JPH11106704A - Reflection reducing film and display unit using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reflection reducing film which has a low reflectance (a reflectance of 1% or less) over a wide range of wave length and, at the same time, has an excellent film strength and resistance to heat. SOLUTION: This film comprises a layer having a low index of reflection formed from a composition comprising (a) 100 pts.wt. of a hydrolyzed product and/or its partially condensed product of an organosilane represented by the formula R<1> Si(OR<2> )3 (wherein R is a 1-8C organic group, and R<2> is a 1-5C alkyl or 1-4C acyl group), in terms of the weight of the organosilane, (b) 0 to 150 pts.wt. of a hydrolyzed product and/or its partially condensed product of a diorganosilane represented by the formula R<1> 2 Si(OR<2> )2 (wherein R<1> and R<2> are each as defined above), in terms of the weight of the diorganosilane, and (c) 2 to 300 pts.wt. of a silyl group-containing vinyl resin having, in its polymer molecule, at least one silyl group which has a silicon atom bonded with a hydrolyzable group and/or a hydroxyl group, at a terminal or a side chain, wherein at least one of R<1> or at least one of the silyl group-containing vinyl resin contains a fluorine atom, and a high reflection layer having an index of reflection of 1.7 or more which is arranged in the vicinity of the above-mentioned layer.

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, 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 as a countermeasure against this, a method of providing an antireflection film on the outermost surface is generally performed. However,
Since this antireflection film is provided on the outermost surface in order to exhibit its function, many issues of high quality are inevitably concentrated on the performance of the antireflection 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. However, for this reason, a conventional antireflection film in which three or more layers of a metal oxide or the like are laminated by means such as physical or chemical vapor deposition has been used. According to the relationship between the refractive index and the film thickness of each layer, which has been optimally designed in advance, it is necessary to perform the deposition in which the film thickness is controlled with high precision many times. They are expensive and have 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
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.

[0006] Also, JP-A-7-92305 discloses that
Refractive index of 1.428 consisting of core and surrounding shell
An anti-reflection film is disclosed which comprises an upper layer portion (low refractive index) having irregularities on the surface formed of air and fine particles and a lower layer portion formed only of fine particles.
And the core of the ultrafine particles is methyl methacrylate, methacrylic acid, trifluoroethyl acrylate,
Formed from N-isobutoxymethylacrylamide,
The shell part is formed from styrene, acrylic acid, and butyl acrylate.

Further, Japanese Patent Application Laid-Open No. Hei 7-168006 discloses that the surface formed of air and fine particles (eg, MgF ₂ ) has an irregular upper layer portion (low refractive index) and a fine particle only middle layer portion (medium refractive index). ), And an antireflection film comprising fine particles and a lower layer portion formed of a binder.

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.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to exhibit a uniformly low reflectance (reflectance of 1% or less) over a wide wavelength range, and at the same time, to obtain film strength, durability, adhesion to dirt, and heat resistance. An object of the present invention is to provide an antireflection film excellent in low cost at low cost and in a method suitable for large-scale and large-area production. 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 to provide at least one of the following (a), (b), (c) or a hydrolyzate of (a), (c) and / or a partial condensate thereof. An antireflection film having a low refractive index layer (1) formed from a composition constituted by (a), (b), (c) or the composition (a).
And (c) the composition has a fluorine atom in at least one of (a), (b) and (c), and the fluorine atom is contained in the repeating unit of R ¹ or a silyl group-containing vinyl resin in the general formula. This has been achieved by an anti-reflection film characterized by the following. (a) Formula R ¹ Si (OR ² ) ₃ (wherein R ¹ is an organic group having 1 to 10 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms) Organosilane represented by: (b) the general formula _{^{R 1 2 Si (OR 2)}} 2 ( wherein, R ^1, R ² is the (a)
Represents the same substituent as defined in the above, but need not be the same substituent as (a)).
0 to 150% by weight based on (a). (c) a silyl group-containing vinyl polymer resin having 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 the polymer, based on (a); 300% by weight.

