JPH11258403A - Antireflection film and display device arranged with the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film excellent in film strength, durability, resistance to dirt adhesion, and heat resistance, obtained by using a coating composition excellent in aging stability. SOLUTION: This antireflection film is formed by coating a low refractive index layer with a composition containing an alkoxysilane represented by formula I:Si(OR<1> )4 (R<1> is a 1-5C alkyl group or 1-4C acyl group) and/or an organosilane represented by formula II: R<2> Si(OR<3> )3 (R<2> is a 1-10C alkyl, alkenyl or aryl group; R<3> is a group synonymous with R<1> ), and/or an organosilane represented by formula III: R<4> 2 Si(OR<5> )2 (R<4> is a group synonymous with R<2> ; R<5> is a group synonymous with R<1> ), and a hydrolyzate of silanol-terminated polysiloxane represented by formula IV (R<6> is a group synonymous with R<2> ; (n) represents repetition; and its number average molecular weight is 300-5000) and/or its partial condensation product.

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 an excellent antireflection effect, 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, improvement in resistance to reflected light (ensure visibility), antifouling property and heat resistance. Is required. 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 a method of providing an anti-reflection film on the outermost surface is generally taken. 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 (reflectance of 1% or less), prevention of adhesion of fingerprints and fats and oils, easy removal, and maintenance of various performances in a high temperature environment such as under the sun or in a car interior.

Conventionally, as an antireflection film having a wide wavelength range and a 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 such as a metal oxide 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. Therefore, as the conventional antireflection film, a film obtained by laminating three or more layers of metal oxide or the like by means such as physical or chemical vapor deposition has been used. 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 that is optimally designed in advance, it is necessary to perform the deposition with its film thickness controlled with high precision many times. It is very expensive and poor in suitability for mass production, which makes it very difficult to obtain a large area film.

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
The SiO ₂ ultrafine particles and MgF ₂ ultrafine particles having an intermediate refractive index of the glass substrate and the MgF ₂ were mixed and applied to a glass substrate, gradually SiO toward the coating film surface from the glass substrate 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 composed of a core portion and a shell portion surrounding the core portion. JP-A-7-168 discloses an antireflection film comprising a low-refractive-index layer and a lower layer formed only of fine particles.
No. 006 discloses that a 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 anti-reflection film comprising a lower layer portion is disclosed.

[0007] However, the above-mentioned Japanese Patent Application Laid-Open No. Hei 2-2457.
02, JP-A-5-13021, JP-A-7-
The antireflection films described in JP-A-92305 and JP-A-7-168006 utilize the principle that the refractive index to air gradually changes in the 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.

Also, 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 cannot obtain a sufficient antireflection effect because the difference in refractive index from the substrate is small, and the stability over time of the composition to be applied is insufficient,
The liquid increased in viscosity and hardened in several hours, and was not suitable for producing an antireflection film by continuous coating.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a coating composition which has excellent stability over time, is suitable for large-scale and large-area production, and the resulting antireflection film has a wide wavelength range. The object of the present invention is to provide an antireflection film which exhibits a uniformly low reflectance (reflectance of 1% or less) and is excellent in film strength, durability, stain resistance and heat resistance. Also,
An object of the present invention is to provide a display device having the antireflection film.

[0010]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is as follows.
Achieved by: An alkoxysilane represented by (a) a general formula Si (OR ¹ ) ₄ (wherein R ¹ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms); / Or
(b) Formula R ² Si (OR ³ ) ₃ (wherein, R ² represents an alkyl group, alkenyl group, or aryl group having 1 to 10 carbon atoms, and R ³ represents a group having the same meaning as R ¹ ) in in organosilane represented, and / or (c) general formula _{^{R 4 2 Si (oR 5)}} 2 ( wherein, R
⁴ represents a group having the same meaning as R ² , R ⁵ represents a group having the same meaning as R ¹ ), and (d) a hydrolyzate of a silanol-terminated polysiloxane represented by the following general formula (A). An antireflection film, which is formed by applying a composition containing a decomposition product and / or a partial condensate thereof.

[0011]

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In the formula, R ⁶ represents a group having the same meaning as R ² ,
n represents repetition, and the number average molecular weight is 300 to 5000
0.

The antireflection film of the present invention is more preferable.
The embodiments are as follows, and the antireflection film of the present invention is
The display devices arranged are as follows. The low refractive index layer is composed of (a) a general formula Si (OR¹)_Four(Where R¹Is charcoal
An alkyl group having 1 to 5 primes or an acyl group having 1 to 4 carbons
Represents an alkoxysilane) and / or
(b) General formula R^TwoSi (OR^Three)_Three(Where R^TwoHas 1 to 10 carbon atoms
Represents an alkyl group, an alkenyl group or an aryl group;
^ThreeIs R¹Represents an equivalent group)
Run and / or (c) general formula R^Four _TwoSi (OR^Five)_Two(Where
R^FourIs R ^TwoA group synonymous with R^FiveIs R¹Synonymous with
And / or (e) an organosilane represented by
Hydrolyzable group and / or hydroxyl group at terminal or side chain
A silyl group having a silicon atom bonded to
A vinyl polymer containing at least one silyl group, and
And (d) a silanol terminated polysilo represented by the following general formula (A)
Including hydrolysates of xane and / or partial condensates thereof.
It is formed by applying a composition having
Anti-reflection film to be featured.

