In the curable composition of the present invention, the compound (A-
It is preferable to add an organic solvent in addition to 1) or (A-2) to (D). The organic solvent is not particularly limited. For example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetylacetone, alcohols such as ethanol, isopropyl alcohol, n-butanol, and diacetone alcohol, ethyl cellosolve, and butyl cellosolve , Ether group-containing alcohols such as propylene glycol monomethyl ether, hydroxy esters such as methyl lactate, ethyl lactate and butyl lactate, ethyl acetoacetate, methyl acetoacetate, β-keto esters such as butyl acetoacetate,
It is preferable to use at least one organic solvent selected from the group consisting of aromatic hydrocarbons such as toluene and xylene. Among these, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetylacetone are more preferred.

The organic solvent is added so that the total solid content of the curable composition is 0.5 to 75%. That is, the amount of the organic solvent to be added is preferably in the range of 33.3 to 19900 parts by weight, when the total solid content is 100 parts by weight. The reason for this is that if the amount of the organic solvent is less than 33.3 parts by weight, the viscosity of the curable composition may increase and the coatability may decrease. This is because the thickness of the cured product to be obtained is too small and sufficient scratch resistance may not be exhibited.

7. Others The curable composition of the present invention includes a photosensitizer, a polymerization inhibitor, a polymerization initiator, a leveling agent, a wettability improver, a surfactant, a plasticizer as long as the object and effects of the present invention are not impaired. Additives such as an agent, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a pigment, and a dye.

8. Preparation Method The curable composition of the present invention is prepared by adding the above-mentioned compounds (A-1) (or (A-2)) to (D), an organic solvent, and if necessary, an additive, respectively, to room temperature or It can be prepared by mixing under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, and a three-roll mill. However, when mixing under heating conditions, the mixing is preferably performed at a temperature not higher than the decomposition initiation temperature of the polymerization initiator. When a thin film having a thickness of 1 μm or less is to be formed, the curable composition may be diluted with an organic solvent before coating, if necessary, before coating.

9. Curing Conditions Curing conditions for the curable composition are not particularly limited. For example, when radiation is used, the amount of exposure is set to 0.1.
The value is preferably in the range of 01 to 10 J / cm ² . The reason for this is that when the exposure amount is less than 0.01 J / cm ² , curing failure may occur, while
If the exposure amount exceeds 10 J / cm ² , the curing time may be excessively long. Further, the above reason, the exposure amount is more preferably within a range of 0.1~5J / cm ² and is more preferably within a range of 0.3~3J / cm ^2.

10. Cured Product The cured product of the present invention is excellent in antistatic properties, scratch resistance, transparency, etc., and is one of antireflective films, antifouling films, water repellent films, electronic components, optical components, packaging containers, or antistatic films. Can be used as a part.

[0049]

Hereinafter, embodiments of the present invention will be described in detail.
The scope of the present invention is not limited to the description of these examples.

(Production Example 1) Preparation of Acicular Antimony-Containing Tin Oxide (Compound (A-1)) Sol A needle-like antimony-containing tin oxide fine powder (FS-12P, manufactured by Ishihara Techno Co., Ltd.) was mixed with 300 parts by weight of methyl ethyl ketone ( Hereinafter, it is abbreviated as MEK.)
Disperse with glass beads for 10 hours, remove the glass beads, and remove the MEK needle-shaped antimony-containing tin oxide sol (hereinafter, referred to as
It may be referred to as an acicular ATO sol. ) 950 parts by weight. Here, 2 g of the obtained needle-like ATO sol was weighed on an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and the total solid concentration was found to be 30% by weight.

(Comparative Production Example 1) Preparation of spherical antimony-containing tin oxide sol 300 parts by weight of spherical antimony-containing tin oxide fine powder (SN-102P manufactured by Ishihara Techno Co., Ltd.) was added to 700 parts by weight of MEK, and the mixture was mixed with glass beads. Dispersion is performed for 10 hours, and the glass beads are removed to remove MEK spherical antimony-containing tin oxide sol (hereinafter sometimes referred to as spherical ATO sol) 95.
0 parts by weight were obtained. Here, 2 g of the obtained spherical ATO sol
Was weighed on an aluminum dish and dried on a hot plate at 120 ° C. for 1 hour to determine the total solid concentration, which was 30% by weight.

