JP2001040284A - Antireflection film and display apparatus provided with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a large amount of an antireflection film of large area showing a uniformly low reflectivity (<=1% reflectivity) in a wide temperature range, capable of having both film strength and brittleness, having excellent durability at a low cost. SOLUTION: In this antireflection film having a low refractive index layer formed by coating a substrate with a composition containing a hydrolytic partial condensation product of an organosilane such as an alkoxysilane, etc., the layer having a low-refractive index is formed by promotion of curing by irradiation with energy rays such as electron beam, etc., after or simultaneously with the coating with the composition to give the objective antireflection film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

Conventionally, as an antireflection film of a wide wavelength range / low reflectance having a performance capable of covering the entire wavelength range of visible light, a transparent thin film of a metal oxide such as magnesium fluoride or silicon dioxide is formed by a method such as vapor deposition. Laminated multilayer films have been used. In accordance with the relationship between the refractive index and the film thickness of each layer, which is optimally designed in advance, it is necessary to perform the operation of controlling the film thickness with high precision many times, which is very expensive. In addition, it is difficult to obtain a film having a large area, and it is not suitable for mass production.

On the other hand, an antireflection film by a coating method is also being developed, but the problem is how to lower the refractive index of the uppermost layer (the air-side interface) of the film and enhance the physical characteristics of the film. There is.

[0005] JP-B-6-98703, JP-A-63-2
No. 1601 discloses a technique for applying a composition comprising a hydrolyzed partial condensate of an alkoxysilane compound to the surface of a plastic substrate to reduce reflected light. Japanese Patent Application Laid-Open No. 5-13021 discloses an antireflection film having two layers using ultrafine particles having MgF ₂ and SiO ₂ dispersed in ethyl silicate. However, the antireflection technology described in these publications has a small refractive index difference from the base material, and has an insufficient antireflection effect. In addition, the film becomes brittle and cracks when the antireflection function is provided on a flexible film. It has problems such as easy handling and difficult handling. In addition, if a heat treatment is applied to promote the curing reaction sufficiently for the purpose of improving the physical properties of the film, the deformation of the plastic support proceeds and good flatness cannot be maintained, so that an antireflection film having uniform optical performance cannot be obtained. It contained the fatal problem of saying.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an antireflection film having a low reflectance (reflectance of 1% or less) uniformly over a wide wavelength range and having excellent durability capable of achieving both film strength and brittleness. It is an object of the present invention to provide a membrane at a low cost in a method suitable for mass production and large-area production. Another object of the present invention is to provide a display device provided with the antireflection film.

[0007]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is as follows.
In an antireflection film having a low-refractive-index layer formed by applying a composition containing a hydrolyzed partial condensate of an organosilane, the low-refractive-index layer is applied after the application of the composition or the application of the composition. At the same time, it was achieved by an anti-reflection film characterized by being formed by accelerating curing by irradiation with energy rays.

[0008] Preferred embodiments of the antireflection film of the present invention are described below, but the present invention is not limited thereto. (1) In an antireflection film having a low refractive index layer formed by coating a composition containing a hydrolyzed partial condensate of an organosilane on a support, the low refractive index layer is coated with the composition. An antireflection film formed by accelerating the curing by irradiating energy rays later or simultaneously with the application of the composition. (2) The antireflection film according to item 1, wherein the energy beam is an electron beam or a microwave. (3) The antireflection film according to item 1 or 2, wherein the organosilane is an alkoxysilane. (4) The low refractive index layer is formed by coating a composition comprising a hydrolyzed partial condensate of a mixture containing 1 to 200% by weight of a silyl group-containing polymer with respect to organosilane. Item 4. The antireflection film according to Item 1 to Item 3. (5) The antireflection film according to any one of Items 1 to 4, wherein at least one of the organosilanes contains a fluorine atom. (6) The low refractive index layer and a refractive index adjacent thereto are 1.7.
Item 1 comprising the high refractive index layer described above.
Item 6. The antireflection film according to item 5. (7) a layer adjacent to the high-refractive-index layer and opposite to the low-refractive-index layer, and further having a layer adjacent to the layer and opposite to the layer and having a refractive index of 1.6 or less. 7. The antireflection film according to claim 1, wherein the layer has a refractive index between the refractive index of the layer and the refractive index of the high refractive index layer. (8) A display device comprising the antireflection film according to any one of Items 1 to 7.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a low refractive index layer formed by coating a composition containing a hydrolyzed partial condensate of an organosilane (hereinafter referred to as a sol solution in the present invention). It is characterized in that it is a low-refractive-index layer formed by accelerating the curing by irradiation with an energy beam, particularly an electron beam or a microwave after or simultaneously with the application of the sol liquid.
The constituent features of the present invention will be described in detail.