[0014]

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In the formula, R ⁶ represents a group having the same meaning as R ² ,
n represents repetition, and the number average molecular weight is 300 to 5000
0. The low refractive index layer (1) and a refractive index adjacent to the low refractive index layer (1) are 1.7.
The antireflection film according to or described above, comprising the high refractive index layer (2) described above. A layer (3) adjacent to the high refractive index layer (2), opposite to the low refractive index layer (1), and further comprising a layer (4) having a refractive index of 1.6 or less; The antireflection film according to any one of claims 1 to 3, wherein 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). A display device comprising the antireflection film according to any one of the above.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is characterized in that a composition formed from a hydrolysis / partial condensate of an organosilane as described above is applied to a low refractive index layer. The constituent features of the present invention will be described in detail.

[Organosilane] An organosilane is a silane compound having at least one functional group capable of providing a silanol by hydrolysis in a molecule, and is obtained by hydrolysis and condensation in the composition of the present invention. It becomes a hydrolyzate and / or a partial condensate and functions as a binder in the composition. In general, the expression
It is a compound represented by (R ⁹ ) ₄ Si. In the formula, R ⁹ is an alkyl group, alkenyl group or aryl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms or 1 to 4 carbon atoms.
Represents an oxyacyl group or a halogen atom. 4 in one molecule
R ^{9 s} may be the same or different from each other as long as they fall within the scope of this definition, and can be freely selected in combination. However, four are simultaneously alkyl, alkenyl, or alkenyl having 1 to 10 carbon atoms. It does not become an aryl group.

R⁹Is an alkyl having 1 to 10 carbon atoms.
Methyl group as an alkyl group, an alkenyl group or an aryl group,
Alkyls such as ethyl group, n-propyl group, i-propyl group, etc.
Kill group, other γ-chloropropyl group, vinyl group, C
F_Three-, 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_TwoOCH_TwoCH_TwoCH_Two-, 3- (perfluorosic
Rohexyloxy) propyl, H (CF_Two)_FourCH_TwoOCH_TwoCH _TwoCH_Two-
 , H (CF_Two)_FourCH_TwoCH_TwoCH_Two-, Γ-glycidoxypropyl
Group, γ-methacryloxypropyl group, γ-mercapto
Propyl group, phenyl group, 3,4-epoxycyclohexyl
And a silethyl group. Arco having 1 to 5 carbon atoms
As the xy group or the oxyacyl group having 1 to 4 carbon atoms,
For example, a methoxy group, an ethoxy group, an n-propoxy group, i
-Propoxy group, n-butoxy group, sec-butoxy group, te
rt-butoxy, acetoxy, halogen
Element, chlorine, bromine, iodine and the like.

Specific examples of these organosilanes include the components (a) to (c) described below. [Component (a)] The component (a) is an alkoxysilane represented by the general formula Si (OR ¹ ) ₄ , and in the composition of the present invention, a hydrolyzate obtained by hydrolysis and condensation and / or Alternatively, it becomes a partial condensate and functions as a binder in the composition. R ^{1 in} such an alkoxysilane is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and i.
-Propyl group, n-butyl group, sec-butyl group, tert-butyl group, acetyl group and the like.

Specific examples of these alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra (n) propoxysilane, tetra (i) propoxysilane, tetra (n) butoxysilane, tetraacetoxysilane and the like. Preferably, tetramethoxysilane, tetraethoxysilane, tetra (n) propoxysilane, tetra (i) propoxysilane and tetraacetoxysilane are preferable, and tetramethoxysilane, tetraethoxysilane and tetraacetoxysilane are particularly preferable. The above alkoxysilanes may be used alone or in combination of two or more.

[Component (b)] The component (b) is represented by the general formula R^TwoSi (O
R^Three)_ThreeIs an organosilane represented by the composition of the present invention.
In the hydrolyzate obtained by hydrolysis, condensation and
And / or becomes a partial condensate and becomes a binder in the composition
It works for all. In such organosilanes
R^TwoIs an alkyl or alkenyl group having 1 to 10 carbon atoms.
Or an aryl group, for example, a methyl group, an ethyl group, n
Alkyl groups such as -propyl group, i-propyl group,
Γ-chloropropyl group, vinyl group, CF_Three-, CF_ThreeCH_Two-
 , CF_ThreeCH_TwoCH_Two-, CF_ThreeCH_TwoCH_TwoCH_Two-, C_TwoF_FiveCH_TwoCH_TwoCH_Two-, C_ThreeF
₇CH_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_TwoOCH_TwoCH_TwoCH_Two-, 3- (perfluorocyclohe
Xyloxy) propyl, H (CF_Two)_FourCH_TwoOCH_TwoCH_TwoCH_Two-, H
(CF_Two)_FourCH_TwoCH_TwoCH_Two-, Γ-glycidoxypropyl group, γ
-Methacryloxypropyl group, γ-mercaptopropyl
Group, phenyl group, 3,4-epoxycyclohexyl
And a tyl group. In addition, R in the organosilane
^ThreeIs an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 4 carbon atoms.
An acyl group, for example, a methyl group, an ethyl group,
Pill group, i-propyl group, n-butyl group, sec-butyl
Group, tert-butyl group, acetyl group and the like.