The following are preferred embodiments of the antireflection film of the present invention, and the following are display devices provided with the antireflection film of the present invention. The composition containing the above (a) to (c) is added with (d) a general formula R ³ OH
(Wherein R ³ represents an alkyl group having 1 to 6 carbon atoms) and R ⁴ COCH ₂ COR ⁵ (wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms, and R ⁵ is A diketone represented by an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 16 carbon atoms) as a ligand, and at least one kind of metal having a central metal selected from Zr, Ti and Al. 0.01 to 50% by weight of the metal chelate compound based on (a), (e) an organic solvent, (f) a general formula R ⁴ COCH ₂ COR ⁵ (wherein R ⁴ and R ⁵
Wherein the β-diketones and / or β-ketoesters represented by 2) are added in an amount of 2 mol or more per 1 mol of the metal chelate compound (d). . 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) and opposite to the low refractive index layer (1), and further having a layer (4),
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).

[0012] A display device comprising the antireflection film described above. A display device, comprising the anti-reflection film according to any one of the preceding claims. A display device, comprising the anti-reflection film according to any one of the preceding claims. A display device, comprising the anti-reflection film according to any one of the preceding claims.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The present invention is as described above.
(a), (b), (c) The low-level formed from (a), (c)
The refractive index layer is characteristic, but especially the components that make up the composition
(a), (b) or (c) contains a fluorine atom
You. The constituent features of the present invention will be described in detail. (a) Component (a) Component is represented by the general formula R¹Si (OR^Two)_ThreeOrganosila represented by
Are hydrolyzed and condensed in the composition of the present invention.
The resulting hydrolyzate and / or partial condensate
It acts as a binder in the product.
R in such organosilane¹Is a group having 1 to 10 carbon atoms
For example, methyl group, ethyl group, n-propyl
Groups, alkyl groups such as i-propyl group, and other γ-
Lolopropyl group, vinyl group, CF_ThreeCH_TwoCH_TwoCH_Two-, C_TwoF_FiveCH_TwoC
H_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)_TwoCHOC
H_TwoCH_TwoCH_Two-, C_FourF₉CH_TwoOCH_TwoCH_TwoCH_Two-, 3- (perfluoro
Cyclohexyloxy) propyl, H (CF_Two)_FourCH_TwoOCH_TwoCH_TwoC
H_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. Also, organosilane
R in^TwoIs an alkyl group having 1 to 5 carbon atoms or 1 carbon atom
To 4, for example, a methyl group, an ethyl group, n
-Propyl group, i-propyl group, n-butyl group, sec-butyl
Tyl group, tert-butyl group, acetyl group and the like.
You.

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_TwoCH_TwoSi (OCH_Three)_Three, C_TwoH_FiveCH_TwoCH_TwoCH_TwoSi (OC
H_Three)_Three, C_TwoF_FiveCH_TwoCH_TwoSi (OCH_Three)_Three, C_ThreeF₇CH_TwoCH_TwoCH_TwoSi (OC
H_Three)_Three, C_TwoF_FiveOCH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three, C_ThreeF₇OCH_TwoCH_TwoCH_TwoSi (O
C_TwoH_Five)_Three, (CF_Three)_TwoCHOCH_TwoCH_TwoCH_TwoSi (OCH _Three)_Three, C_FourF₉CH_TwoOCH_TwoC
H_TwoCH_TwoSi (OCH_Three)_Three, H (CF_Two)_FourCH_TwoOCH_TwoCH_TwoCH_TwoSi (OCH_Three)_Three,
3- (perfluorocyclohexyloxy) propyl
And the like.

Of these, organosilanes having a fluorine atom are preferred. When an organosilane having no fluorine atom is used as R ^1, 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.

[0016] Component (b) Component (b), the general formula _{^{R 1 2 Si (OR 2)}} 2 ( wherein, R ¹ and R
² is a diorganosilane represented by (a) the same as R ¹ and R ² defined in organosilane used for Component). However, R ¹ and R ² need not be the same substituents as the component (a). Hydrolysis in the composition of the present invention;
It becomes a hydrolyzate and / or a partial condensate obtained by condensation, serves as a binder in the composition, softens the coating film, and improves alkali resistance. R ¹ and R in such a diorganosilane
² is the same as R ¹ and R ^{2 of the} organosilane.

