JP2000275403A - Antireflection film and display device with antireflection film arranged thereon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film low in reflectance, excellent in durability, and having large area manufacturing suitability. SOLUTION: In this antireflection film having a low refractive index layer formed by coating and hardening a composition containing hydrolytic partial condensation products of organosilanes, at least one of organosilanes contains a polymerizable ethylenic unsaturated group. In this case, organosilanes are represented by formula Si(OR1)x(R2)4-x, wherein R1 is an alkyl group not containing a 1-5C polymerizable ethylenic unsaturated group or an acyl group not containing a 1-4C polymerizable ethylenic unsaturated group, R2 is an alkyl group not containing a 1-10C polymerizable ethylenic unsaturated group or an aryl group not containing a polymerizable ethylenic unsaturated group, X is an integer of 2 or 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal display (L).
The present invention relates to an antireflection film effective for lowering the reflectance of the surface of an image display device such as a CD) and an image display device having the antireflection film. In particular, the present invention relates to an antireflection film realizing mass productivity and high film strength, and a display device provided with the antireflection film.

[0002]

2. Description of the Related Art In recent years, with the spread of liquid crystal display devices, enlargement and outdoor use, toughness under use conditions, for example, resistance to reflected light (visibility assurance), durability (scratch resistance, stain resistance) And heat resistance) are required to be improved. Improving the visibility of a display device is an issue related to the main function of the device, and naturally has high importance, and measures for improving the visibility are being actively studied. Generally, visibility is reduced by the reflection of scenery due to surface reflection of external light, and as a countermeasure against this, a method of providing an antireflection film on the outermost surface is generally performed. However, since this anti-reflection film is provided on the outermost surface in order to exhibit its function, many high quality issues are inevitably concentrated on the performance of the anti-reflection film from the viewpoint of toughness. For example, reduction of reflectance to the limit, difficulty of scratching, prevention and easy removal of fingerprints and oils and fats, maintenance of various performances in a hot environment such as under the sunshine or in a car interior, etc.

Heretofore, as an antireflection film of a wide wavelength range / low reflectance having a performance capable of covering the entire wavelength range of visible light, a multilayer film formed by laminating a transparent thin film of a metal oxide or the like has been used. Although a single-layer film is effective for monochromatic light, it cannot effectively prevent reflection of light having a certain wavelength range, whereas in such a multilayer film, the larger the number of layers, the wider the wavelength range. This is because it becomes an effective antireflection film. For this reason, a conventional antireflection film has been used in which three or more metal oxides or the like are laminated by means such as physical or chemical vapor deposition. However, such a multi-layer deposited anti-reflection film, in accordance with the relationship between the refractive index and the film thickness of each layer designed optimally in advance, it is necessary to perform the deposition with its film thickness controlled with high precision many times. It is very expensive and has poor suitability for mass production, which makes it very difficult to obtain a film having a large area.

On the other hand, in addition to the above-described method using a multilayer film, there is conventionally known a method for obtaining an effective antireflection effect by a film whose refractive index changes to be removed at an interface with air. For example, JP-A-2-245702 discloses that
A mixture of ultrafine SiO ₂ particles and ultrafine MgF ₂ particles having an intermediate refractive index between a glass substrate and MgF ₂ is applied to a glass substrate, and SiO ₂ is gradually applied from the glass substrate surface toward the coating film surface.
_{It is described that when} the mixing ratio of MgF ₂ is increased by decreasing the mixing ratio of ₂ , the change in the refractive index at the interface between the coating surface and the glass substrate becomes gentle, and an antireflection effect is obtained.

Further, Japanese Patent Application Laid-Open No. 5-13021 discloses that
An antireflection film comprising two layers using ultrafine particles having MgF ₂ and SiO ₂ dispersed in ethyl silicate is disclosed. For example, the first layer is composed of 7 MgF ₂ / SiO _2.
The second layer is a layer in which MgF ₂ / SiO ₂ is 1/1, the refractive index of the first layer is 1.42, and the refractive index of the second layer is 1.44. Therefore, the change in the refractive index cannot be said to be large, and a sufficient antireflection effect cannot be obtained.

Further, Japanese Patent Application Laid-Open No. 7-92305 discloses an ultra-fine particle having a refractive index of 1.428 comprising a core portion and a shell portion surrounding the core portion. An anti-reflection film comprising a low refractive index) and a lower layer formed only of fine particles is disclosed in JP-A-7-168.
No. 006 discloses that the surface formed of air and fine particles (eg, MgF ₂ ) is formed of an upper layer portion (low refractive index) of irregularities, an intermediate layer portion of only fine particles (medium refractive index), and fine particles and a binder. An antireflection film comprising a lower layer portion is disclosed.

[0007] However, the above-mentioned Japanese Patent Application Laid-Open No. 2-2457 / 1990.
02, JP-A-5-13021, JP-A-7-
The antireflection films described in JP-A-92305 and JP-A-7-168006 are based on the principle that the refractive index to air gradually changes in the film thickness direction. These antireflection films require complicated operations and skillful techniques for their preparation, and the obtained films do not have a satisfactory antireflection effect.

Further, Japanese Patent Publication No. Hei 6-98703,
Japanese Patent Application Laid-Open No. 3-21601 discloses a technique for reducing the reflected light by applying a composition comprising a hydrolyzed partial condensate of an alkoxysilane compound to the surface of a plastic substrate. However, the antireflection techniques described in these publications have a small difference in the refractive index from the base material and an insufficient antireflection effect. Problems, such as the difficulty of the task.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an anti-reflection coating which exhibits a low reflectance (reflectance of 1% or less) uniformly over a wide wavelength range, and which has both excellent film strength and brittleness and excellent durability. It is an object of the present invention to provide a membrane in a low-cost, large-scale and large-area manufacturing suitable method. Another object of the present invention is to provide a display device provided with the antireflection film.

[0010]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is as follows.
In an antireflection film having a low refractive index layer formed by coating and curing a composition containing a hydrolyzed partial condensate of an organosilane, at least one of the organosilanes is a polymerizable ethylenically unsaturated group. Has been achieved by an antireflection film characterized by containing:

The preferred embodiments of the antireflection film according to the present invention are described below, but the present invention is not limited to these. (1) An antireflection film having a low refractive index layer formed by coating and curing a composition containing a hydrolyzed partial condensate of an organosilane, wherein at least one of the organosilane is
An antireflective coating, wherein the species contains a polymerizable ethylenically unsaturated group. (2) The antireflection film according to item 1, wherein the organosilane is a mixture of at least one of the following organosilanes (a) and at least one of the organosilanes (b). General formula (a) Si (OR ¹ ) _x (R ² ) _4-x (wherein R ¹ is an alkyl group having 1 to 5 carbon atoms and not containing a polymerizable ethylenically unsaturated group or a 1 to 4 carbon atoms) Represents an acyl group containing no polymerizable ethylenically unsaturated group,
² represents an alkyl group having 1 to 10 carbon atoms not containing a polymerizable ethylenically unsaturated group or an aryl group containing no polymerizable ethylenically unsaturated group, and x represents an integer of 2 to 4. Organosilanes containing no polymerizable ethylenically unsaturated groups. Formula (b) Si (OR ³ ) _y (R ⁵ ) _4-yz (wherein R ³ is the same as defined for R ¹ above, R ⁴ is an organic residue having a polymerizable ethylenically unsaturated group, ⁵ is a group having the same meaning as R ² , y is an integer of 1 to 3, and z is an integer of 1 to 3, provided that 2 ≦ y + z ≦ 4. Organosilanes containing groups. (3) The antireflection film according to the above item (1) or (2), wherein one of the organosilanes contains a perfluoroalkyl group. (4) The antireflection film as described in any one of (1) to (3) above, wherein after applying the low refractive index layer, the film is cured by irradiating ultraviolet light or heating. (5) The low-refractive-index layer (1) and a layer having a refractive index of 1.
The antireflection film according to any one of the above items 1 to 4, comprising a high refractive index layer (2) having 7 or more. (6) a layer (4) having a layer (3) adjacent to the high refractive index layer (2) and on the opposite side of the low refractive index layer (1), and further having a refractive index of 1.6 or less.
The layer (3) has an intermediate refractive index between the refractive index of the layer (4) and the refractive index of the high refractive index layer (2). Anti-reflective coating. (7) A display device comprising the antireflection film according to any one of Items 1 to 6 above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a low refractive index layer formed by applying and curing a composition containing a hydrolyzed partial condensate of an organosilane (hereinafter referred to as a sol solution in the present invention). It is characterized in that at least one of the organosilanes contains a polymerizable ethylenically unsaturated group. The components of the present invention will be described in detail.

Organosilane Organosilane is a silane compound having at least one functional group capable of providing a silanol by hydrolysis in a molecule.
It becomes a hydrolyzate and / or a partial condensate obtained by condensation and functions as a binder in the composition. Generally, a compound represented by the formula (R ⁶ ) ₄ Si is preferably used. In the formula, R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms (for example, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and these groups may have a substituent); Represents an alkoxyl group or an oxyacyl group having 1 to 4 carbon atoms, or a halogen atom.
1 4 R ⁶ in the molecule may be different be the same as each other if the scope of this definition, but can be selected in any combination, carbon four are simultaneously 1-1
It does not become a hydrocarbon group of 0, and preferably two or less hydrocarbon groups having 1 to 10 carbon atoms simultaneously exist in one molecule.