As specific examples of these organosilanes,
Means methyltrimethoxysilane, methyltriethoxy
Orchid, ethyltrimethoxysilane, ethyltriethoxy
Silane, n-propyltrimethoxysilane, n-propyl
Lutriethoxysilane, i-propyltrimethoxysila
, I-propyltriethoxysilane, γ-chloropro
Piltrimethoxysilane, γ-chloropropyltriet
Xysilane, vinyltrimethoxysilane, vinyltrie
Toxysilane, γ-glycidoxypropyltrimethoxy
Silane, γ-glycidoxypropyltriethoxysila
, Γ-methacryloxypropyltrimethoxysila
, Γ-methacryloxypropyltriethoxysila
Γ-mercaptopropyltrimethoxysilane, γ-
Mercaptopropyltriethoxysilane, phenyltri
Methoxysilane, phenyltriethoxysilane, 3,4
-Epoxycyclohexylethyltrimethoxysilane,
3,4-epoxycyclohexylethyl triethoxy
Run, CF_ThreeCH_TwoCH_TwoSi (OCH_Three)_Three, CF_ThreeCH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three,
C_TwoF_FiveCH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three, C_TwoF_FiveCH_TwoCH_TwoSi (OCH_Three)_Three, C_Three
F₇CH _TwoCH_TwoCH_TwoSi (OCH_Three)_Three, C_TwoF_FiveOCH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three, C_Three
F₇OCH_TwoCH_TwoCH_TwoSi (OC_TwoH_Five)_Three, (CF_Three)_TwoCHOCH_TwoCH_TwoCH_TwoSi (OCH_Three)
_Three, C_FourF₉CH_TwoOCH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three, H (CF_Two)_FourCH_TwoOCH_TwoCH_Two
CH_TwoSi (OCH_Three)_Three, 3- (Perfluorocyclohexyloxy)
C) propylsilane and the like.

Of these, organosilanes having a fluorine atom are preferred. In addition, when an organosilane containing no fluorine atom is used as R ^2, it is preferable to use methyltrimethoxysilane or methyltriethoxysilane. One of the above organosilanes may be used alone, or two or more thereof may be used in combination.

[0024] [component (c)] The component (c), the general formula R ⁴ ₂ Si (OR
⁵ ) ₂ (wherein R ⁴ and R ⁵ have the same meanings as R ² and R ³ defined for the organosilane used in component (b) above)
Is a diorganosilane represented by However, R ⁴ and R ⁵ need not be the same substituents as the component (b). In the composition of the present invention, it becomes a hydrolyzate and / or a partial condensate obtained by hydrolysis and condensation, acts as a binder in the composition, and softens the coating film to improve alkali resistance. It is.

Specific examples of these diorganosilanes are dimethyldimethoxysilane, dimethyldiethoxysilane,
Diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane Silane, (CF ₃
CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ , (CF ₃ CH ₂ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ , (C ₃ F
₇ OCH ₂ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ , (H (CF ₂ ) ₆ CH ₂ OCH ₂ CH ₂ CH ₂ ) ₂ Si
(OCH ₃ ) ₂ , (C ₂ F ₅ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) _{2 and the} like can be mentioned, and an organosilane having a fluorine atom is preferable. When an organosilane having no fluorine atom is used as R ⁴ , dimethyldimethoxysilane and dimethyldiethoxysilane are preferred. Such R ⁴ ₂ Si (OR ⁵ )
_The organosilane represented by ₂ may be used alone or in combination of two or more. (c)
The proportions of the components in the composition of the present invention are (a) and (b)
0 to 150% by weight based on the components, preferably 5 to 100%
% By weight, more preferably 10 to 60% by weight,
If it exceeds 50% by weight, the adhesion and curability of the resulting coating film will be reduced.

[Component (d)] The component (d) is a silanol-terminated polysiloxane represented by the following general formula (A), which controls the hydrolysis of chlorosilane chemically or pressurizes cyclic siloxane under pressure. It can be synthesized by a method such as equilibrium polymerization with water. Some types are G
It can be purchased from erest or the like.

[0027]

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Where R⁶Is R^TwoRepresents a synonymous group, and n
Represents repetition. Such silanol terminated polysiloxa
R inside⁶Is an alkyl group having 1 to 10 carbon atoms, alkenyl
Group or aryl group, for example, methyl group, ethyl group
Group, n-propyl group, i-propyl group, t-butyl group, etc.
Any alkyl group, other γ-chloropropyl group, vinyl
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-, H (CF
_Two)_FourCH_TwoCH_TwoCH_Two-, Γ-mercaptopropyl group, phenyl
And the like.

