JPH11202102A - Antireflection film and display device arranged therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film which exhibits uniformly low reflectivity (reflectivity <=1%) in a wide wavelength region and is simultaneously excellent in film strength, heat resistance and production suitability. SOLUTION: This antireflection film is formed by applying a compsn. contg. a compd. to accelerate a curing reaction after coating application of a compsn. contg. the hydrolyzate of organosilanes and/or their partial condensate or simultaneously with the coating application of the compsn. In such a case, the antireflection film consists of a low refractive index layer 11 and a high refractive index layer 12 having a refractive index of >=1.7 adjacently thereto.

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.

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

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

Also, Japanese Patent Publication No. Hei 6-98703,
Japanese Patent Application Laid-Open No. 3-21601 discloses a technique for reducing the reflected light by applying a composition comprising a hydrolyzed partial condensate of an alkoxysilane compound to the surface of a plastic substrate. However, the antireflection techniques described in these publications cannot obtain a sufficient antireflection effect because the difference in refractive index from the substrate is small, and the stability over time of the composition to be applied is insufficient,
The liquid increased in viscosity and hardened in several hours, and was not suitable for producing an antireflection film by continuous coating.

[0009]

SUMMARY OF THE INVENTION 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, stain resistance, and heat resistance. Another object of the present invention is to provide an antireflection film having excellent coating stability and excellent stability over time of the coating composition at low cost by a method suitable for mass production in a large area. Another object of the present invention is to provide a display device provided with the antireflection film.

[0010]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is as follows.
Achieved by: An antireflection film having a low refractive index layer formed by coating a composition containing a hydrolyzate of an organosilane and / or a partial condensate thereof, wherein the low refractive index layer is coated with the composition. An antireflection film formed by applying a composition containing a compound that promotes a curing reaction later or simultaneously with the application of the composition.

The antireflection film of the present invention is more preferable.
The embodiments are as follows, and the antireflection film of the present invention is
The display devices arranged are as follows. When the low refractive index layer is (a)¹)_Four(Where R¹Is charcoal
An alkyl group having 1 to 5 primes or an acyl group having 1 to 4 carbons
Represents an alkoxysilane) and / or
(b) General formula R^TwoSi (OR^Three)_Three(Where R^TwoHas 1 to 10 carbon atoms
Represents an alkyl group or an aryl group;^ThreeIs R¹To
An organosilane represented by the following formula:
Or (c) the general formula R^Four _TwoSi (OR^Five)_Two(Where R^FourIs R^Two
A group synonymous with R^FiveIs R¹Represents a synonymous group)
Hydrolyzate of organosilane and / or part thereof
It is formed by applying a composition containing a polycondensate
The antireflection film according to any one of the preceding claims. The low-refractive index layer has the following (a) with respect to (d): 0 to 100 times
%, (B) from 0 to 200% by weight, (c) from 0 to 200% by weight
% And (a) to (c) cannot be 0 at the same time.
Hydrolyzate and / or partial condensate of the composition
Low refractive index layer formed by applying a composition composed of
The antireflection film according to any one of the preceding claims. (a) General formula Si (OR¹)_Four(Where R¹Is an alkyl having 1 to 5 carbon atoms
Represents a kill group or an acyl group having 1 to 4 carbon atoms)
Alkoxysilane (b) Formula R^TwoSi (OR^Three)_Three(Where R^TwoHas 1 to 10 carbon atoms
Organic group, R^ThreeIs R ¹Represents a synonymous group)
Organosilane (c) General formula R^Four _TwoSi (OR^Five)_Two(Where R^FourIs R^TwoSynonymous with
Group of R^FiveIs R¹Represents a synonymous group)
Luganosilane (d) Hydrolyzable group and / or water at the terminal or side chain
A silyl group having a silicon atom bonded to an acid group in the polymer
Silyl group-containing vinyl polymer having at least one compound which promotes the curing reaction is represented by the following (e) to (h).
At least one compound selected from the group consisting of
Or the anti-reflection described in
film. (e) Inorganic or organic acid compound (f) Inorganic or organic base compound (g) Metal complex compound (h) Organometallic compound (i) Metal salt Refractive index adjacent to the low refractive index layer (1) Is 1.7
Characterized by comprising a high refractive index layer (2) as described above.
An antireflection film according to any one of the above. Adjacent to the high refractive index layer (2) and opposite to the low refractive index layer (1)
A layer (3) on the side and a layer (4) having a refractive index of 1.6 or less.
The layer (3) has a high refractive index and a refractive index of the layer (4).
Characterized by having an intermediate refractive index of the refractive index of the refractive index layer (2).
An antireflection film according to any one of the preceding claims. Note that the anti-reflection coating described in
Display device.