Specific examples of R ⁶ are those having a preferred number of carbon atoms of 1 to 10.
As the hydrocarbon group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, tert-octyl group, n- Decyl group, vinyl group,
Γ-chloropropyl group, CF ₃ −, CF ₃ CH ₂ CH ₂ −, CF ₃ CH
₂ CH ₂ CH _2- , C ₂ F ₅ CH ₂ CH ₂ CH _2- , C ₃ F ₇ CH ₂ CH ₂ CH _2- , C ₂ F ₅ C
H ₂ CH _2- , CF ₃ OCH ₂ CH ₂ CH _2- , C ₂ F ₅ OCH ₂ CH ₂ CH _2- , C ₃ F ₇ OC
H ₂ CH ₂ CH _2- , (CF ₃ ) ₂ CHOCH ₂ CH ₂ CH _2- , C ₄ F ₉ CH ₂ OCH ₂ CH ₂ CH
₂ -, 3- (perfluoro-cyclohexyl) _{propyl, H (CF 2) 4 CH} 2 OCH 2 CH 2 CH 2 -, H (CF 2) 4 CH 2 CH 2 CH 2 -,
γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, 3,4-epoxycyclohexylethyl group and the like. Carbon number 1
Examples of the alkoxy group having 5 to 5 carbon atoms or the oxyacyl group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and acetoxy group. Examples of the group and halogen include fluorine, chlorine, bromine and iodine. In the present invention, from the viewpoint of further functional purpose and structural characteristics, the organosilane (a) and the organosilane (b) containing a polymerizable ethylenically unsaturated group may be used. ).

(A) Contains a polymerizable ethylenically unsaturated group
No organosilane (hereinafter referred to as non-vinyl polymerizable organo
A preferred example of these organosilanes is a compound represented by the general formula
Si (OR¹)_x(R^Two)_4-xAn alkoxysilane represented by
In the composition of the present invention, it is obtained by hydrolysis and condensation.
Hydrolyzate and / or partial condensate in the composition
In the above. Take
R in alkoxysilane¹Is an alkyl having 1 to 5 carbon atoms
Groups or acyl groups having 1 to 4 carbon atoms are preferred.
Tyl group, ethyl group, n-propyl group, i-propyl group,
n-butyl group, sec-butyl group, tert-butyl group, acetyl
And the like. In addition, R in the organosilane^Two
Is preferably an organic group having 1 to 10 carbon atoms, for example, methyl
Group, ethyl group, n-propyl group, i-propyl group, n-
Butyl group, tert-butyl group, n-hexyl group, cycle
Rohexyl group, n-octyl group, tert-octyl
And unsubstituted hydrocarbons such as n-decyl group, phenyl group, etc.
Element group, γ-chloropropyl group, CF_Three-, CF_ThreeCH_Two-, CF_ThreeCH
_TwoCH_Two-, CF_ThreeCH_TwoCH_TwoCH_Two-, C_TwoF_FiveCH_TwoCH_TwoCH_Two-, C_ThreeF₇CH_TwoCH_TwoCH
_Two-, C_TwoF_FiveCH_TwoCH_Two-, CF_ThreeOCH_TwoCH_TwoCH_Two-, C_TwoF_FiveOCH _TwoCH_TwoCH_Two-
 , C_ThreeF₇OCH_TwoCH_TwoCH_Two-, (CF_Three)_TwoCHOCH_TwoCH_TwoCH_Two-, C_FourF₉CH_Two
OCH_TwoCH_TwoCH_Two-, 3- (Perfluorocyclohexyloxy)
C) Propyl, H (CF_Two)_FourCH_TwoOCH_TwoCH_TwoCH_Two-, H (CF_Two)_FourCH_TwoCH_Two
CH_Two-, Γ-glycidoxypropyl group, γ-mercapto
Propyl group, 3,4-epoxycyclohexylethyl group
And the like. x is 2 to 4
Integers are preferred.

Specific examples of these alkoxysilanes are shown below. Those having x = 4 (hereinafter referred to as tetrafunctional organosilane) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-
Acetoxysilane and the like can be mentioned.

X = 3 (hereinafter trifunctional organosilane)
Methyltrimethoxysilane, methyl
Triethoxysilane, ethyltrimethoxysilane, ethyl
Lutriethoxysilane, n-propyltrimethoxysila
, N-propyltriethoxysilane, i-propyl
Limethoxysilane, i-propyltriethoxysilane,
γ-chloropropyltrimethoxysilane, γ-chlorop
Ropirtriethoxysilane, γ-glycidoxypropyl
Trimethoxysilane, γ-glycidoxypropyl trie
Toxic silane, γ-mercaptopropyl trimethoxy
Orchid, γ-mercaptopropyltriethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysila
3,4-epoxycyclohexylethyltrimethoxy
Sisilane, 3,4-epoxycyclohexylethyltri
Ethoxysilane, CF_ThreeCH_TwoCH_TwoSi (OCH_Three)_Three, CF_ThreeCH_TwoCH_TwoCH_TwoSi
(OCH_Three)_Three, C_TwoH_FiveCH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three, C_TwoF_FiveCH_TwoCH_TwoSi (OCH
_Three) _Three, C_ThreeF₇CH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three, C_TwoF_FiveOCH_TwoCH_TwoCH_TwoSi (OCH
_Three)_Three, C_ThreeF₇OCH_TwoCH_TwoCH_TwoSi (OC_TwoH_Five)_Three, (CF_Three)_TwoCHOCH_TwoCH_TwoCH_Two
Si (OCH_Three)_Three, C_FourF₉CH_TwoOCH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three, H (CF_Two) _FourCH_Two
OCH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three, 3- (perfluorocyclohexene
Siloxy) propyltrimethoxysilane
Can be.

X = 2 (hereinafter bifunctional organosilane)
Dimethyldimethoxysilane, dimethyl
Rudiethoxysilane, methylphenyldimethoxysila
, Diethyldimethoxysilane, diethyldiethoxy
Orchid, di-n-propyldimethoxysilane, di-n-propyl
Ropirdiethoxysilane, di-i-propyldimethoxy
Silane, di-i-propyldiethoxysilane, diphenyl
Rudimethoxysilane, diphenyldiethoxysilane, (C
F_ThreeCH_TwoCH_Two)_TwoSi (OCH_Three)_Two, (CF_ThreeCH_TwoCH_TwoCH_Two)_TwoSi (OCH_Three)_Two, (C
_ThreeF₇OCH_TwoCH_TwoCH_Two)_TwoSi (OCH_Three)_Two, [H (CF_Two)₆CH_TwoOCH_TwoCH_TwoCH_Two]
_TwoSi (OCH_Three)_Two, (C_TwoF _FiveCH_TwoCH_Two)_TwoSi (OCH_Three)_TwoTo mention
it can.

When the above-mentioned bifunctional or trifunctional organosilane is used, an organosilane having a fluorine atom in R ² is preferable from the viewpoint of the refractive index. When an organosilane having no fluorine atom is used as R ^2, it is preferable to use methyltrimethoxysilane or methyltriethoxysilane.

The above non-vinyl polymerizable organosilane is 1
Species may be used alone or in combination of two or more. When two or more kinds of the above-mentioned organosilanes are used in combination, the proportion of the bifunctional organosilane in the composition of the present invention is 0 to 150% by weight, preferably 5% by weight, based on the tetrafunctional organosilane and the trifunctional organosilane component. -10
0% by weight, more preferably 10 to 60% by weight.

(B) containing a polymerizable ethylenically unsaturated group
Organosilane (hereinafter referred to as vinyl polymerizable organosilane)
Specific examples of these organosilanes include the general formula Si (O
R^Three)_y(R^Four)_z(R^Five)_4-yz The alkoxysilane represented by
In the composition of the present invention,
Then, the hydrolyzate obtained by hydrolysis and condensation and / or
Or as a partial condensate as a binder in the composition
At the same time as forming a network structure of organic polymer
And acts to impart flexibility to the film. Or
R in the alkoxysilane^ThreeIs an alkyl having 1 to 5 carbon atoms
A kill group or an acyl group having 1 to 4 carbon atoms is preferable.
For example, methyl group, ethyl group, n-propyl group, i-propyl
Group, n-butyl group, sec-butyl group, tert-butyl group,
And a cetyl group. Also, R^FiveHas 1 to 1 carbon atoms
10 organic groups are preferred, for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, sec-
Butyl, tert-butyl, n-hexyl, cyclohexyl
Xyl group, n-octyl group, tert-octyl group, n-de
Unsubstituted hydrocarbon groups such as a sil group and a phenyl group, γ-
Chloropropyl group, CF_Three-, CF_ThreeCH_Two-, CF_ThreeCH_TwoCH_Two-, CF_ThreeC
H_TwoCH_TwoCH_Two-, C_TwoF_FiveCH_TwoCH_TwoCH_Two-, C_ThreeF₇CH_TwoCH_TwoCH_Two-, C_TwoF_FiveCH
_TwoCH_Two-, CF_ThreeOCH_TwoCH_TwoCH_Two-, C_TwoF_FiveOCH_TwoCH_TwoCH_Two-, C_ThreeF₇OCH_Two
CH_TwoCH_Two-, (CF_Three)_TwoCHOCH_TwoCH_TwoCH_Two-, C_FourF₉CH_TwoOCH_TwoCH_TwoCH
_Two-, 3- (perfluorocyclohexyloxy) propyl
, H (CF_Two)_FourCH_TwoOCH_TwoCH_TwoCH_Two-, H (CF_Two)_FourCH_TwoCH _TwoCH_Two-, Γ
-Glycidoxypropyl group, γ-mercaptopropyl
Group, 3,4-epoxycyclohexylethyl group, etc.
And substituted hydrocarbon groups.