Of these, a silanol-terminated polysiloxane having a fluorine atom is preferred. When R ⁶ does not have a fluorine atom, a silanol-terminated polysiloxane using a methyl group or an ethyl group is preferable. The number average molecular weight of the silanol-terminated polysiloxane is preferably from 300 to 50,000, more preferably from 400 to 25.
000. When the average molecular weight is smaller than this range, the antireflection performance of the low refractive index layer obtained from the composition of the present invention decreases, and when the average molecular weight is larger than this range, the obtained film hardness decreases.

The following are specific examples of these silanol-terminated polysiloxanes.

[0031]

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[0032]

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[0033]

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[0034]

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The silanol-terminated polysiloxane is 1
Species may be used alone or in combination of two or more. The proportion of the component (d) in the composition of the present invention is as follows:
(a), (b), (c) and (e) components (simultaneously (a), (b),
(c) and (e) are never 0) 1 to 50% by weight, preferably 2 to 25% by weight, more preferably 5 to 5% by weight.
The content is 20% by weight, and if it exceeds 50% by weight, the adhesion and curability of the obtained coating film decrease.

[(E) Silyl group-containing vinyl polymer] (e)
The silyl group-containing vinyl polymer has at least one silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal or a side chain in a molecule of the polymer. Preferably, it contains two or more, and most of the silyl groups have the following general formula:

[0037]

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Wherein X is a hydrolyzable group such as a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, an amino group and / or a hydroxyl group; R ¹⁰ 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).

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

[0040]

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(Where X, R ¹⁰ and a are the same as those described above;
¹¹ is an organic group having a polymerizable double bond), and a vinyl compound may be produced by polymerizing the silane compound, 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,

[0044]

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[0045]

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[0046]

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A vinyl polymer obtained by copolymerizing a vinyl compound selected from the above with 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.

[0049]

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[0050]

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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 a hydroxyl group 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:

[0053]

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(Wherein R ¹² and R ¹⁴ are a hydrogen atom, a fluorine atom or a methyl group, R ¹³ is a hydrogen atom and an alkyl group having 1 to 12 carbon atoms (for example, 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 ¹⁵ represents a carbon atom having 1 carbon atom such as a methylene group, an ethylene group, a propylene group or a butylene group. And R ¹⁶ are the same as R ¹³ , and m / (l +
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 silyl group-containing vinyl polymer (e) used in the present invention as described above include Kanekazemulak manufactured by Kaneka Corporation and the following polymers. It is not limited to these.

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-methacryloxypropyl trimethoxysilane (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-methacryloxypropyl Trimethoxysilane (25/60/15: weight ratio) P-18: FM-9 / methyl methacrylate / γ-methacryloxypropyl trimethoxysilane (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 component (e) in the composition of the present invention is as follows:
0 to 100% by weight, preferably 2 to 80% by weight, more preferably 5% by weight, based on the total of the components (a), (b) or (c).
５０50% by weight. If (e) is less than 2% by weight, the alkali resistance of the obtained coating film is low, while if it exceeds 100% by weight, the durability of the obtained coating film is deteriorated.

The low refractive index layer of the present invention is formed of a network polymer structure containing organic silicon as a main component and prepared by the above method. Main component (monomer) that constructs this network structure
Are the above-mentioned compounds (a) to (e). Preferred combinations of these organosilicon monomer compounds in the present invention are illustrated below and in the Examples. The mixing ratio indicates the weight (g) of each compound used in preparing the sol.

SP-1: Methyltrimethoxysilane 1
0 g, dimethyldimethoxysilane 5 g, AA-1
2.5 g, P-12 2.5 g SP-2: methyltrimethoxysilane 12 g, dimethyldiethoxysilane 8 g, 3,3,3-trifluoropropyltrimethoxysilane 4 g, AA-22 g, P
-12 3 g SP-3: tetraethoxysilane 15 g, 3,3,3
-Trifluorobutyl triethoxysilane 15 g, A
A-4 1 g SP-4: Tetraethoxysilane 10 g, dimethyldimethoxysilane 5 g, 3,3,3-trifluoropropyltriethoxysilane 10 g, AA-8 0.5
g, P-12 1.5 g SP-5: methyltrimethoxysilane 10 g, dimethyldimethoxysilane 5 g, 3-perfluoroethoxypropyltrimethoxysilane 5 g, AA-111.5
g, P-5 2.5 g SP-6: tetraethoxysilane 10 g, bis (3,
3,3-trifluoropropyl) diethoxysilane 5
g, AA-13 2 g, P-7 3 g SP-7: tetraethoxysilane 5 g, methyltrimethoxysilane 10 g, dimethyldimethoxysilane 5
g, 3,3,3-trifluoropropyltrimethoxysilane 12 g, AA-19 3 g SP-8: cyclohexyltrimethoxysilane 18
g, bis (3,3,3-trifluoropropyl) triethoxysilane 12 g, tetraethoxysilane 15
g, AA-20 5 g SP-9: tetraethoxysilane 12 g, dimethyldichlorosilane 10 g, 3,3,3-trifluoropropyltriethoxysilane 15 g, AA-1 1.0 g SP-10: methyltriethoxysilane 12 g, Dimethyldimethoxysilane 5 g, bis (3,3,3-trifluoropropyl) trimethoxysilane 5 g, AA-1
5.5 g, P-8 4.5 g