[0012]

DETAILED DESCRIPTION OF THE INVENTION As described above, the present invention comprises applying a composition containing a compound that promotes a curing reaction in applying a low refractive index layer formed from a hydrolysis / partial condensate of an organosilane. There is a feature in doing. The constituent features of the present invention will be described in detail.

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, it is a compound represented by the formula (R ⁹ ) ₄ Si. In the formula, R ⁹ represents an alkyl group or an aryl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an oxyacyl group having 1 to 4 carbon atoms, or a halogen atom. 1 four R ⁹ in the molecule may be different be the same as each other if the scope of this definition, but can be selected in any combination, four are simultaneously alkyl having 1 to 10 carbon atoms It cannot be a group or an aryl group.

R⁹Is an alkyl having 1 to 10 carbon atoms.
Methyl group, ethyl group, n-
Alkyl groups such as propyl group, i-propyl group, etc.
Or γ-chloropropyl group, vinyl group, CF_Three-, CF_ThreeCH_TwoCH
_Two-, CF_ThreeCH_TwoCH_TwoCH_Two-, C_TwoF_FiveCH _TwoCH_TwoCH_Two-, C_ThreeF₇CH_TwoCH_TwoCH
_Two-, C_TwoF_FiveCH_TwoCH_Two-, CF_ThreeOCH_TwoCH_TwoCH_Two-, C_TwoF_FiveOCH_TwoCH_TwoCH
_Two-, C_ThreeF₇OCH_TwoCH_TwoCH_Two-, (CF_Three)_TwoCHOCH_TwoCH_TwoCH_Two-, C_FourF₉CH
_TwoOCH_TwoCH_TwoCH_Two-, 3- (Perfluorocyclohexyloxy)
C) Propyl, H (CF_Two)_FourCH_TwoOCH_TwoCH_TwoCH_Two-, H (CF_Two)_FourCH_TwoCH
_TwoCH_Two-, Γ-glycidoxypropyl group, γ-methacryl
Oxypropyl group, γ-mercaptopropyl group, phenyl
Group, 3,4-epoxycyclohexylethyl group, etc.
No. C1-C5 alkoxy group or carbon number
Examples of the 1-4 oxyacyl groups include a methoxy group,
Ethoxy, n-propoxy, i-propoxy, n
-Butoxy, sec-butoxy, tert-butoxy,
Sethoxy groups and halogens include fluorine, chlorine, bromine,
And urine.

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

Specific examples of these alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-acetoxysilane and the like. it can. The above alkoxysilanes may be used alone or in combination of two or more.

Component (b) The component (b) is represented by the general formula R^TwoSi (OR^Three)_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 organosilane^TwoIs 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_Three-, CF_ThreeCH_Two-, CF_ThreeCH_TwoCH
_Two-, CF_ThreeCH_TwoCH_TwoCH_Two-, C_TwoF_FiveCH_TwoCH_TwoCH_Two-, C_ThreeF₇CH_TwoCH_TwoCH
_Two-, C_TwoF_FiveCH_TwoCH_Two-, CF_ThreeOCH_TwoCH_TwoCH_Two-, C_TwoF_FiveOCH_TwoCH_TwoCH_Two-
 , C_ThreeF₇OCH_TwoCH_TwoCH_Two-, (CF_Three)_TwoCHOCH_TwoCH_TwoCH_Two-, C_FourF₉CH_Two
OCH_TwoCH_TwoCH_Two-, 3- (Perfluorocyclohexyloxy)
C) Propyl, H (CF_Two)_FourCH_TwoOCH_TwoCH_TwoCH_Two-, H (CF_Two)_FourCH_TwoCH
_TwoCH_Two-, Γ-glycidoxypropyl group, γ-methacryl
Oxypropyl group, γ-mercaptopropyl group, phenyl
Group, 3,4-epoxycyclohexylethyl group, etc.
No. In addition, R in the organosilane^ThreeIs the carbon number
An alkyl group having 1 to 5 or an acyl group having 1 to 4 carbon atoms
For example, methyl, ethyl, n-propyl, i-
Propyl, n-butyl, sec-butyl, tert-butyl
And an acetyl group.