R ⁴ represents an organic group containing a polymerizable ethylenically unsaturated group. It is preferably an organic group having 2 to 10 carbon atoms. Preferred examples of these groups include a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group, an unsaturated hydrocarbon group such as a styryl group, a γ-acryloxypropyl group, a γ-methacryloxypropyl group, a γ-acrylamidopropyl group. And a hydrocarbon group having an ethylenically unsaturated group as a substituent, such as a γ-methacrylamidopropyl group or a γ-styryloxypropyl group. y
Is preferably an integer of 1 to 3, and z is preferably an integer of 1 to 3. 2 ≦ y + z ≦ 4, where y = 3, z
= 1, y = 2 and z = 2 are particularly preferred.

Specific examples of the vinyl polymerizable alkoxysilane are shown below. Those having z = 1 (hereinafter referred to as one polymerizable organosilane) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, p-vinylphenyltrimethoxysilane , P-vinylphenyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acrylamidopropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacrylamidopropyltri Examples thereof include fluoropropyldimethoxysilane and γ-methacryloxypropyldimethylmethoxysilane.

Examples of those having z = 2 (hereinafter referred to as di-polymerizable organosilane) include divinyldimethoxysilane, divinyldiethoxysilane, vinylallyldimethoxysilane, diallylmethoxysilane, bis (p-vinylphenyl) diethoxysilane, Bis (γ-methacryloxypropyl) dimethoxysilane, bis (γ-acrylamidopropyl) dimethoxysilane, bis (γ-methacryloxypropyl) methylmethoxysilane, bis (γ-methacryloxypropyl) trifluoropropylmethoxysilane, γ-methacryl Oxypropylvinyldimethoxysilane and the like can be mentioned.

Examples of compounds having z = 3 (hereinafter referred to as three polymerizable organosilanes) include trivinylmethoxysilane, trivinylethoxysilane, divinylallylmethoxysilane, triallylmethoxysilane, and tris (p-vinylphenyl) ethoxysilane. , Tris (γ-methacryloxypropyl) methoxysilane, tris (γ-acrylamidopropyl) ethoxysilane, bis (γ-methacryloxypropyl) vinylmethoxysilane, and γ-methacryloxypropylvinylallylmethoxysilane.

The above vinyl polymerizable organosilanes may be used alone or in combination of two or more. When two or more of the above-mentioned vinyl polymerizable organosilanes are used in combination, the proportion of the one polymerizable organosilane in the composition of the present invention is from 0 to 150 with respect to the double synthetic organosilane and the tripolymerizable organosilane component. % By weight, preferably 5 to 100% by weight, more preferably 10 to 60% by weight.
% By weight.

The low refractive index layer of the present invention is formed by applying and curing the composition containing organic silicon as a main component prepared by the above-described method. The essential components in this coating solution are the main components (monomer: organosilane) that form the network structure, and are none other than the compounds (a) and (b) described above. Further, in addition to these organosilanes, various compounds can be added to the composition of the present invention as needed. These compounds can be roughly classified into the following components (c) to (i) according to the purpose. (c) Silyl group-containing vinyl polymer (d) Polymerizable vinyl compound (e) Hydrolysis / condensation catalyst (sol-gel catalyst) (f) Vinyl polymerization catalyst (g) Solvent (h) Chelate ligand compound (i) Water ( j) Fillers (k) Other additives

Hereinafter, each additive used together will be described in detail. (c) Silyl group-containing vinyl polymer The silyl group-containing vinyl polymer has a main chain composed of a vinyl polymer and has a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal or a side chain. The silyl group contains at least one, and preferably two or more, in one molecule.

[0029]

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(Wherein X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, an amino group, etc. and / or a hydroxyl group; R ⁷ is a hydrogen atom; An alkyl group having 10 to 10 or an aralkyl group having 1 to 10 carbon atoms,
3 is an integer of 3).

The silyl group-containing vinyl polymer may be produced by reacting (a) a hydrosilane compound with a vinyl polymer having a carbon-carbon double bond.

[0032]

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(Where X, R ⁷ and a are the same as those described above, and R ⁸
Is an organic group having a polymerizable double bond) and various vinyl compounds, and the production method is not limited.

Here, examples of the hydrosilane compound used in the production method shown in (a) include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyldiethoxysilane, methyl Alkoxysilanes such as dimethoxysilane, phenyldimethoxysilane, trimethoxysilane and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane; methyldiaminoxysilane, triaminoxysilane; Examples include aminosilanes such as dimethylaminoxysilane and triaminosilane.

The vinyl polymer used in the production method shown in (a) is not particularly limited except for a vinyl polymer containing a hydroxyl group. Examples thereof include methyl (meth) acrylate and ethyl (meth) acrylate. Butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth)
(Meth) acrylic acid esters such as acrylate and cyclohexyl (meth) acrylate; carboxylic acids such as (meth) acrylic acid, itaconic acid and fumaric acid and acid anhydrides such as maleic anhydride; epoxy compounds such as glycidyl (meth) acrylate Amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether; (meth) acrylamide, Nt-
Butyl (meth) acrylamide, itaconic acid diamide,
Amide compounds such as α-ethylacrylamide, crotonamide, fumaric diamide, maleic diamide, N-butoxymethyl (meth) acrylamide; acrylonitrile, styrene, vinyltoluene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate ,
N-vinylpyrrolidone,

[0036]

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[0037]

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[0038]

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A vinyl polymer obtained by copolymerizing a vinyl compound selected from the group consisting of a monomer having a double bond in a side chain such as allyl methacrylate is preferable, and a copolymer using at least one fluorine-containing monomer as a copolymer monomer is preferable. Particularly preferred.

On the other hand, examples of the silane compound used in the production method shown in (b) include the following.

[0041]

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[0042]

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As the vinyl compound used in the production method shown in (b), the vinyl compound used in the polymerization of the vinyl polymer in the production method (a) can be used. And vinyl compounds containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyvinyl ether, N-methylol acrylamide, etc., in addition to those described in the production method of (a). Can also be mentioned. Further, one using one kind of fluorine-containing monomer is particularly preferable.

Preferred specific examples of the above silyl group-containing vinyl polymer include, for example, the following general formula:

[0045]

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(Wherein R ⁹ and R ¹¹ are a hydrogen atom, a fluorine atom or a methyl group, R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl, n-propyl,
Allyl, n-butyl, i-butyl, n-pentel, n-
Hexyl, benzyl, (CF ₃ ) ₂ CH-, CF ₃ CH _2- , C ₇ F ₁₅ CH ₂
, C ₂ F ₁₅ CH ₂ CH ₂ —, etc.) and R ¹² represents a carbon atom of 1 such as a methylene group, an ethylene group, a propylene group or a butylene group. And alkylene groups R 4 to R ¹³ are the same as R ¹⁰ , and m / (1+
m) = 0.01-0.4, preferably 0.02-0.2
And a trialkoxysilyl group-containing acrylic polymer represented by the formula: The number average molecular weight of the silyl group-containing vinyl polymer is preferably from 2,000 to 100,
000, more preferably 4,000 to 50,000.

Specific examples of the above silyl group-containing vinyl polymer used in the present invention include Kanekazemulak manufactured by Kaneka Corporation and the following polymers, but are not limited thereto. It is not something to be done.

P-1 Methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (90/10:
Weight ratio) P-2 n-butyl methacrylate / γ-methacryloxypropyltrimethoxysilane (85/15: weight ratio) P-3 methyl methacrylate / γ-acryloxypropyltrimethoxysilane (80/20: weight ratio) P -4 methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (70/30: weight ratio) P-5 methyl methacrylate / ethyl acrylate /
γ-methacryloxypropyltrimethoxysilane (50
/ 35/15: weight ratio)

P-6 Ethyl methacrylate / γ-methacryloxypropyltrimethoxysilane (80/20:
(Weight ratio) P-7 n-butyl methacrylate / styrene / γ-methacryloxypropyltrimethoxysilane (50/35
/ 15: weight ratio) P-8 methyl methacrylate / cyclohexyl acrylate / γ-methacryloxypropyltrimethoxysilane (40/45/15: weight ratio) P-9 methyl methacrylate / methyl acrylate /
γ-acryloxypropyltrimethoxysilane (40 /
40/20: weight ratio) P-10 methyl methacrylate / n-butyl acrylate / vinyltrimethoxysilane (60/30/10: weight ratio)

P-11 FM-1 / γ-methacryloxypropyltrimethoxysilane (85/15: weight ratio) P-12 FM-4 / γ-methacryloxypropyltrimethoxysilane (85/15: weight ratio) P -13 FM-2 / γ-methacryloxypropyltrimethoxysilane (85/15: weight ratio) P-14 FM-4 / γ-methacryloxypropyltrimethoxysilane (70/30: weight ratio) P-15 FM- 4 / FM-7 / γ-methacryloxypropyltrimethoxysilane (30/55/15: weight ratio)

P-16 FM-2 / FM-4 / γ-acryloxypropyltrimethoxysilane (30/50/20: weight ratio) P-17 FM-3 / FM-4 / γ-methacryloxypropyltrimethoxy Silane (25/60/15: weight ratio) P-18 FM-9 / methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (60/25/15:
(Weight ratio) P-19 FM-7 / methyl methacrylate / γ-acryloxypropyltrimethoxysilane (40/45/15: weight ratio) P-20 FM-4 / methyl methacrylate / vinyl trimethoxysilane (65/20 / 15: Weight ratio) The proportion of the silyl group-containing vinyl polymer in the composition is 0 to 200% by weight, preferably 0 to 100% by weight, more preferably 0 to 50% by weight, based on the total organosilane used.