The curing reaction accelerating compound used in the composition of the present invention is not particularly limited, and any compound having a component capable of accelerating the condensation reaction according to the constituent components of the composition used can be suitably used. it can. Generally effective are the following compound groups (f) to (i), from which preferred compounds can be added in required amounts. In addition, two or more of these groups can be appropriately selected and used together as long as the mutual promoting effect is not inhibited. In addition,
The curing accelerating compound is 0.1 to 20 based on the organosilane.
It is preferable to use weight%.

[Component (f)] As the inorganic acid of (f),
Examples of organic acid compounds such as hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, and phosphorous acid include carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, succinic acid, and cyclohexanecarboxylic acid). Octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid, benzoic acid, pentafluorobenzoic acid, phthalic acid, etc., and sulfonic acids (methanesulfonic acid, ethanesulfonic acid, trifluorosulfonic acid) Methanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric / phosphonic acids (dimethyl phosphate, phenylphosphonic acid, etc.), Lewis acids (boron trifluoride etherate, scandium triflate, alkyl Titanic acid, aluminate, etc.), heteropoly acid ( Down molybdate and phosphotungstic acid) can be exemplified.

[Component (g)] As the inorganic base of (g), sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, ammonia and the like, and as the organic base compound, 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).

[Component (h)] The metal chelate compound of (h) is an alcohol represented by the general formula R ¹⁷ OH (where R ¹⁷ represents an alkyl group having 1 to 6 carbon atoms) and R ¹⁸ COC
H ₂ COR ¹⁹ (wherein, R ¹⁸ is an alkyl group having 1 to 6 carbon atoms, R ¹⁹ is an alkyl group having 1 to 5 carbon atoms or 1 to 6 carbon atoms)
Any of those having a transition metal as a central metal having a diketone represented by the following formula (indicating 16 alkoxy groups) as a ligand can be suitably used without particular limitation. In this category, two or more metal chelate compounds may be used in combination.
Particularly preferred as (h) metal chelate compounds of the present invention are those having Al, Ti, and Zr as central metals, and have the general formula Zr (OR ¹⁷ ) _p1 (R ¹⁸ COCHCOR ¹⁹ ) _p2 , Ti (OR ¹⁷ )
_q1 (R ¹⁸ COCHCOR ¹⁹ ) _q2 and Al (OR ¹⁷ ) _r1 (R ¹⁸ COCHCOR ¹⁹ )
A compound selected from the group of compounds represented by _r2 is preferable, and has an effect of accelerating the condensation reaction between the components (a) to (d) and the (e) silyl group-containing vinyl resin.

(H) R ¹⁷ and R ¹⁸ in the metal chelate compound 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, Examples include an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and a phenyl group. Also, R
¹⁹ 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, (h) p _{1 to} r ₂ in the metal chelate compound represent an integer determined to have a tetradentate or hexadentate coordination.

Specific examples of these (h) metal chelate compounds include zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), zirconium n-butoxytris (ethylacetoacetate), 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; aluminum diisopropoxyethyl acetoacetate, aluminum diisopropoxyacetylacetonate, aluminum isopropoxybis (ethylacetoacetate) aluminum, aluminum isopropoxybis (acetylacetonate) , Tris (ethylacetoacetate) aluminum, Tris (acetylacetonate) Aluminum, mono acetyl acetonate bis (ethyl acetoacetate), and the like of aluminum chelate compounds such as aluminum. Among these (h) metal chelate compounds, preferred are tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethylacetoacetate).
Aluminum. These (h) metal chelate compounds can be used alone or in combination of two or more. Further, as the component (h), a partial hydrolyzate of these metal chelate compounds can be used.

(H) The ratio of the metal chelate compound in the composition is 0.1% with respect to the organosilane which is the raw material of the sol.
It is from 0.1 to 50% by weight, preferably from 0.1 to 50% by weight, more preferably from 0.5 to 10% by weight.

[Component (i)] Preferred organic metal of (i)
The compound is not particularly limited, but the organic transition metal is active.
High and preferred. Among them, tin compounds are stable and active
Good and particularly preferred. Examples of these specific compounds include:
(C_FourH₉)_TwoSn (OCOC₁₁H_{twenty three})_Two, (C_FourH₉)_TwoSn (OCOCH = CHCOOC
H_Three)_Two, (C_FourH₉)_TwoSn (OCOCH = CHCOOC_FourH₉)_Two, (C₈H₁₇)_TwoSn (OCO
C₁₁H_{twenty three})_Two, (C₈H₁₇)_TwoSn (OCOCH = CHCOOCH_Three)_Two, (C₈H₁₇)_TwoSn
(OCOCH = CHCOOC_FourH₉)_Two, (C₈H₁₇)_TwoSn (OCOCH = CHCOOC
₈H₁₇)_Two, Sn (OCOCC₈H₁₇)_TwoCarboxylic acid type organotin
Compound; (C_FourH₉)_TwoSn (SCH_TwoCOOC₈H₁₇)_Two, (C_FourH₉)_TwoSn (SCH_TwoCO
OC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC₈H₁₇)_Two, (C ₈H₁₇)_TwoSn (S
CH_TwoCH_TwoCOOC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC₈H₁₇)_Two, (C₈H
₁₇)_TwoSn (SCH_TwoCOOC₁₂H_{twenty five})_Two,