(Production Example 2) Preparation of (reactive) acicular antimony-containing tin oxide (compound (A-2)) sol to which an organic compound having a polymerizable unsaturated group is bound (2-1) Polymerizable unsaturated Synthesis of Organic Compound Having a Group 7.8 g of mercaptopropyltrimethoxysilane and 0.2 of dibutyltin dilaurate in a vessel equipped with a stirrer
g of the mixed solution in 2 g of isophorone diisocyanate.
g in dry air at 50 ° C. over 1 hour.
The mixture was further stirred at 60 ° C. for 3 hours. Subsequently, pentaerythritol triacrylate (trade name: NK ester A-TMM-, manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to the reaction solution.
3L) After dropwise adding 71.4 g at 30 ° C over 1 hour, the mixture was further stirred at 60 ° C for 3 hours to obtain a reaction solution. The amount of residual isocyanate in the product in the reaction solution, that is, in the organic compound having a polymerizable unsaturated group, was determined by FT-IR
Was 0.1% by weight or less, and it was confirmed that each reaction was performed almost quantitatively. In addition, it was confirmed that the molecule had a thiourethane bond, a urethane bond, an alkoxysilyl group, and a polymerizable unsaturated group.

(2-2) Synthesis of Reactive Acicular Antimony-Containing Tin Oxide Sol In a container equipped with a stirrer, acicular antimony-containing tin oxide dispersion (FSS-10M, manufactured by Ishihara Techno Co., Ltd., dispersion solvent:
MEK, total solid content concentration 30% by weight) 95 g, (2-1)
Organic compound 4.0 having a polymerizable unsaturated group obtained in
g, distilled water 0.1 g and p-hydroxyphenyl monomethyl ether 0.01 g were mixed and heated and stirred at 65 ° C. After 5 hours, 0.7 g of orthoformic acid methyl ester was added to the mixture, and the mixture was heated for another 1 hour to obtain a reactive acicular antimony-containing tin oxide sol (hereinafter referred to as reactive acicular ATO).
It may be called a sol. ) Got. Here, 2 g of the obtained reactive needle-like ATO sol was weighed on an aluminum dish,
It was dried on a hot plate at 0 ° C. for 1 hour, and the total solid concentration was determined to be 33% by weight. In addition, 2 g of the reactive needle-like ATO sol was weighed in a magnetic crucible, preliminarily dried on a hot plate at 80 ° C. for 30 minutes, and then calcined in a muffle furnace at 750 ° C. for 1 hour. And the inorganic content in the total solid content was determined from the total solid content concentration, and was found to be 79% by weight. In addition, the inorganic content according to this measurement method corresponds to the content of ATO in the total solid content.

(Production Example 3) Synthesis of a mixture of a reaction product of a hydroxyl group-containing polyfunctional (meth) acrylate and diisocyanate (compound (B)) and a polyfunctional (meth) acrylate (compound (C)) (part 1) Dry air Medium, hexamethylene diisocyanate 6.0 g
And dibutyltin dilaurate in a mixed solution of 0.02 g, dipentaerythritol pentaacrylate (hydroxyl-containing polyfunctional (meth) acrylate) (Nippon Kayaku Co., Ltd.)
Product name KAYARAD DPHA dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate (hereinafter referred to as C-1) = 4 /
6) After dropwise adding 94.0 g at 20 ° C. over 1 hour, the mixture is stirred at room temperature for 1 hour, and further heated and stirred at 60 ° C. for 3 hours to obtain a reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate. (Hereinafter, referred to as B-1) and a mixture of C-1 (hereinafter, referred to as B-1).
M-1. ) Got. Here, when the amount of residual isocyanate in the reaction solution was analyzed, the remaining amount was 0.1% by weight or less, and it was confirmed that the reaction was performed almost quantitatively. Further, the content of B-1 in M-1 was found to be 44% by calculation from the charge ratio of the raw materials.

(Production Example 4) Synthesis of a mixture of a reaction product of a hydroxyl group-containing polyfunctional (meth) acrylate and diisocyanate (compound (B)) and a polyfunctional (meth) acrylate (compound (C)) (part 2) Dry air Medium, pentaerythritol triacrylate (hydroxyl-containing polyfunctional (meth) acrylate) (trade name: NK Ester A-TMM-, manufactured by Shin-Nakamura Chemical Co., Ltd.)
0.1 g of dibutyltin dilaurate was added to a mixed solution of 40.9 g of 3L pentaerythritol triacrylate / pentaerythritol tetraacrylate (hereinafter, referred to as C-2) = 6/4 and 18.3 g of isophorone diisocyanate. , And further stirred at 50 ° C. for 3 hours. Further, 40.9 g of pentaerythritol triacrylate was added dropwise over 1 hour, and the mixture was heated and stirred at 60 ° C. for 3 hours to obtain a reaction product of pentaerythritol triacrylate and isophorone diisocyanate (hereinafter, referred to as B-2). And C-2 (hereinafter, referred to as M-2). Here, when the amount of residual isocyanate in the reaction solution was analyzed, the remaining amount was 0.1% by weight or less, and it was confirmed that the reaction was performed almost quantitatively. Further, the content of B-2 in M-2 was determined from the charge ratio of the raw materials to be 67%.