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 ¹ , dimethyldimethoxysilane and dimethyldiethoxysilane are preferred. Such R ¹ ₂ Si (O
R) The organosilane represented by ₂ may be used alone or in combination of two or more.
The proportion of the component (b) in the composition of the present invention is 0 to 150% by weight, preferably 5 to 100% by weight, more preferably 10 to 60% by weight, based on the component (a).
If the content is more than 10% by weight, the adhesiveness and curability of the obtained coating film are reduced.

(C) Silyl group-containing vinyl resin (c) The silyl group-containing vinyl resin has a main chain composed of a vinyl polymer, and has a hydrolyzable group and / or a terminal or side chain.
Or a polymer containing at least one, preferably two or more silyl groups having a silicon atom bonded to a hydroxyl group, and most of the silyl groups are represented by the following general formula:

[0019]

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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 ⁶ 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).

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

[0022]

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(Where X, R ⁶ and a are the same as those described above;
⁷ is an organic group having a polymerizable double bond), and may be produced by polymerizing a silane compound 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 resin used in the production method shown in (a) is not particularly limited, except for the vinyl resin containing a hydroxyl group. For example, methyl (meth) acrylate, (meth) acryl Ethyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth)
(Meth) acrylic esters such as 2-ethylhexyl acrylate, benzyl (meth) acrylate and cyclohexyl (meth) acrylate; carboxylic acids such as (meth) acrylic acid, itaconic acid and fumaric acid and acid anhydrides such as maleic anhydride An epoxy compound such as glycidyl (meth) acrylate; diethylaminoethyl (meth)
Amino compounds such as acrylate and aminoethyl vinyl ether; (meth) acrylamide, Nt-butyl (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric diamide, maleic diamide, N-butoxymethyl ( Meta)
Amide compounds such as acrylamide; acrylonitrile, styrene, vinyltoluene, α-methylstyrene,
Vinyl chloride, vinyl acetate, vinyl propionate, N-vinyl pyrrolidone,

[0026]

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[0027]

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[0028]

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A vinyl resin 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 at least one fluorine-containing monomer is used as a copolymer monomer. Is particularly preferred.

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

[0031]

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[0032]

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

Preferred examples of the silyl group-containing vinyl resin as described above include, for example, the following general formula:

[0035]

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(Wherein R ⁸ and R ¹⁰ are a hydrogen atom, a fluorine atom or a methyl group, R ⁹ 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.), R ¹¹ 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 to R ¹² are the same as R ⁹ , 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 resin is preferably from 2,000 to 100,00
0, more preferably 4,000 to 50,000.

Specific examples of the silyl group-containing vinyl resin (c) used in the present invention as described above include Kanekazemurak manufactured by Kanegafuchi Chemical Industry Co., Ltd., and the following polymers. However, the present invention is not limited to these.

P-1 methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (90/10:
Weight ratio) P-2 Methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (85/15: weight ratio) P-3 Methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (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 (85/15:
(Weight ratio) P-7 n-butyl methacrylate / styrene / γ-methacryloxypropyltrimethoxysilane (50/35
/ 15: weight ratio) P-8 methyl methacrylate / methyl acrylate /
γ-acryloxypropyltrimethoxysilane (35 /
40/15: 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 (90/10: weight ratio) P -13 FM-4 / 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-methacryloxypropyltrimethoxysilane (30/50/20: weight ratio) P-17 FM-3 / FM-4 / γ-methacryloxypropyltrimethoxy Silane (25/60/15: weight ratio) P-18 FM-4 / 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) (c) The ratio of the silyl group-containing vinyl resin in the composition is as follows:
(a) 2 parts of the organosilane (a ')
%, Preferably from 5 to 200% by weight, more preferably from 10 to 100% by weight. When the amount is less than 2% by weight, the alkali resistance of the resulting coating film is low. This leads to deterioration of the durability of the film.

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
Is a compound of the above (a) to (c). 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.