[0071]

Embedded image

Mercaptide-type organotin compounds such as

[0073]

Embedded image

Sulfide-type organotin compounds such as

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

[Component (j)] As the metal salts of (j), alkali metal salts of organic acids (for example, sodium naphthenate, potassium naphthenate, sodium octanoate,
Sodium ethylhexanoate, potassium laurate and the like) are preferably used.

The composition of the present invention can be used by adding various compounds as required in addition to the above components.
The following describes the main combined materials.

[A: Solvent] The solvents are (a) to (e) in the sol liquid.
The components and the curing reaction accelerating compounds (f) to (j) are uniformly mixed to adjust the solid content of the composition of the present invention, and at the same time, to be applicable to various coating methods, to improve the dispersion stability of the composition and It improves 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, esters and the like are preferred.

Among them, the alcohols include, for example, monohydric alcohols and dihydric alcohols, and among them, saturated aliphatic alcohols having 1 to 8 carbon atoms are preferable. 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.

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 proportion 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.

[B: Chelate Ligand Compound] When the metal complex compound (h) is used in the composition of the present invention, a compound having chelate coordination ability is used from the viewpoint of controlling the curing reaction rate and improving the liquid stability. It is also preferred. Preferably used are β-diketones and / or β-ketoesters represented by the general formula R ¹⁸ COCH ₂ COR ^19, which act as a stability improver of the composition of the present invention. That is, by coordinating to a metal atom in the (g) metal chelate compound (preferably zirconium, titanium and / or aluminum compound) present in the accelerating solution, (a) to (e) It is considered that the action of accelerating the condensation reaction of the components is suppressed and the curing rate of the obtained film is controlled. R ¹⁸ and R ¹⁹ are the same as R ¹⁸ constituting the metal chelate compound (h).
And it is synonymous with R ^19, but need not have the same structure in use.

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 as a mixture of two or more.
Such β-diketones and / or β-ketoesters are (h) 2 mol or more, preferably 3 to 20 mol, per 1 mol of the metal chelate compound, and if less than 2 mol, the storage stability of the obtained composition is poor. Inferior.

[C: Water] The preferred sol solution of the present invention includes:
Water is added for hydrolysis / condensation of the mixture containing the above components (a) to (e) as main components. The amount of water used is usually about 1.2 to 3.0 mol, preferably about 1.3 to 2.0 mol, per 1 mol of the components (a) to (e). The preferred sol solution and accelerating solution of the present invention have a total solid content of 0.1 to 5
The content is 0% by weight, preferably 1 to 40% by weight, and if it exceeds 50% by weight, the storage stability of the composition deteriorates, which is not preferable.

[D: Filler] Colloidal silica can be added to the sol solution of the present invention for the purpose of improving the hardness of the obtained coating film. Examples of the 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 contains the above-mentioned colloidal composition in order to exhibit various properties such as coloring of the resulting coating film, imparting irregularities, preventing UV transmission to the substrate, imparting corrosion resistance, and heat resistance. Fillers other than silica can be added and dispersed. 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, red iron, 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 (a) to
(e) 10 to 300 parts by weight based on 100 parts by weight of the total solid content of the component.
It is about parts by weight.

[E: Other Additives] The sol solution and the accelerating solution of the present invention may further include known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants, and other silanes. Additives such as a coupling 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, and the solvent does not cause precipitation when the above-mentioned components (a) to (e) 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, first, a composition containing the above-mentioned components (a) to (e) is prepared, and water is added to the composition to hydrolyze it. Good. 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 method in which 0.2 to 3 mol of water is added to 1 mol of an organosilane to a solution comprising the components (a) to (e), a solvent and a hydrolysis catalyst to carry out a hydrolysis / condensation reaction.

In a solution comprising the components (a) to (d) and a solvent,
A method in which 0.2 to 3 mol of water is added to 1 mol of organosilanes to carry out hydrolysis / condensation reaction, and then (e) a silyl group-containing vinyl polymer and a hydrolysis catalyst are added. To a solution comprising the components (a) to (d), 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 group-containing vinyl polymer is added, mixed, and then subjected to a condensation reaction.

The sol solution and the accelerating solution of the present invention are applied to a transparent film or a high or middle refractive index layer by a coating method such as curtain flow coating, dip coating, spin coating, roll coating, etc., and dried at normal temperature, or 30 ~
By heating at a temperature of about 200 ° 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 formed. 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.