(A) Organosilane Organosilane represents a silane compound having at least one functional group capable of providing a silanol by hydrolysis in a molecule.
It becomes a hydrolyzate and / or a partial condensate obtained by condensation and functions as a binder in the composition. Generally, a compound represented by the formula (R) ₄ Si is preferably used. In the formula, R represents a hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, which may have a substituent), an alkoxyl group, an oxyacyl group, or a halogen atom. The four Rs in one molecule may be the same or different from each other as long as they fall within this definition, and can be freely combined and selected. Preferably, two or less hydrocarbon groups are simultaneously present in one molecule.

Among these organosilanes, alkoxy
Silanes are more preferably used. Particularly preferred compounds
Is represented by the general formula Si (OR¹)_x(R^Two)_4-xArco represented by
Xysilane. R in such an alkoxysilane
¹Is an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 4 carbon atoms.
Acyl groups are preferred, for example, methyl, ethyl, n-
Propyl group, i-propyl group, n-butyl group, sec-butyl
Tert-butyl group, acetyl group and the like.
Also, R^TwoIs preferably an organic group having 1 to 10 carbon atoms.
For example, methyl, ethyl, n-propyl, i-propyl
Group, n-butyl group, tert-butyl group, n-hexyl
Group, cyclohexyl group, n-octyl group, tert-
Octyl group, n-decyl group, phenyl, vinyl group, ant
Unsubstituted hydrocarbon groups such as
Group, CF_ThreeCH_Two-, CF_ThreeCH_TwoCH_Two-, C_TwoF_FiveCH_TwoCH_Two-, C_ThreeF₇CH_TwoCH_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-
(Perfluorocyclohexyloxy) propyl, H (CF
_Two)_FourCH_TwoOCH_TwoCH_TwoCH_Two-, H (CF_Two)_FourCH_TwoCH_TwoCH_Two-, Γ-glycid
Xypropyl group, γ-mercaptopropyl group, 3,4-
Epoxycyclohexylethyl group, γ-methacryloyl
And substituted hydrocarbon groups such as oxypropyl groups.
x is preferably an integer of 2 to 4.

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

When x = 3 (hereinafter referred to as trifunctional organosilane), methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyl Triethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane,
γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltri Ethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₂ F ₅ CH
₂ CH ₂ Si (OCH ₃ ) ₃ , C ₂ F ₅ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₃ F ₇ OCH ₂ CH
₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CF ₃ ) ₂ CHOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₄ F ₉ C
H ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH
_{3) 3,} 3- (perfluoro-cyclohexyloxy) can be mentioned trimethoxysilane, and the like.

X = 2 (hereinafter bifunctional organosilane)
Dimethyldimethoxysilane, dimethyl
Rudiethoxysilane, methylphenyldimethoxysila
, Diethyldimethoxysilane, diethyldiethoxy
Orchid, di-n-propyldimethoxysilane, di-n-propyl
Ropirdiethoxysilane, di-i-propyldimethoxy
Silane, di-i-propyldiethoxysilane, diphenyl
Rudimethoxysilane, divinyldiethoxysilane, (CF_Three
CH_TwoCH_Two)_TwoSi (OCH_Three)_Two, (C_ThreeF₇OCH_TwoCH_TwoCH_Two)_TwoSi (OCH_Three) _Two, [H
(CF_Two)₆CH_TwoOCH_TwoCH_TwoCH_Two]_TwoSi (OCH_Three)_Two, (C_TwoF_FiveCH_TwoCH_Two)_TwoSi (O
CH_Three)_TwoAnd so on.