Specific examples of these organosilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyl Trimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-gly Sidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4
-Epoxycyclohexylethyltrimethoxysilane,
3,4-epoxycyclohexyl ethyl trimethoxy _{silane, CF 3 CH 2 CH 2 Si} (OCH 3) 3, CF 3 CH 2 CH 2 CH 2 Si (OCH 3) 3,
C ₂ H ₅ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₃ F ₇
CH ₂ 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 (OC
H ₃ ) ₃ , C ₄ F ₉ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H (CF ₂ ) ₄ CH ₂ OCH ₂ C
_{H 2 CH 2 Si (OCH 3} ) 3, 3- can be mentioned (perfluoro cyclohexyl) propyl silane.

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

[0020] Component (c) has the general formula _{^{R 4 2 Si (OR 5)}} 2 ( wherein, R ⁴ and R
⁵ is a diorganosilane represented by (b) R ² and R ³ as defined defined in organosilane used for Component). However, R ⁴ and R ⁵ need not be the same substituents as the component (b). 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.

Specific examples of these diorganosilanes are dimethyldimethoxysilane, dimethyldiethoxysilane,
Diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane Silane, (CF ₃
CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ , (CF ₃ CH ₂ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ , (C ₃ F
₇ OCH ₂ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ , [H (CF ₂ ) ₆ CH ₂ OCH ₂ CH ₂ CH ₂ ] ₂
Si (OCH ₃ ) ₂ , (C ₂ F ₅ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) _{2 and the} like can be mentioned, and an organosilane having a fluorine atom is preferable. When an organosilane having no fluorine atom is used as R ⁴ , dimethyldimethoxysilane and dimethyldiethoxysilane are preferred. Such R ⁴ ₂ Si (OR
⁵ ) The organosilane represented by ₂ may be used alone or in combination of two or more.
The proportion of the component (c) in the composition of the present invention is (a) and
0 to 150% by weight, preferably 5 to 1% by weight of the component (b)
The content is more than 100% by weight, more preferably 10 to 60% by weight, and when it exceeds 150% by weight, the adhesion and curability of the obtained coating film are reduced.

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

[0023]

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

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

[0026]

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(Where X, R ¹⁰ and a are the same as those described above;
¹¹ is an organic group having a polymerizable double bond), and a vinyl compound may be produced by polymerizing the silane compound, and the production method is not limited.

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

The vinyl polymer used in the production method shown in (a) is not particularly limited except for a vinyl polymer having 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,

[0030]

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[0031]

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[0032]

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

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

[0035]

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[0036]

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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 silyl group-containing vinyl polymer as described above include, for example, the following general formula:

[0039]

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(Wherein R ¹² and R ¹⁴ are a hydrogen atom, a fluorine atom or a methyl group, R ¹³ is a hydrogen atom and an alkyl group having 1 to 12 carbon atoms (for example, methyl, ethyl, n-propyl,
Allyl, n-butyl, i-butyl, n-pentel, n-
Hexyl, benzyl, (CF ₃ ) ₂ CH-, CF ₃ CH _2- , C ₇ F ₁₅ CH ₂
, C ₂ F ₁₅ CH ₂ CH ₂ —, etc.), and R ¹⁵ represents a carbon atom having 1 carbon atom such as a methylene group, an ethylene group, a propylene group or a butylene group. And alkylene groups R to R ¹⁶ are the same as R ¹³ , and m / (1+
m) = 0.01-0.4, preferably 0.02-0.2
And a trialkoxysilyl group-containing acrylic polymer represented by the formula: The number average molecular weight of the silyl group-containing vinyl polymer is preferably from 2,000 to 100,
000, more preferably 4,000 to 50,000.