(D) Polymerizable vinyl compound The sol solution of the present invention is bonded to vinyl polymerizable organosilane, which is a network structure forming component of the low refractive index layer, by vinyl polymerization to form a stronger network structure. Various compounds having a polymerizable ethylenically unsaturated bond (hereinafter referred to as vinyl compounds) may be used in combination. The vinyl compound is not particularly limited, and may be suitably used as long as it can be copolymerized by ordinary radical polymerization or ionic polymerization. Preferred examples of such monomers include, for example,
Olefins (ethylene, propylene, isoprene, butadiene, vinyl chloride, vinylidene chloride, 6-hydroxy-1-hexene, cyclopentadiene, 4-pentenoic acid, methyl 8-nonenoate, vinylsulfonic acid, trimethylvinylsilane, etc.), unsaturated Carboxylic acids and salts thereof (acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, ammonium methacrylate, potassium itaconate, etc.), esters of β-unsaturated carboxylic acids (methyl acrylate, cyclohexyl acrylate, 2- Ethylhexyl acrylate, 2-chloroethyl acrylate, benzyl acrylate, 2-
Cyanoethyl acrylate, methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycerin monomethacrylate, 2-acetoxyethyl methacrylate,
Phenyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate, ω-
Methoxy polyethylene glycol methacrylate (additional mole number = 2 to 100), ω-hydroxy polyethylene glycol methacrylate (additional mole number = 2 to 100), ω-hydroxy polypropylene glycol methacrylate (additional mole number = 2 to 100)
), 3-N, N-dimethylaminopropyl methacrylate, chloro-3-N, N, N-trimethylammoniopropyl methacrylate, 2-carboxyethyl methacrylate, 3-sulfopropyl methacrylate,
-Oxysulfobutyl methacrylate, monobutyl maleate, dimethyl maleate, monomethyl itaconate,
Dibutyl itaconate, allyl methacrylate, 2-isocyanatoethyl methacrylate), amides of unsaturated carboxylic acids (acrylamide, methacrylamide, N
-Methylacrylamide, N, N-dimethylacrylamide, N-methyl-N-hydroxyethylmethacrylamide, N-tertbutylacrylamide, N-ter
t-octyl methacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (2-
(Acetoacetoxyethyl) acrylamide, N-acryloylmorpholine, diacetoneacrylamide, itaconic acid diamide, N-methylmaleimide, 2-acrylamido-2-methylpropanesulfonic acid, etc.), unsaturated nitriles (acrylonitrile, methacrylonitrile, etc.) , Styrene derivatives (styrene, vinyltoluene,
p-tertbutyl styrene, vinyl methyl benzoate,
α-methylstyrene, p-chloromethylstyrene, vinylnaphthalene, p-hydroxymethylstyrene, sodium p-styrenesulfonate, potassium p-styrenesulfinate, p-aminomethylstyrene, etc.), vinyl ethers (methyl vinyl ether, Butyl vinyl ether, methoxyethyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, etc.), and other polymerizable monomers (N-vinylimidazole, 4-vinylpyridine) , N-vinylpyrrolidone, etc.)
And the like. However, it is desirable that these monomers are copolymerized and used in a necessary minimum amount which does not increase the refractive index of the film.

Among these, a monomer containing a fluorine atom (hereinafter referred to as a fluorine-containing monomer) is particularly preferably used from the viewpoint of the refractive index. The fluorine-containing monomer is not particularly limited as long as the monomer contains a fluorine atom, but those having a fluorine atom as a perfluoroalkyl group are particularly preferable in view of the fluorine content.

Specific examples of these monomers include, for example, fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3- Dioxole), acrylic or methacrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters (eg, compounds represented by the following general formula), fully or partially fluorinated vinyl ethers, fully or partially fluorinated vinyl esters, These are fully or partially fluorinated vinyl ketones and the like, and the desired polymer can be obtained by copolymerizing any of these monomers in any ratio.

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In the formula, R ¹⁴ is a hydrogen atom, having 1 to 3 carbon atoms.
Represents an alkyl group or a halogen atom. Rf represents a completely or partially fluorinated alkyl group, alkenyl group, heterocycle or aryl group. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a heterocycle, an aryl group or a group defined by Rf. R ¹⁴ , R ¹⁵ , R ¹⁶ and Rf may each have a substituent other than a fluorine atom. Also, any two or more groups of R ¹⁵ , R ¹⁶ and Rf may be bonded to each other to form a ring structure.

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In the formula, A represents a fully or partially fluorinated n-valent organic group. R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom. R ¹⁷ may have a substituent other than a fluorine atom. n represents an integer of 2 to 8.

Examples of preferred fluorine-containing monomers used in the present invention will be shown below, but the present invention is not limited to these specific structures.

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[0061]

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[0062]

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The strength of the film can be further controlled by using an arbitrary polyfunctional monomer in addition to the above monofunctional vinyl monomer. The polyfunctional monomer to be used is not particularly limited and may be suitably used as long as it is commercially available or has a plurality of polymerizable unsaturated groups in one molecule of the synthesis.

Specific examples of the polyfunctional monomer include, for example, olefins (butadiene, pentadiene, 1,4-
Divinylcyclohexane, 1,2,5-trivinylcyclohexane, etc., esters of acrylic acid and methacrylic acid (ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetramethacrylate, pentaerythritol triester Acrylate, trimethylolpropane triacrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol pentamethacrylate, pentaerythritol hexaacrylate, 1,2,4-cyclohexanetetramethacrylate, etc.), styrene derivatives (1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, etc.), vinyl sulfones (eg, divinyl sulfone), Riruamido acids (methylene bisacrylamide, such as diacrylate acryloyl piperazine), such as methacrylamide (methylenebismethacrylamide, dimethacryloyl piperazine, etc.) can be mentioned.

From the viewpoint of lowering the refractive index of the low refractive layer to be formed, it is also preferable to select this polyfunctional monomer from polyfunctional monomers containing a fluorine atom. Specific examples of the fluorine-containing polyfunctional monomer are as follows.

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Preferred combinations of the above-mentioned components (a) to (d) in the present invention are illustrated below and in Examples. The mixing ratio indicates the weight (g) of each compound used. In the present invention, the coating composition of the hydrolysis / partial condensate of the above-mentioned organosilane in the following description is referred to as "sol liquid", and the hydrolysis / partial condensation reaction of the organosilane is referred to as "sol-gelation". ". In the sol-gelation, the components (a) to (c) are essential components, and the component (d) may be used together with the sol-gelation or may be used by adding it to the prepared sol solution.

SP-1 Hydrolysis / partial condensate of 10 g of trifluoropropyltrimethoxysilane and 4 g of vinyltrimethoxysilane SP-2 10 g of trifluoropropyltrimethoxysilane, 3-
Acryloyloxypropyltrimethoxysilane 5g
Hydrolysis and partial condensate of SP-3 tetraethoxysilane 10 g, trifluoropropyltrimethoxysilane 10 g, 3-methacryloyloxypropyltrimethoxysilane 5 g of hydrolysis and partial condensate SP-4 tetraethoxysilane 10 g, bis (tri Fluoropropyl) dimethoxysilane 10g, 3-acryloyloxypropyltrimethoxysilane 2g hydrolysis / partial condensate SP-5 Tetraethoxysilane 10g, trifluoropropyltrimethoxysilane 10g, divinyldimethoxysilane 8
g of hydrolysis / partial condensate SP-6 trifluoropropyltrimethoxysilane 15 g, 3-
Methacryloyloxypropyltrimethoxysilane 3
g, hydrolysis and partial condensate of 2 g of P-12 SP-7 15 g of trifluoropropyltrimethoxysilane, 5 g of divinyldimethoxysilane, hydrolysis and partial condensate of 3 g of P-9

SP-8 10 g of trifluoropropyltrimethoxysilane and 5 g of vinyltrimethoxysilane were hydrolyzed and partially condensed with 1 g
Mixture of 3 g of H, 1H, 2H, 2H-perfluorodecyl acrylate SP-9 10 g of tetraethoxysilane, 5 g of divinyldiethoxysilane, 5 g of 3-acryloxypropyltrimethoxysilane, 3 g of the above compound P-6 SP-10 tetraethoxy 5 g of silane, 10 g of p-vinylphenyltrimethoxysilane, 5 g of dimethyldimethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane 12 g SP-11 5 g allyltrimethoxysilane, 8 g divinyldimethoxysilane, 12 g bis (trifluoropropyl) diethoxysilane, 10 g tetraethoxysilane SP-12 12 g tetraethoxysilane 8 g of dimethyldivinylsilane, 15 g of 3,3,3-trifluoropropyltriethoxysilane, 3 g of the above compound P-4

(E) Sol-gel catalyst Various catalyst compounds can be preferably used in the sol solution of the present invention for the purpose of accelerating the hydrolysis / partial condensation reaction of organosilanes. The catalyst used is not particularly limited, and an appropriate amount may be used according to the constituent components of the sol liquid used. Generally effective are the following compounds (e1) to (e5), and preferred compounds can be added in necessary amounts from these. In addition, two or more of these groups can be appropriately selected and used together within a range in which mutual promoting effects are not inhibited.