SP-1 10 g of methyltrimethoxysilane, 5 g of dimethyldimethoxysilane, 2 g of 3,3,3-trifluoropropyltriethoxysilane, 2 g of the above compound P-2 12 g of SP-2 methyltrimethoxysilane, dimethyldiethoxy 8 g of silane, 2 g of 3,3,3-trifluoropropyltriethoxysilane, 2 g of the above compound P-23 g of SP-3 15 g of ethyltriethoxysilane, 5 g of dimethyldiethoxysilane, 2 g of 3,3,3-trifluorobutyltriethoxysilane Compound P-22g SP-4 methyltrimethoxysilane 10g, dimethyldimethoxysilane 5g, 3,3,3-trifluoropropyltriethoxysilane 2g, compound P-21.5g SP-5 methyltrimethoxysilane 10g, dimethyldimethoxysilane Tokishishiran 5g, 3- perfluoroethoxy trimethoxysilane 5g, the compound P-52.5g SP-6 ethyltrimethoxysilane 20 g, 3,3,3-trifluoro-butyl triethoxysilane 7 g, bis (3,
3,3-trifluoropropyl) diethoxysilane 5
g, the above compound P-7 3 g SP-7 tetraethoxysilane 2 g, methyltrimethoxysilane 10 g, dimethyldimethoxysilane 5 g, 3,
3,3-trifluoropropyltriethoxysilane 2
g, the above compound P-2 2.5 g SP-8 cyclohexyltrimethoxysilane 18 g, bis (3,3,3-trifluoropropyl) triethoxysilane 12 g, tetraethoxysilane 3 g, the above compound P-12 5 g SP-9 1. 12 g of methyltrimethoxysilane, 10 g of dimethyldipropoxysilane, 5 g of 3,3,3-trifluoropropyltriethoxysilane, the above compound P-8
5 g SP-10 12 g of methyltriethoxysilane, 5 g of dimethyldimethoxysilane, 5 g of bis (3,3,3-trifluoropropyl) trimethoxysilane, the above compound P-8
4.5g

(D) Metal chelate compound The metal chelate compound (d) of the present invention has the general formula R ³ OH
(Wherein, R ³ represents an alkyl group having 1 to 6 carbon atoms), and R ⁴ COCH ₂ COR ⁵ (wherein,
R ⁴ is an alkyl group having 1 to 6 carbon atoms, and R ⁵ is an alkyl group having 1 to ⁵ carbon atoms.
A diketone represented by an alkyl group or an alkoxy group having 1 to 16 carbon atoms), Zr, Ti,
Any metal having a central metal selected from Al can be suitably used without any particular limitation. In this category, two or more metal chelate compounds may be used in combination.
The (d) metal chelate compound of the present invention has the general formula Zr (OR ³ ) _p1
(R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 and Al
(OR ³ ) _r1 (R ⁴ COCHCOR ⁵ ) A compound selected from the group of compounds represented by _r2 is preferable, and promotes the condensation reaction between the components (a) to (b) and the (c) silyl group-containing vinyl resin. To act.

(D) R in the metal chelate compound^ThreeAnd R
^FourIs an alkyl having 1 to 6 carbon atoms which may be the same or different
Group, specifically ethyl group, n-propyl group, i-pro
Pill group, n-butyl group, sec-butyl group, t-butyl
Group, n-pentyl group, phenyl group and the like. Also, R
^FiveIs an alkyl group having 1 to 6 carbon atoms as described above,
An alkoxy group having 1 to 16 carbon atoms, such as a methoxy group,
Toxic group, n-propoxy group, i-propoxy group, n-
Butoxy group, sec-butoxy group, t-butoxy group, lau
Examples thereof include a luyl group and a stearyl group. (D) Metal sharpness
P in the salt compound ₁~ R_TwoBecomes a tetradentate or hexadentate configuration
Represents an integer determined as follows.