Specific examples of the above-mentioned (d) silyl group-containing vinyl polymer used in the present invention include Kanekazemulak manufactured by Kaneka Corporation and the following polymers. It is not limited to these.

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

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

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

P-16 FM-2 / FM-4 / γ-acryloxypropyltrimethoxysilane (30/50/20: weight ratio) P-17 FM-3 / FM-4 / γ-methacryloxypropyltrimethoxy Silane (25/60/15: weight ratio) P-18 FM-9 / methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (60/25/15:
(Weight ratio) P-19 FM-7 / methyl methacrylate / γ-acryloxypropyltrimethoxysilane (40/45/15: weight ratio) P-20 FM-4 / methyl methacrylate / vinyl trimethoxysilane (65/20 / 15: weight ratio) (d) The proportion of the silyl group-containing vinyl polymer in the composition is
(b) 0 to 20 parts of organosilane as a raw material of the component.
0% by weight, preferably 2 to 150% by weight, more preferably 10 to 100% by weight. When the amount is less than 2% by weight, the alkali resistance of the obtained coating film is low. Causes deterioration of durability. Or
(a) is 0 to 100% by weight, and (b) is 0% based on the component (d).
It is preferable that the content of (c) is from 0 to 200% by weight, and that (a) to (c) do not become 0 at the same time.

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 (d). Preferred combinations of these organosilicon monomer compounds in the present invention are illustrated below and in the Examples. The mixing ratio indicates the weight (g) of each compound used in preparing the sol.

SP-1 10 g of methyltrimethoxysilane, 5 g of dimethyldimethoxysilane, 2.5 g of the above compound P-12 SP-2 12 g of methyltrimethoxysilane, 8 g of dimethyldiethoxysilane, 3,3,3-trifluoropropyltriphenyl Methoxysilane 4 g, the above compound P-12 3 g SP-3 tetraethoxysilane 15 g, 3,3,3-trifluorobutyltriethoxysilane 15 g SP-4 tetraethoxysilane 10 g, dimethyldimethoxysilane 5 g, 3,3,3- Trifluoropropyltriethoxysilane 10 g, compound P-121.5 g SP-5 methyltrimethoxysilane 10 g, dimethyldimethoxysilane 5 g, 3-perfluoroethoxypropyltrimethoxysilane 5 g, compound P-52.5 g SP -6 10 g of tetraethoxysilane, 5 g of bis (3,3,3-trifluoropropyl) diethoxysilane, 3 g of compound P-7 5 g of SP-7 tetraethoxysilane, 10 g of methyltrimethoxysilane, 5 g of dimethyldimethoxysilane ,
3,3-trifluoropropyltrimethoxysilane 1
2 g SP-8 18 g of cyclohexyltrimethoxysilane, 12 g of bis (3,3,3-trifluoropropyl) triethoxysilane, 15 g of tetraethoxysilane 12 g of SP-9 tetraethoxysilane, 10 g of dimethyldichlorosilane, 3,3,3- 15 g of trifluoropropyltriethoxysilane SP-12 12 g of methyltriethoxysilane, 5 g of dimethyldimethoxysilane, 5 g of bis (3,3,3-trifluoropropyl) trimethoxysilane, the above compound P-8
4.5g

In the present invention, the coating composition of the above-mentioned hydrolysis / partial condensate of an organosilane in the following description contains a "sol solution", which contains a compound which promotes a curing reaction used in coating the sol solution. The liquid of the composition is referred to as “promoting liquid”. Also, "simultaneous application" refers to simultaneously applying two liquids of a sol liquid and an accelerating liquid to the surface of a substrate on which a low refractive index layer is to be formed.
Applying the accelerating liquid on the sol liquid application surface in a completely or incompletely dried state after the sol liquid application is referred to as “overcoat (OC)”.

The curing reaction accelerating compound used in the accelerating solution of the present invention is not particularly limited, and any compound having a component capable of accelerating the condensation reaction according to the constituent components of the sol liquid used can be suitably used. it can. Generally effective are the following compound groups (e) to (h), of which preferred compounds can be added in required amounts. In addition, two or more of these groups can be appropriately selected and used together as long as the mutual promoting effect is not inhibited. In addition,
The compound for accelerating the curing reaction is 1-2 with respect to the organosilane.
It is preferable to use 0% by weight.