(E1) Organic or inorganic acid As the inorganic acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid,
Organic acid compounds such as sulfurous acid, nitric acid, nitrous acid, phosphoric acid, and phosphorous acid include carboxylic acids (formic acid, acetic acid, propionic acid,
Butyric acid, succinic acid, cyclohexanecarboxylic acid, octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid, benzoic acid, pentafluorobenzoic acid, phthalic acid, etc., sulfonic acids (methane) Sulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid
Phosphonic acids (dimethyl phosphate, phenylphosphonic acid, etc.), Lewis acids (boron trifluoride etherate, scandium triflate, alkyltitanic acid, aluminate, etc.), and heteropolyacids (molybdophosphoric acid, phosphotungstic acid, etc.) Can be.

(E2) Organic or inorganic base As the inorganic base, sodium hydroxide, potassium hydroxide,
Examples of organic base compounds such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and ammonia include amines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, triethylamine, dibutylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine , Ethanolamine, diazabicycloundecene, quinuclidine, aniline, pyridine, etc.), phosphines (eg, triphenylphosphine, trimethylphosphine), and metal alkoxides (eg, sodium methylate, potassium ethylate).

(E3) Metal chelate compound An alcohol represented by the general formula R ¹⁸ OH (where R ¹⁸ represents an alkyl group having 1 to 6 carbon atoms) and R ¹⁹ COCH ₂ C
OR ²⁰ (wherein, R ¹⁹ is an alkyl group having 1 to 6 carbon atoms, R ²⁰
Represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 16 carbon atoms), as long as the ligand is a diketone represented by the following formula: Can be. In this category, two or more metal chelate compounds may be used in combination. Particularly preferred as the metal chelate compound of the present invention is that the central metal has A
having the general formula Zr (OR ¹⁸ )
_p1 (R ¹⁹ COCHCOR ²⁰ ) _p2 , Ti (OR ¹⁸ ) _q1 (R ¹⁹ COCHCOR ²⁰ ) _q2 and Al (OR ¹⁸ ) _r1 (R ¹⁹ COCHCOR ²⁰ ) _r2 (R ¹⁹ COCHCOR ²⁰ ) It acts to promote the condensation reaction of components (a) to (c).

R ¹⁸ and R in the metal chelate compound
¹⁹ may be the same or different and may be an alkyl group having 1 to 6 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, Examples include an n-pentyl group and a phenyl group. Also, R
²⁰ is the same alkyl group having 1 to 6 carbon atoms as described above,
An alkoxy group having 1 to 16 carbon atoms, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-
Butoxy, sec-butoxy, t-butoxy, lauryl, stearyl and the like. Further, p _{1 to} r ₂ in the metal chelate compound represent an integer determined to be tetradentate or hexadentate.

Specific examples of these metal chelate compounds include zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), zirconium n-butoxytris (ethylacetoacetate), zirconium tetrakis (n Zirconium chelate compounds such as -propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, and tetrakis (ethylacetoacetate) zirconium; diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetate) titanium Titanium chelate compounds such as diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum , Diisopropoxy acetylacetonate aluminum, diisopropoxy bis (ethylacetoacetate) aluminum, diisopropoxy bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, mono-acetylacetonate ·
Aluminum chelate compounds such as bis (ethylacetoacetate) aluminum and the like can be mentioned. Preferred of these metal chelate compounds are tri-n-
Butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonate) titanium,
Aluminum diisopropoxyethyl acetoacetate and aluminum tris (ethylacetoacetate). These metal chelate compounds can be used alone or in combination of two or more. In addition, partial hydrolysates of these metal chelate compounds can also be used.

(E4) Organometallic Compound The preferred organometallic compound is not particularly limited, but is preferably an organic metal compound.
Transition metals are preferred because of their high activity. Among them, tin compounds
Is particularly preferred because of its good stability and activity. Embody these
Examples of compounds include (C_FourH₉)_TwoSn (OCOC₁₁H_{twenty three})_Two, (C_FourH₉)_TwoSn
(OCOCH = CHCOOCH_Three)_Two, (C_FourH₉)_TwoSn (OCOCH = CHCOOC_FourH₉)_Two,
(C₈H₁₇)_TwoSn (OCOC₁₁H_{twenty three})_Two, (C₈H₁₇)_TwoSn (OCOCH = CHCOOCH_Three)
_Two, (C₈H₁₇)_TwoSn (OCOCH = CHCOOC_FourH₉)_Two, (C₈H₁₇)_TwoSn (OCOCH
= CHCOOC₈H_{1 7})_Two, Sn (OCOCC₈H₁₇)_TwoCarboxylic acid type available
Machine tin compound; (C_FourH₉)_TwoSn (SCH_TwoCOOC ₈H₁₇)_Two, (C_FourH₉)_TwoSn
(SCH_TwoCOOC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC₈H₁₇)_Two, (C₈H
₁₇)_TwoSn (SCH_TwoCH_TwoCOOC₈H₁₇)_Two, (C₈H₇)_TwoSn (SCH_TwoCOOC
₈H₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC₁₂H_{twenty five})_Two,

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Mercaptide-type organotin compounds such as

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Sulfide-type organotin compounds such as

(C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO or (C ₄ H ₉ )
Organotin oxide such as ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO and ethyl silicate dimethyl maleate, diethyl maleate,
Examples thereof include organotin compounds such as reaction products with an ester compound such as dioctyl phthalate.

(E5) Metal Salts As the metal salts, alkali metal salts of organic acids (for example, sodium naphthenate, potassium naphthenate, sodium octanoate, sodium 2-ethylhexanoate, potassium laurate, etc.) are preferably used.

The proportion of the sol-gel catalyst compound in the composition is as follows:
With respect to organosilane as a raw material of the sol liquid, 0.01 to 0.01
It is 50% by weight, preferably 0.1 to 50% by weight, more preferably 0.5 to 10% by weight.

(F) Vinyl Polymerization Catalyst Various vinyl polymerization catalyst compounds can be preferably used in the composition of the present invention for the purpose of accelerating the polymerization of the vinyl polymerizable group of the film. The polymerization catalyst used is not particularly limited,
An appropriate amount may be used depending on the vinyl polymerizable compound used. Generally effective are the following thermal polymerization initiators or photopolymerization initiator compounds, of which preferred compounds can be added in necessary amounts. In addition, two or more of these groups can be appropriately selected and used together within a range in which mutual promoting effects are not inhibited.

Examples of the thermal polymerization initiator include inorganic peroxides (eg, potassium persulfate, ammonium persulfate), organic peroxides (eg, lauryl peroxide, benzoyl peroxide, tert-butyl peroctoate), Azo compounds (eg, 2,2′-azobisisobutyronitrile, 2,
2′-azobis (2,4-dimethylvaleronitrile),
Dimethyl-2,2'-azobis (2-methylpropionate), dimethyl-2,2'-azobisisobutyrate, azonitrile compound (eg, sodium azobiscyanovalerate), azoamidine compound (eg, 2,2 '-Azobis (2-methylpropionamide) hydrochloride), cyclic azoamidine compounds (eg, 2,2'-azobis [2-
(5-methyl-2-imidazolin-2-yl) propane hydrochloride), azoamide compounds (eg, 2,2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl) -2-) Hydroxyethyl] propionamide).

Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, and 2,3-dialkyldione compounds. , Disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p
-Dimethylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

(G) Solvent The solvent uniformly mixes each component in the sol solution, adjusts the solid content of the composition of the present invention, and enables the composition to be applied to various coating methods. And to improve the storage stability. These solvents are not particularly limited as long as they can achieve the above objects. Preferred examples of these solvents include, for example, water, alcohols, aromatic hydrocarbons, ethers, ketones, and esters.

Among them, the alcohols include, for example, monohydric alcohols and dihydric alcohols. Among them, the monohydric alcohol is preferably a saturated aliphatic alcohol having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, and ethylene glycol. Monobutyl ether and ethylene glycol monoethyl ether acetate can be exemplified.

Further, specific examples of aromatic hydrocarbons include benzene, toluene and xylene, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and methyl. Isobutyl ketone, diisobutyl ketone and the like, specific examples of esters, ethyl acetate,
Examples thereof include propyl acetate, butyl acetate, and propylene carbonate. These organic solvents can be used alone or in combination of two or more. The ratio of the organic solvent in the composition is not particularly limited, and an amount that adjusts the total solid concentration according to the purpose of use is used.

(H) Chelating ligand compound When a metal complex compound is used in the sol solution, the curing reaction rate
Compounds with chelate coordination ability from the viewpoint of control and improvement of liquid stability
It is also preferable to use a substance. Preferably used
Is the general formula R¹⁸COCH_TwoCOR¹⁹Β-diketones represented by
And / or β-ketoesters, wherein
It acts as a stability improver for the product. Sand
That is, a metal chelate compound (preferably,
Or zirconium, titanium and / or aluminum
Coordination with metal atoms in
Condensation of components (a) to (c) with these metal chelates
The effect of accelerating the reaction is suppressed, and the curing speed of the resulting film is reduced.
It is considered to control. R¹⁸And R
¹⁹Represents R which constitutes the metal chelate compound¹⁸And R
¹⁹Synonymous with, but it is necessary that
Absent.

Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate and acetoacetate-n-
Propyl, acetoacetic acid-i-propyl, acetoacetic acid-n
-Butyl, acetoacetic acid-sec-butyl, acetoacetic acid-t-
Butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, 5-methyl-hexane-dione and the like Can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters can be used alone or in combination of two or more.
Such β-diketones and / or β-ketoesters are used in an amount of 2 mol or more, preferably 3 to 20 mol, per mol of the metal chelate compound, and if less than 2 mol, the storage stability of the obtained composition is poor. Become.

(I) Water To the preferred sol solution of the present invention, water is added for the hydrolysis / condensation reaction of the components (a) to (c). The amount of water to be used is usually 1.2 to 3 to 1 mol of the components (a) to (c).
0 mol, preferably about 1.3 to 2.0 mol.
The preferred sol solution of the present invention has a total solid content of 0.1%.
1 to 50% by weight, preferably 1 to 40% by weight;
If it exceeds 0% by weight, the storage stability of the composition deteriorates, which is not preferable.

(J) Filler Colloidal silica can be added to the sol solution of the present invention for the purpose of improving the hardness of the resulting coating film. Examples of this colloidal silica include colloidal silica dispersed in water and colloidal silica dispersed in an organic solvent such as methanol or isopropyl alcohol.

The composition of the present invention is prepared by adding the above-mentioned colloidal composition to the coating film to impart various properties such as coloring, imparting unevenness, preventing ultraviolet light transmission to the substrate, imparting corrosion resistance, and heat resistance. It is also possible to add and disperse a filler in addition to silica. As the filler, for example, organic pigments, water-insoluble pigments such as inorganic pigments or particles other than pigments,
Examples thereof include fibrous or flaky metals and alloys, and oxides, hydroxides, carbides, nitrides, and sulfides thereof. Specific examples of the filler include particles, fibrous or scaly iron, copper, aluminum, nickel,
Silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide,
Cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, Zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, schöre green, green top, manganese green, pigment green, ultramarine,
Navy blue, Pigment green, Rock ultramarine, Cobalt blue, Cerulean blue, Copper borate, Molybdenum blue, Copper sulfide, Cobalt purple, Mars purple, Manganese purple, Pigment violet, Lead oxide, Calcium plumbate, Zinc yellow, Lead sulfide, Chromium Yellow, loess, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, bengala, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, Lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black,
Examples include thermatomic black, vegetable black, potassium titanate whisker, and molybdenum disulfide.

The average particle size or average length of these fillers is usually 5 to 500 nm, preferably 10 to 200 nm. When the filler is used, the proportion in the composition is about 10 to 300 parts by weight based on 100 parts by weight of the total solid content of the sol liquid.

(K) Other Additives The sol solution and the accelerating solution of the present invention include other known dehydrating agents such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane, various surfactants, and other silane cups. Additives such as a ring agent, a titanium coupling agent, a dye, a dispersant, a thickener, and a leveling agent can also be added.

Further, the sol solution of the present invention may contain a solvent other than the above-mentioned solvents. Such a solvent does not cause precipitation when the above-mentioned components (a) to (d) are mixed. Any solvent may be used, and aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ketones, esters, ethers, ketone ethers used in general paints, coating agents, etc. , Ketone esters, ester ethers and the like, and specific examples thereof include, for example, benzene, toluene,
Xylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isoamyl acetate and the like. These organic solvents are usually used in an amount of 10 parts by weight per 100 parts by weight of the composition of the present invention.
It is used in an amount of about 0 parts by weight or less.

In preparing the sol solution of the present invention, any method may be used as long as it is a method of adding water to the composition containing the above components (a) to (c) and hydrolyzing the composition. At this time, if necessary, a catalyst may be used to promote the hydrolysis. The amount of the catalyst to be used is not particularly limited as long as the stability of the solution over time is not impaired. For example, the following preparation methods are preferred. A solution comprising the components (a) and (b) (if necessary, (c) a silyl group-containing vinyl polymer), a solvent and a hydrolysis catalyst,
A method in which 0.2 to 3 mol of water is added to 1 mol of an organosilane to carry out a hydrolysis / condensation reaction.

To a solution comprising the components (a) and (b) and a solvent, 0.2 to 3 mol of water is added to 1 mol of the organosilane to carry out a hydrolysis / condensation reaction. Adding a silyl group-containing vinyl polymer according to the above. To a solution comprising the components (a) and (b), a solvent and a hydrolysis catalyst, 0.2 to 3 mol of water is added to 1 mol of the organosilane to carry out a hydrolysis / condensation reaction. A method in which a polymer is added and mixed, followed by a condensation reaction.

The sol solution of the present invention is subjected to curtain flow coating,
Apply to a transparent film or a high refractive index layer or a medium refractive index layer by a coating method such as dip coating, spin coating, or roll coating, and dry at room temperature, or
By heating at a temperature of about 00 ° C. for about 1 minute to 100 hours, a low refractive index layer is formed.

In the case of simultaneous multi-layer coating, the discharge flow rate is adjusted so that the lower layer coating liquid and the upper layer coating liquid each have a required coating amount on a slide gheeser having a multistage discharge port, and the formed multilayer flow is Is preferably applied to the support continuously and dried (simultaneous layering method).

In the antireflection film of the present invention, the low refractive index layer (1) formed by applying the composition by the above method is different from the high refractive index layer (2) having a higher refractive index. Formed on
It is preferred to be composed of more than two layers. The refractive index of the low refractive index layer is preferably 1.45 or less, and particularly preferably 1.40 or less. The refractive index of the high refractive index layer is preferably 1.7 or more, and particularly preferably 1.75 or more. Further, it is preferable that these layers are provided on a support, preferably a transparent film.

Further, the antireflection film of the present invention is characterized in that the low refractive index layer (1) formed by applying the composition by the above method is different from the high refractive index layer (2) having a higher refractive index. ), Adjacent to the high-refractive-index layer (2), opposite the low-refractive-index layer (1), to a medium-refractive-index layer (3), and to a further layer (4)
It is particularly preferable to include four layers in which a high refractive index layer is formed on a medium refractive index layer having an intermediate refractive index between the refractive index of the high refractive index layer and that of the high refractive index layer. The refractive index of the high refractive index layer adjacent to the low refractive index layer is preferably 1.7 or more, and particularly preferably 1.75 or more. Also, these layers are the support,
Preferably, it is coated on a transparent film.

The thickness of each layer is 50 to 2 for layer (1).
00 nm, layer (2) 50-200 nm, layer (3) 50-20
0 nm, the layer (4) preferably has a thickness of 1 μm to 100 μm, more preferably the layer (1) has a thickness of 60 to 150 nm and the layer (2) has a thickness of 50 to 15
0 nm, layer (3) 60-150 nm, layer (4) 5-20 μm
m, particularly preferably 60 to 120 nm for layer (1), 50 to 100 nm for layer (2), 60 to 120 nm for layer (3), and 5 for layer (4).
〜１０10 μm. The layer (4) preferably has a refractive index of 1.60 or less, and the layer (3) preferably has an intermediate refractive index between the layers (2) and (4).

FIG. 1 shows a typical example of the antireflection film of the present invention. A high refractive index layer 12 is formed on a transparent film (support) 13, and a low refractive index layer 11 is formed on the high refractive index layer 12. The increase in the number of layers constituting the anti-reflection film
Generally, the wavelength range of light to which the antireflection film can be applied is expanded.
This is based on the conventional principle of forming a multilayer film using a metal compound.

In the antireflection film having the two layers, the high refractive index layer 12 and the low refractive index layer 11 have the following conditions (1)
And (2) are generally satisfied. mλ / 4 × 0.7 <n ₁ d ₁ <mλ / 4 × 1.3 (1) nλ / 4 × 0.7 <n ₂ d ₂ <nλ / 4 × 1.3 (2) And m is a positive integer (generally 1, 2, or 3)
Where n ₁ represents the refractive index of the high refractive index layer, d ₁ represents the layer thickness (nm) of the high refractive index layer, and n is a positive odd number (generally,
1), n ₂ represents the refractive index of the low refractive index layer, and d ₂ represents the layer thickness (nm) of the low refractive index layer. The refractive index n ₁ of the high refractive index layer is generally at least 0.0
5 and the refractive index n ₂ of the low refractive index layer is generally at least 0.1 lower than the refractive index of the high refractive index layer and at least 0.05 lower than the transparent film. Furthermore, the refractive index n ₁ of the high refractive index layer is generally in the range of 1.7 to 2.2.
The above conditions (1) and (2) are conventionally well-known conditions, and are described, for example, in JP-A-59-50401.

FIG. 2 shows another typical example of the antireflection film of the present invention. An undercoat layer 20 and a medium refractive index layer 22 are formed on a transparent film (support) 23, and a high refractive index layer 24 is formed on the medium refractive layer 2.
2 and the low refractive index layer 21 is further formed on the high refractive index layer 2.
4 is formed. The refractive index of the medium refractive index 22 has a value between the high refractive index layer 24 and the undercoat layer 20. The antireflection film of FIG. 2 has a wider applicable wavelength range of light than the antireflection film of FIG.