Hereinafter, examples of preparation of the curable composition and the cured product of the present invention are shown in Examples 1 to 5 and Comparative Examples 1 to 5. (Example 1) As shown in Table 1, a needle-like ATO (A-1) sol 1 prepared in Production Example 1 was placed in a container shielding ultraviolet rays.
90 g (57.0 g as needle-like ATO fine particles), 28.9 g of the mixture (M-1) prepared in Production Example 3 (12.7 g as B-1 and 16.2 g as C-1), prepared in Production Example 4 10.6 g of the obtained mixture (M-2) (7.1 g as B-2, 3.5 g as C-2), 3.5 g of 1-hydroxycyclohexylphenyl ketone (hereinafter referred to as D-1) and 37 g of MEK. Each plus 5
The mixture was stirred at 0 ° C. for 2 hours to obtain a uniform solution of the curable composition. The total solid content in the curable composition and the inorganic content in the total solid content were measured in the same manner as in Production Examples 1 and 2, and were 37% by weight and 57% by weight, respectively.

After diluting with methyl isobutyl ketone until the total solid content in the obtained curable composition becomes 5% by weight, one-sided easy-adhesion polyethylene terephthalate (PET) was used using a wire bar coater (# 6). Film A41
00 (Toyobo Co., Ltd., film thickness of 188 μm) coated with a diluent of the curable composition on the easily treated surface or the untreated surface,
The coating was dried at 80 ° C. for 1 minute in an oven to form a coating film.
Then, under nitrogen, using a high pressure mercury lamp, 0.3 J /
This coating film was cured by ultraviolet light under a light irradiation condition of cm 2 to form a cured product layer having a thickness of 0.1 μm. However,
The curable compositions of Example 3 and Comparative Example 2 were applied without dilution with methyl isobutyl ketone.

(Examples 2 to 6) Acicular ATO sol or reactive acicular ATO sol shown in Table 1 and compounds (B) to
A curable composition was prepared in the same manner as in Example 1, except that (D) was added in accordance with the amounts shown in Table 1. However, Example 4
Then, as for the compound (B) and the compound (C), the mixture (M-2) was added, and further, trimethylolpropane triacrylate (hereinafter, referred to as C-3) was added. In Example 6, each compound was mixed in the same manner as in Example 1, and concentrated using a rotary evaporator until the total solid content concentration became 52% by weight to obtain a curable composition. Further, as in Example 1, the total solid content concentration in the curable composition,
And the inorganic content in the total solid content was measured. Further, these curable compositions were cured in the same manner as in Example 1 to obtain a cured product.

(Comparative Examples 1 to 6) Spherical ATO sol or needle-like ATO sol shown in Table 1, and compounds (B) to (D)
Was added in accordance with the amounts shown in Table 1, except that curable compositions of Comparative Examples 1-2 and Comparative Examples 4-6 were prepared in the same manner as in Example 1. In Comparative Example 3, a curable composition was obtained by concentration in the same manner as in Example 6. Further, in the same manner as in Example 1, the total solid content concentration in the curable composition and the inorganic content in the total solid content were measured. Further, these curable compositions were cured in the same manner as in Example 1 to obtain a cured product. Here, Comparative Example 1
No. 4 to No. 4 show the compound (A-1) in the curable composition as an acicular AT.
Comparative Example 5 is an example in which compounds (A-1) and (B) are changed from O to spherical ATO, and Comparative Example 6 is an example in which compound (D) is a value outside the range of the present invention. It is.

(Test Example 1) Examples 1 to 6 and Comparative Example 1
The surface resistance of the cured products obtained in Nos. To 6 was measured by the following measurement method. Also, the adhesiveness of the obtained cured product,
Adhesion after QUV and abrasion resistance were evaluated according to the following criteria.

(1) Surface resistance Surface resistance (Ω / □) of the cured product formed on the PET untreated surface
Was measured using a high resistance meter (HP4339, manufactured by Hewlett-Packard Company) with a main electrode diameter of 26 mm.
It was measured under the conditions of Φ and an applied voltage of 100 V. Table 1 shows the obtained results.