(E) The inorganic acid of component (e) includes hydrochloric acid, hydrogen bromide, hydrogen iodide,
Organic acid compounds such as sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, and phosphorous acid include carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, succinic acid, cyclohexanecarboxylic acid, octanoic acid, maleic acid, and 2-chloropropionic acid). , Cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid,
Benzoic acid, pentafluorobenzoic acid, phthalic acid, etc.),
Sulfonic acids (methanesulfonic acid, ethanesulfonic acid,
Trifluoromethanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid / phosphonic acids (dimethyl phosphate, phenylphosphonic acid, etc.), Lewis acids (boron trifluoride etherate, scandium triflate, alkyl titanium) Acid, aluminate, etc.) and heteropoly acids (molybdophosphoric acid, tungstophosphoric acid, etc.).

(F) The inorganic base of component (f) is sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, ammonia and the like, and the organic base compound is amines (ethylenediamine, diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, triethylamine, dibutylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine, ethanolamine, diazabicycloundecene, quinuclidine, aniline, pyridine, etc., phosphines (triphenylphosphine, trimethylphosphine) And the like, and metal alkoxides (sodium methylate, potassium ethylate, etc.).

(G) The metal chelate compound of the component (g) is represented by the general formula R ¹⁷ OH (wherein
R ¹⁷ represents an alkyl group having 1 to 6 carbon atoms), and R ¹⁸ COCH ₂ COR ¹⁹ (where R ¹⁸ is an alkyl group having 1 to 6 carbon atoms, and R ¹⁹ is an alkyl group having 1 to 6 carbon atoms). No particular limitation is imposed on the transition metal as the central metal, with the ligand being a diketone represented by 5 alkyl groups or an alkoxy group having 1 to 16 carbon atoms). In this category, two or more metal chelate compounds may be used in combination. Particularly preferred as the (g) metal chelate compound of the present invention are those having Al, Ti, and Zr as central metals, and have the general formula Zr (OR ¹⁷ ) _p1 (R ¹⁸ COCHCOR ¹⁹ )
_p2 , Ti (OR ¹⁷ ) _q1 (R ¹⁸ COCHCOR ¹⁹ ) _q2 and Al (O
R ¹⁷ ) _r1 (R ¹⁸ COCHCOR ¹⁹ ) A compound selected from the group of compounds represented by _r2 is preferred, which promotes the condensation reaction between the components (a) to (c) and the (d) silyl group-containing vinyl resin. Works.

(G) R in metal chelate compound¹⁷And R
¹⁸Is 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. In addition, (g)
P in the salt compound ₁~ R_TwoBecomes a tetradentate or hexadentate configuration
Represents an integer determined as follows.

Specific examples of these (g) 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 and 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 (g) metal chelate compounds are
Tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, aluminum diisopropoxyethylacetoacetate, and tris (ethylacetoacetate) aluminum. These (g) metal chelate compounds are:
These can be used alone or in combination of two or more. Further, as the component (g), partially hydrolyzed products of these metal chelate compounds can also be used.

(G) The ratio of the metal chelate compound in the composition is 0.0
It is 1 to 50% by weight, preferably 0.1 to 50% by weight, and more preferably 0.5 to 10% by weight.

(H) The preferred organometallic compound of component (h) is not particularly limited.
The organic transition metal is preferable because of its high activity. Among them, tin
Compounds are particularly preferred because of their good stability and activity. These utensils
Examples of physical compounds include (C_FourH₉)_TwoSn (OCOC₁₁H_{twenty three})_Two, (C_FourH
₉)_TwoSn (OCOCH = CHCOOCH_Three)_Two, (C_FourH₉)_TwoSn (OCOCH = CHCOOC_FourH₉)
_Two, (C₈H₁₇)_TwoSn (OCOC₁₁H_{twenty three})_Two, (C₈H₁₇)_TwoSn (OCOCH = CHCOO
CH_Three)_Two, (C₈H₁₇)_TwoSn (OCOCH = CHCOOC_FourH₉)_Two, (C₈H₁₇)_TwoSn (O
COCH = CHCOOC₈H₁₇)_Two, Sn (OCOCC₈H₁₇)_TwoCarboxylic acids such as
Type organotin compound; (C_FourH₉)_TwoSn (SCH_TwoCOOC₈H₁₇)_Two, (C_FourH₉)
_TwoSn (SCH_TwoCOOC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC₈H₁₇)_Two, (C
₈H ₁₇)_TwoSn (SCH_TwoCH_TwoCOOC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC₈H
₁₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC₁₂H_{twenty five})_Two,