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. ), A medium-refractive-index layer (3) on the opposite side of the low-refractive-index layer (1), adjacent to the high-refractive-index layer (2), and further a layer (4) (support undercoating, etc.)
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, and more preferably the layer (1) has a thickness of 60 to 150 nm and the layer (2) has a thickness of 50 to 15 μm.
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, heterocycle, alicyclic group other than polycarbonate or polystyrene, or a polymer having a halogen group other than fluorine); thermosetting resin composition (eg, melamine resin, phenol resin, epoxy resin, etc.) A curing agent); a urethane-forming composition (e.g., a combination of an alicyclic compound to an aromatic isocyanate and a polyol); and a radical polymerizable composition (a double bond to the above compound (polymer or the like)) And a composition containing a modified resin or a prepolymer that has been made radically hardenable by introducing the same. 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. Such materials include, in addition to the organic materials described above, vinyl-based copolymers including acrylics, polyesters, alkyd resins, cellulose-based polymers, urethane resins and various curing agents for curing these, curable Examples of various organic materials that are transparent and can stably disperse inorganic fine particles, such as a composition having a functional group, can be given.

Further, an organic-substituted silicon compound can be included in the compound. These silicon compounds are compounds represented by the following general formula, or hydrolysis products thereof. R ⁵¹ mR ⁵² _n SiZ _(4-mn) (where R ⁵¹ and R ⁵² are an alkyl group, an alkenyl group, an allyl group, or a hydrocarbon substituted with halogen, epoxy, amino, mercapto, methacryloyl to cyano, respectively) Z represents a hydrolyzable group selected from an alkoxyl group, an alkoxyalkoxyl group and a halogen atom to an acyloxy group, and m and n are each 0 or 1 under the condition that m + n is 1 or 2. Or 2.)

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 finely divided form, i.e., a powder 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 a material for forming a layer having a higher refractive index than the above, 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, an anti-moisture layer, an anti-static layer and the like may be provided on the transparent film as an intermediate layer. 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.

[0108]

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.

(1) Silyl group-containing vinyl resin (P-12)
Preparation of In a 1-liter three-necked flask equipped with a reflux condenser and a stirrer, 30.6 g of the fluoromonomer FM-4 and 5.4 g of γ-methacryloxypropyltrimethoxysilane were added.
The mixture was heated and stirred at 70 ° C. under a nitrogen stream. 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.)
4.8 g dissolved in 25 ml of methyl ethyl ketone.
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. Thereafter, 280 ml of methyl ethyl ketone was added, followed by cooling to obtain 635 g of a solution of the title P-12. . 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 A reactor equipped with a stirrer was charged with (b) 100 g of methyltrimethoxysilane, (c) 50 g of dimethyldimethoxysilane, and (d)
5 g of AA-1 and 50 g of (f) 0.01N hydrochloric acid ethanol were added and mixed, and reacted at 25 ° C. for 48 hours to obtain a sol liquid SA for a low refractive index layer. If necessary, the same reaction was carried out using (a) tetraethoxysilane, and the sol liquid SB shown in Table 1 was obtained.
~ SH, SX, SY were obtained. Further, (b) methyltrimethoxysilane 100 was added to a reactor equipped with a stirrer and a reflux condenser.
g, (c) 50 g of dimethyldimethoxysilane, (d) AA-
110g, (e) Silanol group-containing polymer P-12
50 g, (f) aluminum diisopropoxy acetoacetate 20 g, methyl ethyl ketone 30 g, water 10 g
After reacting at 60 ° C. for 4 minutes, the mixture was cooled to room temperature to obtain a sol liquid PA for a low refractive index layer. As needed (a)
The same reaction was carried out using tetraethoxysilane to obtain sol solutions PB to PH, PX and PY shown in Table 2.

[0111]

[Table 1]

[0112]

[Table 2]

(3) Coating of the first layer (hard coat layer) 25 parts by weight of dipentaerythritol penta / hexaacrylate (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.)
25 parts by weight of a urethane acrylate oligomer (trade name: UV-6300B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.),
2 parts by weight of a photopolymerization initiator (trade name: Irgacure 90)
7, Ciba-Geigy) and 0.5 parts by weight of a sensitizer (trade name: Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
Was dissolved in 50 parts by weight of methyl ethyl ketone and applied to a TAC film having a thickness of 90 μm by using a wire bar, and then the applied film was irradiated with ultraviolet rays to form a hard coat layer (refractive index: 1.53, layer (Thickness: 5 μm).

(4) Coating of Second Layer (Medium Refractive Index Layer) A coating liquid containing TiO ₂ fine dispersion and polymethyl methacrylate (refractive index: 1.48) as a binder (solid content: 2% by weight, TiO ₂ / binder = 22/78, weight ratio) was applied on the hard coat layer using a wire bar, dried at 100 ° C., and dried at a medium refractive index layer (refractive index:
1.62, layer thickness: 78 nm). (5) Coating of third layer (high refractive index layer) Coating liquid containing fine dispersion of TiO ₂ and the above binder (solid content: 2% by weight, TiO ₂ / binder = 68/32,
(Weight ratio) was applied on the middle refractive index layer using a wire bar, and dried at 100 ° C. to obtain a high refractive index layer (refractive index: 2.
00, layer thickness: 127 nm).