In the case of an antireflection film having three layers, the middle, high and low refractive index layers generally satisfy the following conditions (3) to (5), respectively. hλ / 4 × 0.7 <n ₃ d ₃ <hλ / 4 × 1.3 (3) kλ / 4 × 0.7 <n ₄ d ₄ <kλ / 4 × 1.3 (4) jλ / 4 × 0.7 <n ₅ d ₅ <jλ / 4 × 1.3 (5) In the above formula, h is a positive integer (generally 1, 2, or 3)
And n ₃ represents the refractive index of the medium refractive index layer, d ₃ represents the layer thickness (nm) of the medium refractive index layer, and k is a positive integer (generally,
1, 2 or 3), n ₄ represents the refractive index of the high refractive index layer, d ₄ represents the layer thickness (nm) of the high refractive index layer, and j represents a positive odd number (generally, 1). , N ₅ represent the refractive index of the low refractive index layer, and d ₅ represents the layer thickness (nm) of the low refractive index layer. Refractive index n ₃ of the intermediate refractive index layer is generally in the range of 1.5 to 1.7, the refractive index n ₄ of the high refractive index layer is generally 1.7 to
It is in the range of 2.2.

The antireflection film of the present invention generally comprises a support and a low refractive index layer provided thereon. The support is usually a transparent film. Materials for forming the transparent film include cellulose derivatives (eg, diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, and nitrocellulose), polyamides, polycarbonates (eg, US Pat. No. 023,101), polyesters (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-di) Carboxylates and Tokiko Sho48
Patent No. -40414), polystyrene, polyolefins (eg, polyethylene, polypropylene and polymethylpentene), polymethylmethacrylate, syndiotactic polystyrene, polysulfone, polyethersulfone, polyetherketone, polyetherimide and polyoxy. Ethylene can be mentioned. Triacetyl cellulose, polycarbonate and polyethylene terephthalate are preferred. The refractive index of the transparent film is preferably from 1.40 to 1.60.

When the antireflection film of the present invention is a multilayer film, the low refractive index layer generally has at least one layer having a higher refractive index than the low refractive index layer (that is, the high refractive index layer, (Refractive index layer). As an organic material for forming a layer having a higher refractive index than the above, a thermoplastic resin (eg, polystyrene, polystyrene copolymer,
A polymer having an aromatic ring, a heterocyclic ring, an alicyclic group other than polycarbonate or polystyrene, or a polymer having a halogen group other than fluorine); a thermosetting resin composition (eg, a melamine resin, a phenol resin, or an epoxy resin) A curing agent); a urethane-forming composition (eg, a combination of an alicyclic or aromatic isocyanate and a polyol); and a radically polymerizable composition (a double bond is formed in the above compound (polymer or the like). A composition containing a modified resin or a prepolymer which is capable of radical curing by being introduced). Materials having high film forming properties are preferred. For the layer having a higher refractive index than the above, inorganic fine particles dispersed in an organic material can also be used. As the organic material used in the above, an inorganic fine particle generally has a high refractive index, so that a material having a lower refractive index than that when the organic material is used alone can also be used. As such materials, in addition to the organic materials described above, vinyl copolymers including acrylics, polyesters, alkyd resins, cellulose polymers,
Examples thereof include various organic materials which are transparent and stably disperse inorganic fine particles, such as urethane resins, various curing agents for curing these, and compositions having a curable functional group.

Further, an organic-substituted silicon-based compound can be included therein. These silicon compounds have the general formula: R ⁵¹ _m R ⁵² _n SiZ _(4-mn) (where R ⁵¹ and R ⁵² are an alkyl group, an alkenyl group, an allyl group, or a halogen, epoxy, amino, mercapto, Represents a hydrocarbon group substituted with methacryloyl or cyano, Z represents a hydrolyzable group selected from an alkoxyl group, an alkoxyalkoxyl group, a halogen atom and an acyloxy group, and under the condition that m + n is 1 or 2, , M and n are each 0, 1, or 2) or a hydrolysis product thereof.

Preferred inorganic compounds of the inorganic fine particles dispersed therein include oxides of metal elements such as aluminum, titanium, zirconium and antimony. These compounds are commercially available in particulate form, ie, as a powder or as a colloidal dispersion in water and / or other solvents. These are further mixed and dispersed in the above organic material or organosilicon compound for use.

As the material for forming the layer having a higher refractive index, inorganic materials which are film-forming and can be dispersed in a solvent or are themselves liquid (eg, alkoxides of various elements, salts of organic acids, A coordination compound (eg, a chelate compound) bonded to a coordination compound, an active inorganic polymer) can be exemplified. Preferred examples thereof include titanium tetraethoxide, titanium tetra-i-propoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, titanium tetra-sec-butoxide, titanium tetra-tert-butoxide, Aluminum triethoxide,
Aluminum tri-i-propoxide, aluminum tributoxide, antimony triethoxide, antimony tributoxide, zirconium tetraethoxide, zirconium tetra-i-propoxide, zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium Metal alcoholate compounds such as tetra-sec-butoxide and zirconium tetra-tert-butoxide; diisopropoxytitanium bis (acetylacetonate), dibutoxytitanium bis (acetylacetonate), diethoxytitanium bis (acetylacetonate), Bis (acetylacetone zirconium), aluminum acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate,
Chelating compounds such as aluminum di-i-propoxide monomethyl acetoacetate and tri-n-butoxide zirconium monoethyl acetoacetate; and active inorganic polymers containing zirconium ammonium or zirconium as a main component. In addition to those described above, various alkyl silicates or hydrolysates thereof, particularly fine particles of silica, particularly silica gel dispersed in a colloidal form can be used as those having a relatively low refractive index but which can be used in combination with the above compounds. .

The antireflection film of the present invention can be treated so that the surface has an antiglare function (that is, a function of scattering incident light on the surface to prevent a scene around the film from shifting to the film surface). . For example, an antireflection film having such a function forms fine irregularities on the surface of a transparent film, and forms an antireflection film (eg, a low refractive index layer, etc.) on the surface.
Is obtained. The formation of the fine irregularities is performed, for example, by forming a layer containing inorganic or organic fine particles on the surface of the transparent film. 50nm ~ 2
The fine particles having a particle size of μm are added to the coating liquid for forming the low refractive index layer,
It may be introduced in an amount of 0.1 to 50% by weight to form irregularities on the uppermost layer of the antireflection film. An anti-reflection coating having an anti-glare function (ie, anti-glare treatment) generally has a haze of 3 to 30%.

The antireflection film of the present invention (preferably an antireflection film having an antiglare function) is used for a liquid crystal display (LC).
D), an image display device such as a plasma display (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CRT).
In the image display device having such an antireflection film, reflection of incident light is prevented, and visibility is remarkably improved. A liquid crystal display (LCD) provided with the antireflection film of the present invention has, for example, the following configuration. A liquid crystal display comprising a pair of substrates having transparent electrodes, a nematic liquid crystal sealed between the substrates, and a polarizing plate disposed on both sides of the liquid crystal cell, wherein at least one of the polarizing plates has a surface on which the present invention is applied. Liquid crystal display device having an anti-reflection film.

In the present invention, a hard coat layer, a moisture proof layer, an antistatic layer, an electromagnetic wave absorbing layer, an ultraviolet absorbing layer, a visible light absorbing layer, an infrared absorbing layer, etc. may be provided on the transparent film as an intermediate layer. it can. As the hard coat layer, in addition to acrylic-based, urethane-based, and epoxy-based polymers and / or oligomers and monomers (eg, an ultraviolet curable resin), a silica-based material can also be used.

[0117]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.
In Examples, parts and% are by weight unless otherwise specified.

Example 1 Preparation and Evaluation of Antireflection Film (1) Preparation of Silyl Group-Containing Vinyl Resin (P-12) Fluorine monomer FM-4 was placed in a 1-liter three-necked flask equipped with a reflux condenser and a stirrer. 30.6 g, γ-methacryloxypropyltrimethoxysilane 5.4 g,
The mixture was heated and stirred at 70 ° C. under a nitrogen stream. 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.)
(Commercially available under the name V-65) in a solution of 4.8 g in 25 ml of methyl ethyl ketone.
The dropping of a solution in which 19.2 g of V-65 was dissolved in 5.4 g of FM-4 and 48.6 g of γ-methacryloxypropyltrimethoxysilane was started, and the solution was dropped at a constant speed over 6 hours. After completion of the dropwise addition, 4.8 g of V-65 and 25 ml of a methyl ethyl ketone solution were added, and the mixture was further heated and stirred at 80 ° C. for 4 hours, and then 280 ml of methyl ethyl ketone was added. . The solid content was 54.4%, and the polymer obtained had a number average molecular weight in terms of polystyrene of 9,600 as determined by gel permeation chromatography.

(2) Preparation of Sol Liquid for Low Refractive Index Layer In a reactor equipped with a stirrer and a reflux condenser, (a) 100 g of trifluoropropyltrimethoxysilane, (b) 50 g of 3-methacryloxypropyltrimethoxysilane, (c) Silyl group-containing vinyl resin P-9 (adjusted to a solid content of 50%) 5
After adding 0 g and (e) 40 g of ethanol and mixing, 30 g of ion-exchanged water was added and reacted at 60 ° C. for 4 minutes, and then cooled to room temperature to obtain a sol solution A for a low refractive index layer. By changing the components (a) to (c) as necessary and performing the same reaction using tetraethoxysilane in combination, sol solutions B to H belonging to the present invention shown in Table 1 and sol solutions X and Y for comparison are obtained. Was.

[0120]

[Table 1]

(3) Preparation of Coating Solution for First Layer (Hard Coat Layer) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPH)
A, 125 g of urethane acrylate oligomer (UV-6300B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dissolved in 439 g of industrially modified ethanol. To the obtained solution, 7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
A solution of 5.0 g dissolved in 49 g of methyl ethyl ketone was added. After stirring the mixture, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for the hard coat layer.