[0057]

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Mercaptide-type organotin compounds such as

[0059]

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Sulfide-type organotin compounds such as

(C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, or (C ₄ H ₉ )
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.

(I) As the metal salts of the component (i), alkali metal salts of organic acids (eg, sodium naphthenate, potassium naphthenate, sodium octanoate, sodium 2-ethylhexanoate, potassium laurate, etc.) are preferably used. Can be

The "sol solution" and "promoting solution" of the present invention can be used by adding various compounds, if necessary, in addition to the above components. The following describes the main combined materials.

A: Solvent The solvent is composed of the components (a) to (d) in the sol solution and (e) in the accelerating solution.
To uniformly mix the components (i) to (i) to adjust the solid content of the composition of the present invention and to apply the composition to various coating methods, thereby improving the dispersion stability and storage stability of the composition. . These solvents are not particularly limited as long as they can achieve the above objects. The solvent of the sol solution and the solvent of the accelerating solution may be the same or different. However, in the case of manufacturing by the OC method, a solvent having a high permeability to the completely or incompletely dried lower layer film is used. When it is used, since the diffusion of the accelerating compound in the film is likely to occur, it is preferable because effective curing can be promoted. Preferred examples of these solvents include, for example, water, alcohols, aromatic hydrocarbons, ethers, ketones,
Esters and the like are preferred.

Among them, the alcohols include, for example, monohydric alcohols and dihydric alcohols. 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 (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.

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

Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, 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.
The 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 (g). Inferior.

C: Water To a preferred sol solution of the present invention, water is added for hydrolysis / condensation of a mixture containing the above components (a) to (d) as main components. The amount of water used is usually about 1.2 to 3.0 mol, preferably about 1.3 to 2.0 mol, per 1 mol of the components (a) to (d). The preferred sol solution and accelerating solution of the present invention have a total solid content of 0.1 to 50% by weight, preferably 1 to 40% by weight. It is not preferable because it deteriorates.

D: 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 is prepared by adding the above-mentioned colloidal compound to the coating film to obtain various properties such as coloring, imparting unevenness, preventing ultraviolet light 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 (a) to
(d) 10 to 300 parts by weight based on 100 parts by weight of the total solid content of the component.
It is about parts by weight.

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

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

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

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

The sol solution and the accelerating solution of the present invention are applied to a transparent film or a high or medium refractive index layer by a coating method such as curtain flow coating, dip coating, spin coating, roll coating, etc., and dried at normal temperature, or 30 ~
By heating at a temperature of about 200 ° C. for about 1 minute to 100 hours, a low refractive index layer is formed.

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

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

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

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

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

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

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

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

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

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

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

The antireflection film of the present invention (preferably an antireflection film having an antiglare function) is used for a liquid crystal display 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, 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.

[0094]

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

(1) Silyl group-containing vinyl resin (P-12)
Preparation of In a 1-liter three-necked flask equipped with a reflux condenser and a stirrer, 30.6 g of the fluoromonomer FM-4 and 5.4 g of γ-methacryloxypropyltrimethoxysilane were added.
The mixture was heated and stirred at 70 ° C. under a nitrogen stream. 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.)
4.8 g dissolved in 25 ml of methyl ethyl ketone.
Dropping of a solution in which 19.2 g of V-65 was dissolved in 5.4 g of FM-4 and 48.6 g of γ-methacryloxypropyltrimethoxysilane was started, and the solution was dropped at a constant speed over 6 hours. After completion of the dropwise addition, 4.8 g of V-65 and 25 ml of a methyl ethyl ketone solution were added, and the mixture was further heated and stirred at 80 ° C. for 4 hours. Thereafter, 280 ml of methyl ethyl ketone was added, followed by cooling to obtain 635 g of a solution of the title P-12. . The solid content was 54.4%, and the polymer obtained had a number average molecular weight in terms of polystyrene of 9,600 as determined by gel permeation chromatography.