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

The above-mentioned organosilanes may be used alone or in combination of two or more. When two or more of the above-mentioned organosilanes are used in combination, the proportion of the bifunctional organosilane in the composition of the present invention is 0 with respect to the tetrafunctional organosilane and the trifunctional organosilane component.
The amount is from 150 to 150% by weight, preferably from 5 to 100% by weight, more preferably from 10 to 60% by weight.

The low refractive index layer of the present invention is formed by applying and curing a composition containing an organosilane as a main component prepared by the above method. The essential components in this coating solution are none other than the above-mentioned (a) organosilane compound which forms a network structure. Further, in addition to these organosilanes, various compounds can be added to the composition of the present invention as needed. These compounds can be roughly classified into the following components (b) to (h) according to the purpose. (b) Silyl group-containing polymer (c) Hydrolysis / condensation catalyst (sol-gel catalyst) (d) Solvent (e) Chelating ligand compound (f) Water (g) Filler (h) Other additives

Hereinafter, each additive used together will be described in detail. (b) Silyl group-containing polymer The silyl group-containing polymer is composed of a main chain polymer, and has at least one silyl group having a hydrolyzable group and / or a silicon atom bonded to a hydroxyl group at a terminal or a side chain in one molecule of the polymer. One, preferably two or more, and the preferred structure of the silyl group is 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 ³ is a hydrogen atom; An alkyl group having 10 to 10 or an aralkyl group having 7 to 10 carbon atoms,
3 is an integer of 3).

Particularly preferred as the silyl group-containing polymer is a silyl group-containing vinyl polymer whose main chain is composed of a vinyl polymer. These can generally be easily synthesized by the following method. The manufacturing method is not limited to these methods.

(A) A hydrosilane compound is reacted with a vinyl polymer having a carbon-carbon double bond. (B) The following general formula

[0023]

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(Where X, R ³ and a are the same as those described above, and R ⁴
Is an organic group having a polymerizable double bond) and various vinyl compounds.

Here, as the hydrosilane compound used in the production method shown in (a), for example, 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,

[0027]

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[0028]

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A vinyl polymer obtained by copolymerizing a vinyl compound selected from the group consisting of a monomer having a double bond in the 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.

[0031]

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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:

[0034]

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(Wherein R ⁵ and R ⁷ are a hydrogen atom, a fluorine atom or a methyl group, R ⁶ is a hydrogen atom and 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
R ⁸ represents a methylene group, an ethylene group, or a fluorine atom-containing alkyl group described in the component (a), such as ₂ F ₅ CH ₂ CH ₂ —.
R ⁹ is an alkylene group having 1 to 4 carbon atoms such as a propylene group and a butylene group, and has the same meaning as R ¹ , and n / (m + n)
= 0.01 to 0.4, and preferably 0.02 to 0.2). The number average molecular weight of the silyl group-containing vinyl polymer is preferably from 2,000 to 100,000.
And more preferably 4,000 to 50,000.

Specific examples of the silyl group-containing vinyl polymer preferably used in the present invention include Kanebuchi Chemical Industry Co., Ltd.
Manufactured by Kanekazemurak and the following polymers, but are not limited thereto.