(4) Preparation of titanium dioxide dispersion 30 parts by weight of titanium dioxide (primary particle weight average particle diameter: 50 nm, refractive index: 2.70), anionic diacrylate monomer (PM21, manufactured by Nippon Kayaku Co., Ltd.) ) 4.5 parts by weight of a cationic methacrylate monomer (DMAEA,
0.3 parts by weight of Okijin Co., Ltd.) and 65.2 parts by weight of methyl ethyl ketone were dispersed by a sand grinder,
A titanium dioxide dispersion was prepared.

(5) Preparation of coating solution for second layer (medium refractive index layer) To 151.9 g of cyclohexanone and 37.0 g of methyl ethyl ketone, a photopolymerization initiator (Irgacure 907,
0.14 g of Ciba-Geigy Corporation and 0.04 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were dissolved. Further, 6.1 g of the above titanium dioxide dispersion and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPH)
A, 2.4 g of Nippon Kayaku Co., Ltd.) was added, and the mixture was stirred at room temperature for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a medium refractive index layer.

(6) Preparation of Coating Solution for Third Layer (High Refractive Index Layer) A photopolymerization initiator (Irgacure 90) was added to 1152.8 g of cyclohexanone and 37.2 g of methyl ethyl ketone.
7, Ciba Geigy) and 0.02 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.). Furthermore, the above titanium dioxide dispersion 13.1
3 g and 0.76 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added, followed by stirring at room temperature for 30 minutes, followed by filtration through a polypropylene filter having a pore size of 1 μm. To prepare a coating liquid for a high refractive index layer.

(7) Preparation of anti-reflection film A triacetyl cellulose film (T
AC-TD80U, manufactured by Fuji Photo Film Co., Ltd.)
A gelatin subbing layer was provided. On the gelatin undercoat layer,
The coating solution for the hard coat layer is applied using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays.
The coating layer was cured to form a hard coat layer having a thickness of 7.5 μm. The coating liquid for a middle refractive index layer is applied on the hard coat layer using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays to cure the coating layer, thereby forming a medium refractive index layer (refractive index: 1.72, thickness: 0.081 μm). The coating liquid for a high refractive index layer is applied on the middle refractive index layer using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays to cure the coating layer, and the high refractive index layer (refractive index :
1.92, thickness: 0.053 μm). The coating solution for the low refractive index layer is applied on the high refractive index layer using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays to cure the coating layer, and the low refractive index layer (refractive index : 1.40,
(Thickness: 0.072 μm).

(8) Performance Evaluation of Coated Film The following performance evaluation was carried out on the thus obtained film coated with the first to fourth layers.

(1) Average reflectance: 380-7 using a spectrophotometer (manufactured by JASCO Corporation)
In the wavelength region of 80 nm, the spectral reflectance at an incident angle of 5 ° was measured. Since the antireflection performance is better as the reflectance is smaller in a wide wavelength range, the measurement results show that
The average reflectance at 50 to 650 nm was determined. (2) Surface Contact Angle After the antireflection film was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%, the contact angle with water was measured. (3) Fingerprint Adhesion A fingerprint was attached to the surface of the antireflection film, and the state when the fingerprint was wiped off with a cleaning cloth was observed. A: The fingerprint was completely wiped off B: A part of the fingerprint remained without being wiped C: Most of the fingerprint remained without being wiped (4) Scratch resistance The antireflection film was subjected to a temperature of 25 ° C. and a relative humidity of 60%. After humidifying for 2 hours, using a test pencil specified by JIS-S-6006, according to a pencil hardness evaluation method specified by JIS-K-5400, a hardness at which no scratch is recognized at all under a load of 1 kg. It was measured. (5) Membrane surface strength Membrane surface strength is determined by rubbing with fingertip, tissue, eraser, fingertip and fingertip, respectively, visually observing, rubbing with fingertip is 0, rubbing with tissue is 1, and rubbing with eraser is 1. The score was 2 for those that were damaged, 3 for those that were scratched by rubbing their fingertips, and 4 for those that did not show any damage by any method. Table 2 summarizes the results.

[0128]

[Table 2]

As is clear from this example, it is understood that the antireflection film of the present invention has a very low surface reflectance, a wide wavelength range, and a sufficiently strong film strength. Further, the fingerprint trace could be easily erased by wiping off the tissue, and the stain resistance was excellent. On the other hand, in the comparative example, the surface reflectance was insufficient, or the film strength and the surface contamination prevention performance were not compatible.

(Example 2) Preparation and evaluation of a display device provided with an antireflection film The antireflection films 1 to 5 of the present invention prepared in Example 1 above were prepared.
11 and Comparative Examples 1 and 2 were pasted on the liquid crystal display surface of a personal computer PC9821NS / 340W manufactured by NEC Corporation to produce a surface device sample,
The degree of scenery reflection due to the surface reflection was visually evaluated. The display device provided with the antireflection films 1 to 8 of the present invention hardly reflects surrounding scenery, shows comfortable visibility and has sufficient surface strength,
The display device on which the comparative films 1 and 2 were installed had many reflections around it and had poor visibility. Also, the surface strength was poor.

[0131]

According to the present invention, the composition obtained by coexisting an organosilane having a polymerizable ethylenically unsaturated bond at the time of the partial hydrolysis reaction of the compound having an organosilane structure and the partial condensation reaction thereof. A low-refractive-index layer is formed by applying a material, and the refractive index of the layer immediately below the low-refractive-index layer is set to 1.7 or more. And in a form having manufacturing suitability.

[Brief description of the drawings]

FIG. 1 shows a cross-sectional view of a typical example of an antireflection film of the present invention.

FIG. 2 is a cross-sectional view of another typical example of the antireflection film of the present invention.

[Explanation of symbols]

 11, 21: low refractive index layer 12, 24: high refractive index layer 22: medium refractive index layer 13, 23: transparent film 20: lower layer (primer layer, hard coat layer)

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08G77 / 385 C08G77 / 385 4J038 77/442 77/442 C08J 7/04 CEP C08J 7/04 CEPZ CES CESZ CEZ CEZZ C09D 5/00 C09D 5/00 M 143/04 143/04 183/02 183/02 183/04 183/04 // C08L 101: 00 F term (reference) 2K009 AA06 AA06 BB28 CC03 CC42 DD05 DD06 EE04 4F006 AA02 AA12 AA15 AA22 AA31 AA35 AA36 AA38 AA39 AA40 AB39 AB54 BA14 CA05 DA04 EA03 EA05 4F100 AH05B AH06B AJ06 AK02B AL05B AT00A BA02 BA42 BA44 EH46 EJ08 EJ42 EJ54 GB41 JK01 JL02 JNBA BA03 BA03 BA08 AF03 AF03 BA15 BA17 BA18 BA19 BA20 BA23 BA24 BA25 BA28 CA02 CA03 CA05 CA09 CA10 CA12 CA14 CA16 CA18 CA20 CA22 CA28 CA29 CA31 CA34 CA36 CB00 CB02 CB03 CB08 CB09 CB10 CC02 CC05 CD08 4J035 AA03 BA01 BA11 CA061 CA101 CA131 CA141 CA161 CB01 4 CL002 DL021 DL0 22 DL031 DL032 DL071 DL072 NA19 PA17 PA19

Claims (7)

[Claims] 1. An antireflection film having a low refractive index layer formed by coating a composition containing a partial hydrolysis product of an organosilane on a support and curing the composition, wherein at least one of the organosilane is used. An antireflection film characterized by containing a polymerizable ethylenically unsaturated group. 2. The antireflection film according to claim 1, wherein the organosilane is a mixture of at least one of the following organosilanes (a) and at least one of the organosilanes (b). . General formula (a) Si (OR ¹ ) _x (R ² ) _4-x (wherein R ¹ is an alkyl group having 1 to 5 carbon atoms and not containing a polymerizable ethylenically unsaturated group or a 1 to 4 carbon atoms) Represents an acyl group containing no polymerizable ethylenically unsaturated group,
² represents an alkyl group having 1 to 10 carbon atoms not containing a polymerizable ethylenically unsaturated group or an aryl group containing no polymerizable ethylenically unsaturated group, and x represents an integer of 2 to 4. Organosilanes containing no polymerizable ethylenically unsaturated groups. Formula (b) Si (OR ³ ) _y (R ⁵ ) _4-yz (wherein R ³ is the same as defined for R ¹ above, R ⁴ is an organic residue having a polymerizable ethylenically unsaturated group, ⁵ is a group having the same meaning as R ² , y is an integer of 1 to 3, and z is an integer of 1 to 3, provided that 2 ≦ y + z ≦ 4. Organosilanes containing groups. 3. The anti-reflection coating according to claim 1, wherein one of the organosilanes contains a perfluoroalkyl group. 4. The antireflection film according to claim 1, wherein after the low refractive index layer is applied, the film is cured by irradiating ultraviolet light or heating. 5. The reflection according to claim 1, comprising the low refractive index layer (1) and a high refractive index layer (2) having a refractive index of 1.7 or more adjacent thereto. Prevention film. 6. A low refractive index layer adjacent to said high refractive index layer (2).
A layer (3) on the opposite side of (1), further comprising a layer (4) having a refractive index of 1.6 or less, wherein the layer (3) has a refractive index higher than that of the layer (4). 6. The antireflection film according to claim 1, wherein the antireflection film has an intermediate refractive index of the refractive index of the refractive index layer. 7. A display device comprising the anti-reflection film according to claim 1.