(2) Preparation of sol liquid for low refractive index layer A reactor equipped with a stirrer and a reflux condenser was charged with (b) 100 g of methyltrimethoxysilane, (c) 50 g of dimethyldimethoxysilane, and (d) vinyl containing a silyl group. After adding and mixing 50 g of the resin (prepared to a solid content of 50%) and (e) 40 g of ethanol, 30 g of ion-exchanged water was added, and the mixture was reacted at 60 ° C. for 4 minutes, and then cooled to room temperature. Liquid A was obtained. If necessary, the same reaction was carried out using (a) tetraethoxysilane to obtain sol solutions BF, X, and Y shown in Table 1.

[0097]

[Table 1]

(3) Preparation of low-refractive-index layer accelerating liquid In a reactor equipped with a stirrer, the following curing reaction accelerating compound and a solvent are added, mixed and, if necessary, heated and dissolved to form a low-refractive-index layer. Use promoting liquids I to E were obtained. Accelerating solution b: 5 g of 10N hydrochloric acid solution and 1 of methyl ethyl ketone
00 g solution Promoter solution b: Solution of 2 g of trifluoroacetic acid and 100 g of methyl ethyl ketone Promoter solution C: Solution of 3 g of diazabicycloundecene and 100 g of methyl ethyl ketone Promoter solution d: 2.7 g of aluminum diisopropoxyacetoacetonate and 100 g of methyl ethyl ketone Solution Accelerating solution e: solution of 3 g of tin dibutyl dilaurate and 100 g of methyl ethyl ketone

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

(5) Coating of Second Layer (Medium Refractive Index Layer) Coating liquid containing fine dispersion of TiO ₂ 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). (6) Coating of Third Layer (High Refractive Index Layer) A coating liquid containing a fine dispersion of TiO ₂ and the 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).

(7) Coating of Fourth Layer (Low Refractive Index Layer) The composition of Table 1 was coated on the high refractive index layer by a wire bar so as to have a thickness of 95 nm according to the method described in Table 2 below. And dried at 120 ° C. for 5 minutes to form a low refractive index layer. The refractive index of the layer ranged from 1.3 to 1.5.

[0102]

[Table 2]

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

[0104]

[Table 3]

As is clear from this example, it is understood that the antireflection film of the present invention has a very low surface reflectance, a wide wavelength range, and a sufficiently strong film strength. Further, the fingerprint trace could be easily erased by wiping off the tissue, and the stain resistance was excellent. On the other hand, many of the comparative examples had insufficient surface reflectivity or film strength.

(9) Evaluation of Stability of Coating Solution over Time The sol solutions A to G, X, and Y prepared above were stored at a temperature of 40 ° C. for 72 hours, and the sol solutions A ′ to G ′, X ′, and Y ′ over time. I got This aged sol solution was used for the A to G, X, Y in Table 2 of the above (7).
And dried to obtain a sample for evaluation (Table 4).

[0107]

[Table 4]

Using this sample, the performance as a film was evaluated according to the evaluation method described in (8) above. The results are shown in Table 5.

[0109]

[Table 5]

As is apparent from the present example, the antireflection film prepared by the method of the present invention hardly showed any deterioration in performance due to a change with time of the coating solution or a decrease in suitability for coating. On the other hand, a membrane prepared by a method not depending on the present invention, even if it is a liquid capable of expressing sufficient performance before storage over time, is significantly deteriorated by storage over time, and does not have satisfactory manufacturing suitability after storage over time. It has gone.

(10) (Preparation of Display Device with Antireflection Film Installed) The antireflection films of Examples 1 to 11 and Comparative Example 3 prepared in the above example were obtained from a personal computer PC9821NS / 340W obtained from NEC Corporation. Was attached to the surface of the liquid crystal display to prepare a surface device sample, and the degree of reflection of the landscape due to the surface reflection was visually evaluated. The display devices provided with the anti-reflection films of Examples 1 to 11 of the present invention showed almost no surrounding scenery, showed comfortable visibility, and had sufficient surface strength, while the comparative examples The display device in which the film No. 3 was installed had many reflections in the surroundings and was inferior in visibility.
Also, the surface strength was poor.