P-1 methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (85/15:
(Weight ratio) P-2 methyl methacrylate / γ-acryloxypropyltrimethoxysilane (75/25: weight ratio) P-3 methyl methacrylate / ethyl acrylate /
γ-methacryloxypropyltrimethoxysilane (45
/ 45/10: weight ratio) P-4 methyl methacrylate / methyl acrylate /
γ-acryloxypropyltrimethoxysilane (50 /
35/15: weight ratio) P-5 FM-1 / γ-methacryloxypropyltrimethoxysilane (85/15: weight ratio)

P-6 FM-4 / γ-methacryloxypropyltrimethoxysilane (85/15: weight ratio) P-7 FM-4 / FM-7 / γ-methacryloxypropyltrimethoxysilane (50/40 / 10: weight ratio) P-8 FM-4 / methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (70/22/8: weight ratio) P-9 FM-7 / methyl methacrylate / γ-acryloxypropyl trimethoxy Silane (65/25/10: weight ratio)

The proportion of the silyl group-containing limer in the composition is 1 to 200% by weight, preferably 3 to 100% by weight, more preferably 5 to 50% by weight, based on the total organosilane used.

Preferred combinations of the above-mentioned components (a) and (b) in the present invention are illustrated below and in the examples. The mixing ratio indicates the weight (g) of each compound used. In the present invention, in the following description, the above-mentioned coating composition of the hydrolysis / partial condensate of an organosilane is referred to as “sol liquid”, and the hydrolysis / partial condensation reaction of the organosilane is referred to as “sol-gelation”. ". In the sol-gelation, the component (a) is an essential component, and the component (b) may be used by coexisting at the time of the sol-gelation or may be added to the prepared sol solution.

SP-1 10 g of trifluoropropyltrimethoxysilane, hydrolyzed / partially condensed product of 10 g of tetraethoxysilane SP-2 10 g of trifluoropropyltrimethoxysilane, 2 g of tetraethoxysilane, methyltrimethoxysilane
Hydrolysis / partial condensate of 3 g SP-3 tetraethoxysilane 10 g, trifluoropropyltrimethoxysilane 10 g, bis (trifluoropropyl) dimethoxysilane 10 g, hydrolysis / partial condensate SP-4 5 g of tetraethoxysilane Hydrolysis / partial condensate of 3 g of fluoropropyltrimethoxysilane 10 g, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane SP-5 5 g of tetraethoxysilane, 10 g of trifluoropropyltrimethoxysilane, 10 g of bis (trifluoropropyl ) Hydrolysis and partial condensate of 10 g of dimethoxysilane, 3 g of methyltrimethoxysilane and 3 g of dimethyldimethoxysilane

15 g of SP-6 trifluoropropyltrimethoxysilane, 3 g of tetraethoxysilane, a hydrolyzed / partially condensed product of 2 g of the above P-6 SP-7 15 g of trifluoropropyltrimethoxysilane, 5 g of divinyldimethoxysilane, 5 g of the above P- 6 5 g of hydrolysis and partial condensate SP-8 10 g of trifluoropropyltrimethoxysilane, 5 g of hydrolysis and partial condensate of vinyltrimethoxysilane and 1 g of 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane Hydrolysis of 7 g of P-6, partial condensate SP-9 7 g of tetraethoxysilane, 10 g of pentafluorobutyltrimethoxysilane, hydrolysis of 3 g of the above compound P-6, 5 g of partial condensate SP-10 5 g of tetraethoxysilane, bis (Trifluoropropyl) diethoxy 12 g of silane, compound P-4
3g hydrolysis, partial condensate

(C) Sol-gel catalyst Various catalyst compounds can be preferably used in the sol solution of the present invention for the purpose of promoting the hydrolysis / partial condensation reaction of organosilanes. The catalyst used is not particularly limited, and an appropriate amount may be used according to the constituent components of the sol liquid used. Generally, the following compounds (c1) to (c5) are effective, and a desired compound can be added in a required amount from these compounds. In addition, two or more of these groups can be appropriately selected and used together within a range in which mutual promoting effects are not inhibited.

(C1) Organic or inorganic acid As the inorganic acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid,
Organic acid compounds such as sulfurous acid, nitric acid, nitrous acid, phosphoric acid, and phosphorous acid include carboxylic acids (formic acid, acetic acid, propionic acid,
Butyric acid, succinic acid, cyclohexanecarboxylic acid, octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid, benzoic acid, pentafluorobenzoic acid, phthalic acid, etc., sulfonic acids (methane) Sulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid
Phosphonic acids (dimethylphosphoric acid ester, phenylphosphonic acid, etc.), Lewis acids (boron trifluoride etherate, scandium triflate, alkyltitanic acid, aluminate, etc.), and heteropolyacids (phosphomolybdic acid, phosphotungstic acid, etc.) Can be.