(6) Coating of Fourth Layer (Low Refractive Index Layer) The compositions shown in Tables 1 and 2 were coated on the high refractive index layer using a wire bar so as to have a thickness of 94 nm. , 120
C. for 5 minutes to form a low refractive index layer. The refractive index of the layer ranged from 1.3 to 1.5.

(7) Performance Evaluation of Coated Film The surface reflectance (average reflectance at a light wavelength of 400 to 650 nm) and the film surface strength of the thus obtained film coated with the first to fourth layers were measured. did. The film surface strength is rubbed with fingertips, tissue, eraser, fingertips, respectively, and visually observed, 0 is rubbed with fingertips, 1 is rubbed with tissue, 1 is rubbed with eraser, 2 is rubbed with eraser. A sample was given a score of 3 when it was scratched by fingertip toe rubbing, and a sample was given 4 when no scratch was found by any method. The results are shown in Table 3.

[0117]

[Table 3]

As is apparent from the present 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, many of the comparative examples had insufficient surface reflectivity or film strength.

(8) (Preparation of Display Device with Antireflection Film Installed) The antireflection films of Examples 1 to 14 and Comparative Examples 1 and 4 prepared in the above example were obtained from a personal computer PC9821NS obtained from NEC Corporation. A surface device sample was prepared by adhering to a surface of a / 340 W liquid crystal display, and the degree of reflection of the scenery by surface reflection was visually evaluated. The display device provided with the antireflection film of Examples 1 to 14 of the present invention has almost no surrounding scenery reflection,
While the display device showed comfortable visibility and had sufficient surface strength, the display devices on which the films of Comparative Examples 1 and 4 were installed showed a large amount of surrounding reflection and were inferior in visibility.

[0120]

According to the present invention, a low refractive index layer is formed by applying a composition obtained by a polycondensation reaction of a silanol-terminated polysiloxane, an alkoxysilane and / or an organic polymer. When the ratio is 1.7 or more, a large-area antireflection film having excellent optical characteristics and excellent film strength can be provided at low cost and in a form having suitability for production.

[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: undercoat layer

Claims (5)

[Claims] 1. A low refractive index layer comprising: (a) a compound represented by the general formula Si (OR ¹ ) ₄ (wherein R ¹ is an alkyl group having 1 to 5 carbon atoms or 1 to 4 carbon atoms)
And / or (b) a general formula R ² Si (OR ³ ) ₃ (wherein R ² has 1 carbon atom)
10 alkyl group, an alkenyl group or an aryl group, organosilanes R ³ is represented by representing) a group synonymous with the R ^1, and / or (c) general formula R ⁴ ₂ Si (OR ⁵⁾ _Two
(Wherein, R ⁴ represents a group having the same meaning as R ² , and R ⁵ represents a group having the same meaning as R ¹ ), and
(d) A reflection formed by applying a composition containing a hydrolyzate of a silanol-terminated polysiloxane represented by the following general formula (A) and / or a partial condensate thereof: Prevention film. Embedded image In the formula, R ⁶ represents a group having the same meaning as R ² , n represents repetition, and has a number average molecular weight of 300 to 50,000. 2. The method according to claim 1, wherein the low refractive index layer comprises (a) a compound represented by the general formula Si (OR ¹ ) ₄ (wherein R ¹ is an alkyl group having 1 to 5 carbon atoms or
And / or (b) a general formula R ² Si (OR ³ ) ₃ (wherein R ² has 1 carbon atom)
10 alkyl group, an alkenyl group or an aryl group, organosilanes R ³ is represented by representing) a group synonymous with the R ^1, and / or (c) general formula R ⁴ ₂ Si (OR ⁵⁾ _Two
Wherein R ⁴ represents a group having the same meaning as R ² , and R ⁵ represents a group having the same meaning as R ¹ , and / or (e) a hydrolyzable group at a terminal or a side chain. And / or a silyl group-containing vinyl polymer having at least one silyl group having a silicon atom bonded to a hydroxyl group in the polymer, and (d) a hydrolyzate of a silanol-terminated polysiloxane represented by the following general formula (A): And / or an antireflection film formed by applying a composition containing a partial condensate thereof. Embedded image In the formula, R ⁶ represents a group having the same meaning as R ² , n represents repetition, and has a number average molecular weight of 300 to 50,000. 3. The reflection according to claim 1, wherein the low-refractive-index layer (1) and the high-refractive-index layer (2) having a refractive index of 1.7 or more are adjacent thereto. Prevention film. 4. A low refractive index layer adjacent to said high refractive index layer (2).
A layer (3) on the opposite side of (1), and 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). The antireflection film according to any one of claims 1 to 3, wherein the antireflection film has an intermediate refractive index of the refractive index of the refractive index layer (2). 5. A display device comprising the anti-reflection film according to claim 1.