Specific examples of these (d) metal chelate compounds include zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), zirconium n-butoxytris (ethylacetoacetate), Zirconium chelate compounds such as tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetyl) Titanium chelate compounds such as acetate) titanium and diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum Aluminum, aluminum diisopropoxyacetylacetonate, aluminum isopropoxybis (ethylacetoacetate), aluminum isopropoxybis (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), monoacetylacetonate -Aluminum chelate compounds such as bis (ethylacetoacetate) aluminum. Preferred of these (d) metal chelate compounds are
Tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, aluminum diisopropoxyethylacetoacetate, and tris (ethylacetoacetate) aluminum. These (d) metal chelate compounds are:
These can be used alone or in combination of two or more. Further, as the component (d), a partial hydrolyzate of these metal chelate compounds can also be used.

The proportion of the metal chelate compound (d) in the composition is 0.01 to 50% by weight, preferably 0.1 to 50% by weight, based on the (a ') organosilane as the raw material of the component (a). %, More preferably 0.5 to 10% by weight,
If the amount is less than 0.01% by weight, the formation of a copolymer of the components (a) to (b) and the component (c) is insufficient, and the durability of the coating film is deteriorated. In addition, the storage stability of the composition is deteriorated, and cracks may occur in the obtained coating film, which is not preferable.

(E) Organic Solvent (e) The organic solvent mainly mixes the components (a) to (d) uniformly 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 and storage stability of the composition. The (e) organic solvent is not particularly limited as long as it can uniformly mix the components (a) to (d) .Examples include alcohols, aromatic hydrocarbons, ethers, ketones, and esters. Is preferred.

Among them, examples of the alcohols include 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 (e) organic solvents may be used alone or in combination of two or more.
(e) The proportion of the organic solvent in the composition is not particularly limited, and an amount for adjusting the total solid content concentration according to the intended use is used.

Component (f) The component (f) used in the present invention has a general formula R^FourCOCH_TwoCOR^Fiveso
Β-diketones and / or β-ketoesters represented
And acts as a stability improver for the composition of the present invention.
Is what you do. That is, the components (a) to (e) are mainly
(D) metal chelate compound present in the composition
(Zirconium, titanium and / or aluminum
Coordinated to the metal atom in the
(A)-(b) components and / or
Or the effect of accelerating the condensation reaction of component (c) is suppressed.
It is thought to improve the storage stability of the composition
You. (f) R constituting the component^FourAnd R^FiveIs the (d) gold
R of the genus chelate compound ^FourAnd R^FiveSame as
You.

The (f) β-diketones and / or β
-Specific examples of the ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, and acetoacetate. 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 are
One type may be used alone, or two or more types may be used in combination. The (f) β-diketones and / or β-ketoesters are used in an amount of 2 mol or more, preferably 3 to 20 mol, per 1 mol of the metal chelate compound (d). Inferior in stability.

The preferred composition of the present invention is as described above.
Components (a) to (f) are the main components, but usually the component (a) is used when preparing a composition containing the components (a) to (e).
Water is added for hydrolyzing and condensing (a ') the organosilane and / or (b') the diorganosilane constituting the component (b). The amount of water to be used is generally 1.2 to 3.0 mol, preferably 1. mol, per 1 mol of (a ') organosilane.
3 to 2.0 mol, and usually 0.8 to 2.0 mol, preferably 0.9 to 2.0 mol, per 1 mol of (b ') diorganosilane.
It is about 1.5 mol.

The preferred composition of the present invention comprises the above (a)
(f) component, the total solid content of which is 1 to
The content is 50% by weight, preferably 3 to 40% by weight, and if it exceeds 50% by weight, the storage stability of the composition deteriorates, which is not preferable.

Incidentally, colloidal silica can be added to the composition 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.

In addition, the composition of the present invention is separately added to the coating film so as to exhibit various properties such as coloring, imparting irregularities, preventing ultraviolet light transmission to the base, imparting corrosion resistance, and heat resistance. It is also possible to add and disperse a filler. As the filler, for example, organic pigments, non-water-soluble pigments such as inorganic pigments or particles other than pigments, fibrous or flaky metals and alloys and their oxides, hydroxides, carbides, nitrides, Sulfide and the like. 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, shale green, green top, manganese green, pigment green, ultramarine, navy blue, pigment green, rock ultramarine, cobalt blue, cerulean blue, boric acid Copper, molybdenum blue, copper sulfide, cobalt purple, mars purple,
Manganese purple, Pigment violet, Lead suboxide, Calcium plumbate, Zinc yellow, Lead sulfide, Chrome 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, bunchesone white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, etc. be able to.