(C2) Organic or inorganic base As the inorganic base, sodium hydroxide, potassium hydroxide,
Examples of organic base compounds such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and ammonia include amines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, triethylamine, dibutylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine , Ethanolamine, diazabicycloundecene, quinuclidine, aniline, pyridine, etc.), phosphines (triphenylphosphine, trimethylphosphine, etc.), and metal alkoxides (sodium methylate, potassium ethylate, etc.).

(C3) Metal chelate compound An alcohol represented by the general formula R ¹⁰ OH (where R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms) and R ¹¹ COCH ₂ C
OR ¹² (wherein, R ¹¹ is an alkyl group having 1 to 6 carbon atoms, R ¹²
Represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 16 carbon atoms), as long as the ligand is a diketone and the metal is the central metal. Can be. In this category, two or more metal chelate compounds may be used in combination. Particularly preferred as the metal chelate compound of the present invention is that the central metal has A
l, Ti, and Zr, and has the general formula Zr (OR ¹⁰ )
_p1 (R ¹¹ COCHCOR ¹² ) _p2 , Ti (OR ¹⁰ ) _q1 (R ¹¹ COCHCOR ¹² ) _q2 and Al (OR ¹⁰ ) _r1 (R ¹¹ COCHCOR ¹² ) _r2 (R ¹¹ COCHCOR ¹² ) Acts to promote the condensation reaction of components (a) and (b).

R ¹⁰ and R in the metal chelate compound
¹¹ may be the same or different and may be an alkyl group having 1 to 6 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, Examples include an n-pentyl group and a phenyl group. Also, R
¹² is, in addition to the same alkyl group having 1 to 6 carbon atoms described above,
An alkoxy group having 1 to 16 carbon atoms, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-
Butoxy, sec-butoxy, t-butoxy, lauryl, stearyl and the like. Further, p _{1 to} r ₂ in the metal chelate compound represent an integer determined so as to be tetradentate or hexadentate.

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

(C4) Organometallic Compound The preferred organometallic compound is not particularly limited, but an organic transition metal is preferred because of its high activity. Among them, tin compounds are particularly preferable because of their high stability and activity. Specific examples of these compounds include (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ and (C ₄ H ₉ ) ₂ Sn (O
COCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂
Carboxylic organotin compounds such as Sn (OCOCH = CHCOOC ₄ H ₉ ) 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 CH 2 COOC
_{8 H 17) 2, (C} 8 H 17) 2 Sn (SCH 2 COOC 12 H 25) 2,

[0050]

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Mercaptide-type and 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.

(C5) Metal Salts As the metal salts, alkali metal salts of organic acids (eg, sodium naphthenate, potassium naphthenate, sodium octanoate, sodium 2-ethylhexanoate, potassium laurate, etc.) are preferably used.

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

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

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

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.

(E) Chelate Ligand Compound When a metal complex compound is used in the sol solution, it is preferable to use a compound having chelate coordination ability from the viewpoint of controlling the curing reaction rate and improving the liquid stability. As those used preferably represented by the general formula R ¹⁰ COCH ₂ COR ¹¹ is a β- diketones and / or β- ketoesters, it is to act as a stability improver of the composition of the present invention. That is, by coordinating to a metal atom in a metal chelate compound (preferably zirconium, titanium and / or aluminum compound) present in the accelerating solution, the components (a) and (b) of these metal chelate compounds are It is considered that the effect of accelerating the condensation reaction is suppressed and the curing rate of the obtained film is controlled. R ¹⁰ and R
¹¹ represents R ¹⁰ and R constituting the metal chelate compound
Synonymous with ¹¹ , but need not have the same structure for use.

Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, 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 used in an amount of 2 mol or more, preferably 3 to 20 mol, per mol of the metal chelate compound, and when less than 2 mol, the storage stability of the obtained composition is inferior. Become.

(F) Water To the preferred sol solution of the present invention, water is added for the hydrolysis / condensation reaction of the components (a) and (b). The amount of water used is usually 1.2 moles per mole of the components (a) and (b).
About 3.0 mol, preferably about 1.3 to 2.0 mol. The preferred sol solution of the present invention has a total solid content of 0.1 to 50% by weight, preferably 1 to 40% by weight, and if it exceeds 50% by weight, the storage stability of the composition deteriorates. Not preferred.

(G) Filler Colloidal silica can be added to the sol solution of the present invention for the purpose of improving the hardness of the resulting coating film. Examples of 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 unevenness, preventing UV transmission to the base, 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 about 10 to 300 parts by weight based on 100 parts by weight of the total solid content of the sol liquid.

(H) 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 silane cups. Additives such as a ring agent, a titanium coupling agent, a dye, a dispersant, a thickener, and a leveling agent can also be added.

Further, the sol solution of the present invention may contain a solvent other than the above-mentioned solvents, and such a solvent does not cause precipitation when the above-mentioned components (a) to (c) are mixed. Any solvent can be used, including general paints,
Examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ketones, esters, ethers, ketone ethers, ketone esters, and ester ethers used in coating agents and the like. ,
Specific examples thereof include benzene, toluene, xylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and isoamyl acetate. These organic solvents are
Usually, about 100 parts by weight or less is used per 100 parts by weight of the composition of the present invention.

In preparing the sol solution of the present invention, any method may be used as long as it is a method in which water is added to the composition containing the above components (a) and (b) to hydrolyze the composition. At this time, if necessary, a catalyst may be used to promote the hydrolysis. The amount of the catalyst to be used is not particularly limited as long as the stability of the solution over time is not impaired. For example, the following preparation methods are preferred.

A solution containing the components (a) and (b), a solvent and a hydrolysis catalyst is added in an amount of 0.1 to 1 mol of the organosilane.
A method of performing hydrolysis / condensation reaction by adding 2-3 mol of water. (a) Organosilanes 1 in a solution comprising component and solvent
A method of adding 0.2 to 3 moles of water to the moles to carry out a hydrolysis / condensation reaction, and then adding a hydrolysis catalyst and, if necessary, the component (b). To a solution comprising the component (a), 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, and then the component (b) is added and mixed. And further performing a condensation reaction.

The sol solution of the present invention is subjected to curtain flow coating,
Apply to a transparent film, a high refractive index layer or a medium refractive index layer, etc. by a coating method such as dip coating, spin coating, roll coating, etc., and dry at room temperature, or 30 to 2
By heating at a temperature of about 00 ° C. for about 1 minute to 100 hours, a low refractive index layer is formed.

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

The purpose of the energy ray irradiation of the present invention is to promote the curing of the film caused by the condensation reaction of silanol or alkoxysilane in the sol solution, and the type of the irradiation ray is not particularly limited. In consideration of the influence on the denaturation of the support, irradiation with an electron beam or microwave can be particularly preferably used. Irradiation intensity is 30 mJ / cm ²
To 500 mJ / cm ² , particularly preferably 50 mJ / cm ^2.
mJ / cm ² to 400 mJ / cm ² . The irradiation temperature can be adopted without limitation between room temperature and the deformation temperature of the support, and is preferably 25 ° C to 150 ° C, particularly preferably 50 ° C to 130 ° C.

The antireflection film of the present invention comprises a low-refractive-index layer formed by applying the composition according to the above-described method and a high-refractive-index layer having a higher refractive index formed thereon. 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,
In particular, 1.75 or more is preferable. 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 formed by applying the composition by the above method is formed on the high refractive index layer having a higher refractive index. ,
A medium refractive index layer is adjacent to the high refractive index layer and opposite the low refractive index layer, and further has a medium refractive index having a refractive index intermediate between the refractive index of the layer (such as a base coat for the support) and the refractive index of the high refractive index layer. It is particularly preferable that it is composed of four layers in which a high refractive index layer is formed on the 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. Further, it is preferable that these layers are provided on a support, preferably a transparent film.