[0112]

According to the present invention, a composition obtained by partial hydrolysis of a compound having an organosilane structure and a composition containing a compound having a condensation reaction accelerating ability are applied as separate liquids to form a low refractive index layer. And by setting the refractive index of the layer immediately below it to 1.6 or more, a large-area antireflection film having good optical properties and excellent film strength can be provided at a low cost and in a form suitable for production. .

[Brief description of the drawings]

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

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

[Explanation of symbols]

 11, 21: low refractive index layer 12, 24: high refractive index layer 22: medium refractive index layer 13, 23: transparent film 20: lower layer

Claims (7)

[Claims] 1. An antireflection film having a low refractive index layer formed by coating a composition containing a hydrolyzate of an organosilane and / or a partial condensate thereof, wherein the low refractive index layer is An antireflection film formed by applying a composition containing a compound that promotes a curing reaction after or simultaneously with the application of the composition. 2. The low refractive index layer is represented by (a) a general formula Si (OR ¹ ) ₄ (wherein R ¹ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms). Alkoxysilane and / or
Or (b) the general formula R ² Si (OR ³ ) ₃ (wherein R ² has 1 to 1 carbon atoms)
Represents 10 alkyl group or aryl group, R ³ is the organosilane represented by the representative of the same groups as those in R ^1), and / or (c) general formula _{^{R 4 2 Si (OR 5)}} 2 ( wherein , R ⁴ represents a group having the same meaning as R ² , and R ⁵ represents a group having the same meaning as R ¹ )
The antireflection film according to claim 1, wherein the composition is formed by applying a composition containing a hydrolyzate of an organosilane represented by the formula (1) and / or a partial condensate thereof. 3. The method according to claim 1, wherein the low-refractive-index layer is defined as follows:
100% by weight, (b) 0 to 200% by weight, (c) 0 to 200% by weight.
200% by weight and (a) to (c) are simultaneously 0
Hydrolyzate of the composition and / or parts thereof
Low coating formed by applying a composition composed of polycondensates
2. The anti-reflection coating according to claim 1, wherein the anti-reflection coating is a refractive index layer.
Stop film. (a) General formula Si (OR¹)_Four(Where R¹Is an alkyl having 1 to 5 carbon atoms
Represents a kill group or an acyl group having 1 to 4 carbon atoms)
Alkoxysilane (b) Formula R^TwoSi (OR^Three)_Three(Where R^TwoHas 1 to 10 carbon atoms
Organic group, R^ThreeIs R ¹Represents a synonymous group)
Organosilane (c) General formula R^Four _TwoSi (OR^Five)_Two(Where R^FourIs R^TwoSynonymous with
Group of R^FiveIs R¹Represents a synonymous group)
Luganosilane (d) Hydrolyzable group and / or water at the terminal or side chain
A silyl group having a silicon atom bonded to an acid group in the polymer
Group-containing vinyl polymer having at least one silyl group 4. The compound for accelerating the curing reaction is represented by the following (e):
4. The antireflection film according to claim 1, wherein the antireflection film is at least one compound selected from the group consisting of compounds represented by (h) to (h). (e) Inorganic or organic acid compound (f) Inorganic or organic base compound (g) Metal complex compound (h) Organometallic compound (i) Metal salt 5. The reflection according to claim 1, wherein said low-refractive-index layer comprises a high-refractive-index layer having a refractive index of 1.7 or more adjacent thereto. Prevention film. 6. A low refractive index layer adjacent to said high refractive index layer (2).
A layer (3) on the opposite side of (1), and further comprising a layer (4) having a refractive index of 1.6 or less, wherein the layer (3) has a refractive index higher than that of the layer (4). 6. The antireflection film according to claim 1, wherein the antireflection film has an intermediate refractive index of the refractive index of the refractive index layer. 7. A display device comprising the antireflection film according to claim 1.