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
(f) 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. Further, in curing the composition of the present invention faster, a curing accelerator may be used depending on curing conditions, and in order to cure at a relatively low temperature,
It is more effective to use a curing accelerator together.

As such a curing accelerator, naphthenic acid,
Alkali metal salts such as octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; alkyltitanic acid, phosphoric acid, p
-Acidic compounds such as toluenesulfonic acid and phthalic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, metaphenylenediamine, ethanolamine, triethylamine, various types used as curing agents for epoxy resins Modified amine, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-
Amine compounds such as (aminoethyl) -aminopropylmethyldimethoxysilane and γ-anilinopropyltrimethoxysilane, (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OC
OCH = CHCOOCH ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H
₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ ,
(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHC
Carboxylic acid type organotin compounds such as OOC ₈ H ₁₇ ) ₂ and Sn (OCOCC ₈ H ₁₇ ) ₂ ; (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂
(COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn
(SCH ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C
_{8 H 17) 2 Sn (SCH} 2 COOC 12 H 25) 2,

[0059]

Embedded image

A mercaptide-type organotin compound such as

[0061]

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 compounds such as reaction products of organic tin oxides such as ₂ SnO and (C ₈ H ₁₇ ) ₂ SnO with ester compounds such as ethyl silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate are used. . The proportion of these curing accelerators in the composition is usually 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on the solid content of the composition of the present invention.

The composition of the present invention may further contain other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants, other silane coupling agents, titanium coupling agents, and the like. Additives such as dyes, dispersants, thickeners, and leveling agents can also be added.

Further, the composition of the present invention contains (e)
An organic solvent other than an organic solvent can be contained, and such an organic solvent may be any solvent that does not cause precipitation when the components (a) to (d) are mixed. Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ketones, esters, ethers, ketone ethers, ketone esters, ester ethers, etc. used in paints, coating agents, etc. Specific examples thereof include benzene, toluene, xylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and isoamyl acetate.
These organic solvents are generally used in an amount of about 100 parts by weight or less based on 100 parts by weight of the composition of the present invention.

In preparing the composition of the present invention, any method may be used as long as the composition containing the components (a) to (e) is first prepared and the component (f) is added thereto. However, for example, the following preparation methods are preferred. (a) Organosilane constituting component (a), (b) Diorganosilane constituting component (b), (c) vinyl resin containing silyl group, (d) metal chelate compound and (e) organic Hydrolysis is performed by adding 1.2 to 3 mol of water to 1 mol of (a ') organosilane and 0.8 to 2 mol of water to 1 mol of (b') diorganosilane to a solvent solution. A method of performing a condensation reaction to form a composition comprising the components (a) to (e), and then adding (f) β-diketones and / or β-ketoesters.

The (a) organosilane constituting the component (a), the (b ′) diorganosilane constituting the component (b) and
(e) In a solution comprising an organic solvent, (a ') organosilane 1
The hydrolysis / condensation reaction is carried out by adding 1.2 to 3 mol of water per mol and 0.8 to 2 mol of water per mol of (b ') diorganosilane. A method in which a vinyl resin, (d) a metal chelate compound are added and mixed, a condensation reaction is further carried out to form a composition comprising components (a) to (e), and then component (f) is added. (a ′) an organosilane, (b ′) a diorganosilane,
In a solution comprising (d) a metal chelate compound and (e) an organic solvent, (a ') 1.2 to 3 moles of water per 1 mole of organosilane, and (b') 0.1 to 3 moles of diorganosilane. 8 ~
Hydrolysis / condensation reaction is performed by adding 2 mol of water, and then
(c) A method of adding and mixing a silyl group-containing vinyl resin, further performing a condensation reaction to form a composition comprising components (a) to (e), and then adding component (f).

The composition of the present invention is applied to a transparent film or a high or medium refractive index layer by a coating method such as curtain flow coating, dip coating, spin coating, roll coating and the like, and dried at room temperature, or 200
By heating at a temperature of about 1 ° C. for about 1 minute to 100 hours, a low refractive index layer is formed.