The thickness of each layer is 50 to 20
0 nm, layer 50-200 nm, layer 50-200 nm,
The layer is preferably 1 μm to 100 μm, more preferably the layer is 60 to 150 nm, the layer is 50 to 150 nm, the layer is 60 to 150 nm, the layer is 5 to 20 μm, particularly preferably the layer is 60 to 120 nm, and the layer is 50 to 100 nm. The layer is 60-120 nm and the layer is 5-10 μm. The layer preferably has a refractive index of 1.60 or less, and the layer preferably has an intermediate refractive index between the layers.

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)
And 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. Refractive index n of high refractive index layer
₁ is generally at least 0.05 higher than that of the transparent film, and the refractive index n ₂ of the low refractive index layer is generally at least 0.05 lower than at least 0.1 lower, transparent film than the refractive index of the high refractive index layer. 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,
For example, it is described 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 medium, 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, 1, 2).
2 or 3), and n ₄ represents the refractive index of the high refractive index layer;
d ₄ represents a thickness of the high refractive index layer (nm), j is (generally 1) a positive odd number represent, n ₅ represents a refractive index of the low refractive index layer, and d ₅ low refractive index layer Represents the layer thickness (nm). 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 from 1.7 to 2.
2 range.

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

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

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

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

[0086]

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

Example 1 Preparation and Evaluation of Antireflection Film (1) Preparation of Silyl Group-Containing Vinyl Resin (P-6) Fluorine monomer FM-4 was placed in a 1-liter three-necked flask equipped with a reflux condenser and a stirrer. 17 g, γ-methacryloxypropyltrimethoxysilane 3 g, and methyl ethyl ketone 30 ml were added, and the mixture was heated and stirred at 80 ° C. under a nitrogen stream. 2,2'-azobis (2,4-dimethylvaleronitrile) (commercially available under the name V-65 from Wako Pure Chemical Industries, Ltd.)
A solution of 1.2 g in 25 ml of methyl ethyl ketone was added, and at the same time, 255 g of FM-4 and 45 g of γ-
Dropping of a solution in which 12 g of V-65 was dissolved in a mixture of methacryloxypropyltrimethoxysilane was started, and thereafter the entire amount was dropped at a constant speed over 6 hours. After completion of dropping, 2.
A solution obtained by dissolving 4 g of V-65 in 25 ml of methyl ethyl ketone was added, and the mixture was further heated and stirred at 80 ° C. for 4 hours.
By adding 280 ml of methyl ethyl ketone and cooling, 607 g of a solution of the title P-6 was obtained. The solids content is 53.
6%, the number average molecular weight of the obtained polymer was 1 in terms of polystyrene by gel permeation chromatography.
0200.

(2) Preparation of Sol Liquid for Low Refractive Index Layer In a reactor equipped with a stirrer and a reflux condenser, 10 g of trifluoropropyltrimethoxysilane, 10 g of tetraethoxysilane and 20 g of ethanol were added and mixed. After adding 10 g and reacting at 50 ° C. for 30 minutes, the mixture was cooled to room temperature to obtain a sol liquid A for a low refractive index layer. Table 1 shows a similar reaction in which the components added as necessary were changed.
The sol liquids B to H belonging to the present invention shown in the following were obtained.

[0089]

[Table 1]

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

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

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

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

(7) Preparation of anti-reflection film An 80 μm-thick triacetyl cellulose film (T
AC-TD80U, manufactured by Fuji Photo Film Co., Ltd.)
A gelatin subbing layer was provided. On the gelatin undercoat layer,
The coating solution for the hard coat layer is applied using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays.
The coating layer was cured to form a hard coat layer having a thickness of 6.5 μm. The coating liquid for a medium refractive index layer is applied on the hard coat layer using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays to cure the coating layer, thereby forming a medium refractive index layer (refractive index: 1.72, thickness: 0.081 μm). The coating liquid for a high refractive index layer is applied on the medium refractive index layer using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays to cure the coating layer, and the high refractive index layer (refractive index :
1.92, thickness: 0.053 μm). The coating liquid for a low refractive index layer was applied on the high refractive index layer using a bar coater, dried at 100 ° C.
The coating layer was cured by irradiating it for 0 second to form a low refractive index layer (refractive index: 1.39, thickness: 0.069 μm), and an antireflection film sample 1 (the present invention) was obtained.