The following surface resistance values are shown in FIG. 1 in order to show the relationship between the content of needle-like ATO or spherical ATO in the cured product and the surface resistance of the cured product. Cured product containing 40.0 wt% needle-like ATO (Example 6) Cured product containing 49.9 wt% needle-like ATO (Example 3) Cured product containing 57.0 wt% needle-like ATO (Example 6) Example 1) Cured product containing 74.9% by weight of needle-like ATO (Example 2) Cured product containing 40.0% by weight of spherical ATO (Comparative Example 3) Curing containing 49.9% by weight of spherical ATO (Comparative Example 2) A cured product containing 57.0% by weight of spherical ATO (Comparative Example 1) A cured product containing 74.9% by weight of spherical ATO (Comparative Example 4)

(2) Adhesion and Adhesion after QUV The adhesion of the cured product formed on the PET easily-adhesive treated surface was determined by J
Based on the cross-cut cellophane tape peeling test in IS K5400, the evaluation was made on the residual film ratio (%) in a total of 100 squares of 1 mm square. Further, the cured product film was irradiated with ultraviolet rays for 150 hours using a QUV accelerated weathering tester (manufactured by Q-Panel), and then the adhesion was similarly evaluated. Table 1 shows the obtained results.

(3) Scratch resistance The surface of the cured product formed on the PET easily-adhered surface was treated with # 00
Rubbing was performed 10 times with 00 steel wool under a load of 40 g / cm 2, and the abrasion resistance of the cured product was visually evaluated based on the following criteria. Table 1 shows the obtained results. Evaluation 5: No scratch was observed. Evaluation 4: Generation of 1 to 5 scratches was observed. Evaluation 3: Generation of 6 to 50 scratches was observed. Evaluation 2: 51 to 100 scratches were observed. Evaluation 1: Peeling of the coating film was observed. A scratch resistance of evaluation 3 or more is within a practically acceptable range, and a scratch resistance of evaluation 4 or more is preferable because of excellent practical durability. If it is present, it can be said that it is more preferable because practical durability is remarkably improved.

[0065]

[Table 1]

The abbreviations in Table 1 are as follows. B-1: hydroxyl group-containing polyfunctional (meth) synthesized in Production Example 3
Reaction product of acrylate and hexamethylene diisocyanate B-2: hydroxyl-containing polyfunctional (meth) synthesized in Production Example 4
Reaction product of acrylate and isophorone diisocyanate C-1: dipentaerythritol hexaacrylate C-2: pentaerythritol tetraacrylate C-3: trimethylolpropane triacrylate D-1: 1-hydroxycyclohexyl phenyl ketone D-2: 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone

[0067]

According to the curable composition and the cured product of the present invention, it contains needle-like ATO, which is suitable as a material for an antireflection film, and has an antistatic property and an antistatic property after curing. A curable composition having excellent scratch resistance and transparency,
And its cured product can be provided.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the content of needle-like ATO or spherical ATO and the surface resistance of a cured product.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z (72) Inventor Hiroki Nakajima 2-11-24 Tsukiji 2-chome, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Takayoshi Tanabe 2--11-24 Tsukiji, Chuo-ku, Tokyo FSR in JSR Co., Ltd. SA31 SA61 SA63 SA64 SA82 SA84 UA01 VA01 WA02 4J027 AG01 AG12 AG23 AG24 AG36 BA17 BA19 BA23 BA24 BA25 CA20 CB10 CC04 CD08 4J038 FA111 FA161 HA216 JA33 JC01 JC21 KA04 KA06 KA19 NA05 NA07 NA11 NA17 NA19 NA20 PA17PB67P BA02P BA02Q BA03P BA38Q BA39Q BC02Q BC43Q BC75P CA04 FA03 JA00 JA32

Claims (5)

[Claims] 1. The following compounds (A-1) to
An organic solvent-based curable composition containing (D) and having a total solid content of 0.5 to 75%. (A-1) 40 to 80% by weight of acicular antimony-containing tin oxide (B) 5 to 40% by weight of a hydroxyl-containing polyfunctional (meth) acrylate and a diisocyanate (C) 5 to 30% by weight of a polyisocyanate Functional (meth) acrylate (D) 0.5 to 10% by weight of photopolymerization initiator 2. The following compounds (A-2) to
(D), wherein the content of the acicular antimony-containing tin oxide in the total solid content is 40 to 80% by weight, and the total solid content concentration is 0.5 to 75%. System curable composition. (A-2) 40 to 89.5% by weight of surface-treated acicular antimony-containing tin oxide (B) 5 to 40% by weight of a hydroxyl-containing polyfunctional (meth) acrylate and a diisocyanate reactant (C) 5 -30% by weight of polyfunctional (meth) acrylate (D) 0.5-10% by weight of photopolymerization initiator 3. The curable composition according to claim 2, wherein the surface treatment combines the acicular antimony-containing tin oxide with an organic compound having a polymerizable unsaturated group. 4. The curable composition according to claim 1, wherein the compound (D) contains at least 1-hydroxycyclohexyl phenyl ketone. 5. A cured product obtained by curing the curable composition according to any one of claims 1 to 4.