The antireflection film of the present invention comprises a low-refractive-index layer (1) formed by coating the above composition, and a low-refractive-index layer (2) having a higher refractive index than the low-refractive-index layer (2). It is preferable that it is formed and composed of two or more layers. 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. 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 above composition is different from the high refractive index layer (2) having a higher refractive index. Formed on top, adjacent to the high refractive index layer (2), opposite the low refractive index layer (1), to the middle refractive index layer (3), and further to the refractive index of the layer (4) (such as a support primer). 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 that 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, particularly 1.75.
The above is preferred. Further, it is preferable that these layers are provided on a support, preferably a transparent film.

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 <n1 d1 <mλ / 4 × 1.3 (1) nλ / 4 × 0.7 <n2 d2 <nλ / 4 × 1.3 (2) In the above equation, m is Positive integer (typically 1, 2, or 3)
And n1 represents the refractive index of the high refractive index layer, d1 represents the layer thickness (nm) of the high refractive index layer, and n is a positive odd number (generally,
1), n2 represents the refractive index of the low refractive index layer, and d2 represents the layer thickness (nm) of the low refractive index layer. The refractive index n1 of the high refractive index layer is generally at least 0.0
5 and the refractive index n2 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. Further, the refractive index n1 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 <n3 d3 <hλ / 4 × 1.3 (3) kλ / 4 × 0.7 <n4 d4 <kλ / 4 × 1.3 (4) jλ / 4 × 0.7 < n5 d5 <jλ / 4 × 1.3 (5) In the above formula, h is a positive integer (generally 1, 2, or 3)
And n3 represents the refractive index of the medium refractive index layer, d3 represents the layer thickness (nm) of the medium refractive index layer, and k is a positive integer (generally,
1, 2 or 3), n4 represents the refractive index of the high refractive index layer, d4 represents the layer thickness (nm) of the high refractive index layer, j represents a positive odd number (generally 1), and n5 Represents the refractive index of the low refractive index layer, and d5 represents the layer thickness (nm) of the low refractive index layer. The refractive index n3 of the middle refractive index layer is generally in the range of 1.5 to 1.7, and the refractive index n4 of the high refractive index layer is generally 1.7 to 1.7.
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 is generally composed of 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 a material for forming a layer having a higher refractive index as described 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 (ie, 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.

[0083]

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 Into a 1-liter three-necked flask equipped with a reflux condenser and a stirrer, 32.4 g of a fluorine monomer FM-4 and 3.6 g of γ-methacryloxypropyltrimethoxysilane were added.
The mixture was heated and stirred at 75 ° C. under a nitrogen stream. 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.)
(Commercially available under the name V-65) and a mixed solution of 4.8 g of methyl ethyl ketone and 25 ml of methyl ethyl ketone.
g of FM-4, 32.4 g of γ-methacryloxypropyltrimethoxysilane, and 19.2 g of V-65 were started to be added dropwise 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 75 ° C. for 4 hours, 280 ml of methyl ethyl ketone was added, and the mixture was cooled to obtain 640 g of a solution of the title P-12. . The solid content was 54.0%, and the polymer obtained had a number average molecular weight in terms of polystyrene of 8,300 as determined by gel permeation chromatography.

(2) Preparation of Low Refractive Index Layer Composition A reactor equipped with a stirrer and a reflux condenser, (a) 100 g of methyltrimethoxysilane, (b) 50 g of dimethyldimethoxysilane, (c) a vinyl resin containing a silyl group (Prepared to a solid content of 50%) 50 g, (d) 20 g (0.07 molar equivalent) of diisopropoxyaluminum ethyl acetoacetate, (e)
After adding and mixing 40 g of i-propanol, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours. After cooling to room temperature, (f) 20 g (0.2 mol equivalent) of acetylacetone was added, and A refractive index layer composition A was obtained. Using the same reactor, compositions BF, X, and Y shown in Table 1 were obtained.