The sol solutions B to H of the present invention shown in Table 1 were applied as a fourth layer to a thickness of 0.07 μm on the film coated up to the third layer in the same manner as in the above example, and dried. Thereafter, the film is cured by irradiating with an electron beam or a microwave, and anti-reflection film samples 2 to 8 (the present invention) are irradiated with a non-irradiated film W, an ultraviolet-irradiated film X, and a visible light as shown in Table 2 as comparative examples. Film Y, heat treated film Z
Was prepared.

(8) Performance Evaluation of Coated Films Films 1 to 8 obtained by coating the first to fourth layers thus obtained.
The following performance evaluations were carried out for W and Z.

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

[0098]

[Table 2]

As is apparent from this example, it is understood that the antireflection film of the present invention has a very low surface reflectance, a wide wavelength range, and a sufficiently strong film strength. Further, the fingerprint trace could be easily erased by wiping off the tissue, and the stain resistance was excellent. On the other hand, in the comparative example, although a reduction in surface reflectance was recognized, it was impossible to achieve compatibility with film strength, surface stain prevention performance, wiping properties, and flatness.

(Example 2) Preparation and evaluation of a display device provided with an antireflection film The antireflection films 1 to 5 of the present invention prepared in Example 1 above.
Sample Nos. 8 and Comparative Films W to Z were attached to the surface of a liquid crystal display of a personal computer PC9821NS / 340W manufactured by NEC Corporation to prepare a surface device sample, and the degree of scenery reflection due to surface reflection was visually evaluated. The display device provided with the antireflection films 1 to 8 of the present invention showed little visibility of the surrounding scenery, showed comfortable visibility and had sufficient surface strength, while the comparative films W to Z Although the display device provided with, the reflection of the surroundings was reduced, the surface strength and the flatness were extremely poor.

[0101]

According to the present invention, in forming a low refractive index layer by coating a composition containing a hydrolyzed partial condensate of an organosilane, an energy ray is irradiated after or simultaneously with the application of the composition. To form a low-refractive-index layer, and by setting the refractive index of the layer immediately below the low-refractive-index layer to 1.7 or more, a large-area antireflection film having excellent optical properties, film strength, and brittleness can be obtained at low cost. It 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 (primer layer, hard coat layer)

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H091 FA37X FB02 FB12 FC01 FC23 FD06 KA01 LA12 2K009 AA02 AA05 AA06 AA15 BB28 CC03 CC24 CC37 CC42 DD02 DD05 DD06 4J038 CL002 DL021 DL031 DL071 GA12 NA19 PA17

Claims (6)

[Claims] 1. An anti-reflection film having a low refractive index layer formed by coating a composition containing a hydrolyzed partial condensate of an organosilane on a support, wherein the low refractive index layer is formed of the composition. An anti-reflection film formed by accelerating the curing by irradiating an energy ray after application of the composition or simultaneously with application of the composition. 2. The antireflection film according to claim 1, wherein said energy beam is an electron beam or a microwave. 3. The anti-reflection coating according to claim 1, wherein said organosilane is an alkoxysilane. 4. The low refractive index layer is formed by coating a composition comprising a hydrolyzed partial condensate of a mixture containing 1 to 200% by weight of a silyl group-containing polymer with respect to organosilane. 4. The anti-reflection film according to claim 1, wherein: 5. The method according to claim 1, wherein at least one of said organosilanes contains a fluorine atom.
2. The antireflection film according to 1. 6. A display device comprising the antireflection film according to claim 1.