[0086]

[Table 1]

(3) Coating of 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 composition shown in Table 1 above was coated on the high refractive index layer using a wire bar, and dried at 100 ° C. for 1 hour to obtain a low refractive index. A rate layer (layer thickness: 93 nm) was formed. The refractive index of the layer is 1.3-1.5
Was in the range.

(7) Performance Evaluation of Coated Film The first to fourth layers thus obtained were coated, and the film was measured for surface reflectance (average reflectance at a light wavelength of 400 to 800 nm) and film surface strength. Carried out. The film surface strength was rubbed with a fingertip, tissue, eraser, and toe, and observed visually. 0 was rubbed with a fingertip, 1 was rubbed with a tissue, 1 was rubbed with an eraser, and 2 was rubbed with a toe. The sample was marked as "3" and marked as "4" without any damage. The results are shown in Table 2.

[0091]

[Table 2]

As is clear from this example, it is understood that the antireflection film of the present invention has a very low surface reflectivity, 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 or the film strength was insufficient.

(8) (Preparation of Display Device with Antireflection Film Installed) The antireflection films of Examples 1 to 5 and Comparative Example 1 prepared in the above example were obtained from a personal computer PC9821NS / 340W obtained from NEC Corporation. To the surface of the liquid crystal display to create a surface device sample,
The degree of scenery reflection due to the surface reflection was visually evaluated. The display devices provided with the antireflection films of Examples 1 to 5 of the present invention showed almost no reflection of surrounding scenery and showed comfortable visibility, whereas the display devices provided with the film of Comparative Example 1 showed the surroundings. And the visibility was inferior.

[0094]

According to the present invention, a low refractive index layer is formed from a composition obtained by a polycondensation reaction between an organic polymer and an alkoxysilane, and the refractive index of a high refractive index layer adjacent thereto is adjusted to 1.7 or more. By doing so, an inexpensive and large-area antireflection film having good optical characteristics and excellent film strength can be provided 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

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI H01J 29/88 B05D 7/24 302Y // B05D 7/24 302 G02B 1/10 A

Claims (5)

[Claims] (1) The following (a), (b), (c) or (a),
a low refractive index layer (1) formed from a composition at least composed of a hydrolyzate of (c) and / or a partial condensate thereof;
Wherein the composition (a), (b), (c) or the composition (a), (c) is fluorine-containing at least one of (a), (b), (c). An anti-reflection film comprising an atom, wherein a fluorine atom is contained in a repeating unit of the vinyl resin having R ¹ or a silyl group in the general formula. (a) Formula R ¹ Si (OR ² ) ₃ (wherein R ¹ is an organic group having 1 to 10 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms) Organosilane represented by: (b) the general formula _{^{R 1 2 Si (OR 2)}} 2 ( wherein, R ^1, R ² is the (a)
Represents the same substituent as defined in the above, but need not be the same substituent as (a)).
0 to 150% by weight based on (a). (c) a silyl group-containing vinyl polymer resin having 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 the polymer, based on (a); 300% by weight. 2. A composition comprising (a) to (c) described above, and (d) represented by the general formula R ³ OH (where R ³ represents an alkyl group having 1 to 6 carbon atoms). (wherein, R ⁴ is an alkyl group having 1 to 6 carbon atoms, R ⁵ represents an alkyl or alkoxy group having 1 to 16 carbon atoms having 1 to 5 carbon atoms) alcohol and R ⁴ COCH ₂ COR ⁵ is represented by At least one metal chelate compound having a metal selected from Zr, Ti, and Al as a central metal having a diketone as a ligand, 0.01 to 50% by weight based on (a);
(e) an organic solvent, (f) a β-diketone and / or β-ketoester represented by the general formula R ⁴ COCH ₂ COR ⁵ (wherein R ⁴ and R ⁵ are the same as described above), as (d) 2. The antireflection film according to claim 1, wherein 2 mol or more is added to 1 mol of the metal chelate compound. 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).
(1) has a layer (3) on the opposite side, and further has a layer (4), wherein the layer (3) has a refractive index of the layer (4) and a refractive index of the high refractive index layer (2). The antireflection film according to any one of claims 1 to 3, wherein the antireflection film has an intermediate refractive index. 5. A display device comprising the antireflection film according to claim 1.