KR20040002587A - Reflection Inhibiting Layer and Display Device Employing the Same - Google Patents

Abstract

PURPOSE: To provide an antireflection film useful to enhance heat resistance and the luminance of a display element and formed between a transparent base plate and a transparent conductive electrode, and a laminate having the antireflection film between the transparent base plate and the transparent conductive electrode and the display element having the laminate. CONSTITUTION: The antireflection film is formed between the transparent base plate and the transparent conductive electrode. Its refractive index in 633nm wavelength is set to <=1.33.

Description

Anti-reflection film and display device having the same {Reflection Inhibiting Layer and Display Device Employing the Same}

The present invention relates to an antireflection film formed between a transparent substrate and a transparent conductive electrode, a laminate having an antireflection film between the transparent substrate and the transparent conductive electrode, and a display element having the laminate. More specifically, transparent, useful for increasing the heat resistance and the brightness of the display element, which is preferably used in display elements such as liquid crystal display elements, electroluminescent display elements, plasma display elements, field emission display elements, electrophoretic display elements, and the like. An antireflection film formed between a substrate and a transparent conductive electrode, a laminate having the antireflection film between a transparent substrate and a transparent conductive electrode, and a display element having the laminate.

As an electrode substrate for driving a display element, the transparent conductive electrode formed on transparent substrates, such as glass, is used normally. However, a part of the light from a light source is reflected by the refractive index difference of a transparent substrate and a transparent conductive electrode, and the brightness of a display element fell.

For this problem, for example, in [MRS Fall Meeting Proceedings, Vol. 660, JJ 5.19 (2000)], if a low refractive index transparent layer is provided between a transparent substrate and a transparent conductive electrode, the reflected light can be reduced, Proposals have been made to be effective for improving screen brightness.

However, when a (meth) acrylic polymer, a fluorine-containing organic polymer, or the like, which is commonly known as a material for forming the low refractive index layer, is used as the low refractive index layer described above, practical heat resistance in the formation process of the transparent conductive electrode and the display element manufacturing process is poor. It was difficult to apply to a display element.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object thereof is an antireflection film and a transparent substrate having excellent low refractive index and heat resistance formed between a transparent substrate and a transparent conductive electrode, which are suitable for use to improve the brightness of various display elements. It is providing the laminated body which has the said antireflection film between a transparent conductive electrode, and a display element provided with this laminated body.

Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are firstly achieved by an antireflection film, wherein the antireflection film formed between the transparent substrate and the transparent conductive electrode has a refractive index of 1.33 or less at a wavelength of 633 nm.

According to the present invention, the above objects and advantages of the present invention are secondly achieved by a laminate having the antireflection film between the transparent substrate and the transparent conductive electrode.

Moreover, according to this invention, the said objective and advantage of this invention are 3rd achieved by the display element provided with the said laminated body.

Hereinafter, the antireflection film of the present invention will be described in detail.

The antireflection film of the present invention is an antireflection film formed between a transparent substrate and a transparent conductive electrode, and has a refractive index of 1.33 or less at a wavelength of 633 nm. It is preferable that it is 1.30 or less, and, as for the refractive index in wavelength 633 nm, it is more preferable that it is 1.28 or less.

Moreover, it is preferable that the antireflection film of this invention has practical heat resistance which can endure the heating in a display element manufacturing process.

The heat resistance can be evaluated by, for example, heating at 350 ° C. under nitrogen for 5 hours by the rate of change of the film thickness before and after heating, that is, the ratio of the film thickness after heating to the film thickness before heating. It is preferable that the absolute value of this change rate value is 5% or less, It is more preferable that it is 3% or less, It is especially preferable that the antireflection film of this invention is 2% or less.

As long as the antireflection film of the present invention has the above refractive index and heat resistance, the raw material and the formation method may be used, but for example, the valence of at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (3) It may contain a decomposition / condensation product.

R _a Si (OR ¹ ) _4-a

In the formula, R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is 1 or 2.

Si (OR ² ) ₄

In the formula, R ² represents a monovalent organic group.

R ³ _b (R ⁴ O) _3-b Si- (R ⁷ ) _d -Si (OR ⁵ ) _3-c R ⁶ _c

In the formula, R ³ to R ⁶ are the same or different and each represents a monovalent organic group, and R ⁷ is an oxygen atom, a phenylene group or a group represented by-(CH ₂ ) _n- , where n is 1 to 6 B and c are the same or different and are integers from 0 to 2, and d is 0 or 1.

As the monovalent organic group for R and R ¹ in the general formula (1) above, for example, an alkyl group, an aryl group, an allyl group, a glycidyl group or the like.

R in the formula (1) is preferably a monovalent organic group, more preferably an alkyl group or a phenyl group.

Here, the alkyl group preferably has 1 to 5 carbon atoms. These may be chained or may be branched. As a specific example of a preferable alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned. In addition, the hydrogen atom contained in these groups may be substituted by the fluorine atom or the like.

As said aryl group, a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group etc. are mentioned, for example.

Specific examples of the compound represented by the formula (1) include trimethoxysilane, triethoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and ethyltrimethoxysilane , Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltree -iso-propoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane , Diethyldimethoxysilane, diethyldie And the like diethoxysilane, divinyl dimethoxysilane, divinyl diethoxysilane - sisilran, diphenyl dimethoxysilane, diphenyl.

Preferred among these compounds represented by the formula (1) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and phenyl Trimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and diethyldiethoxysilane.

In the formula (2), examples of the monovalent organic group represented by R ² include the same groups as the specific examples of the monovalent organic group in the formula (1).

Specific examples of the compound represented by the formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane and tetra-sec-part. Oxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, etc. are mentioned.

Among these, tetramethoxysilane and tetraethoxysilane are preferable.

In the formula (3), examples of the monovalent organic group represented by R ³ to R ⁶ include the same groups as the specific examples of the monovalent organic group in the formula (1).

In said Formula (3), as a compound whose R <^7> is an oxygen atom, for example, hexamethoxy disiloxane, hexaethoxy disiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1, 1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraethoxy -1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldi Siloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1 , 1,3,3-tetraethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraethyldisiloxane, and the like.

Among them, hexamethoxy disiloxane, hexaethoxy disiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyl Disiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane are mentioned as a preferable example.

In addition, in the said Formula (3), as a compound whose d is 0, for example, hexamethoxy disilane, hexaethoxy disilane, 1,1,2,2- tetramethoxy-1,2-dimethyldisilane, 1 , 1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetra Oxy-1,2-diethyldisilane, etc. are mentioned.

In the above Formula 3, R ⁷ is - (CH _{2) n} - in compounds include, for example, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (tri Methoxy silyl) ethane, 1,2-bis (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane and the like.

In the present invention, the compounds represented by the above formulas (1) to (3) may be used alone or in combination of two or more.

For hydrolysis / condensation products of one or more compounds selected from the compounds represented by Formulas 1 to 3 used in the present invention, "hydrolysis" is one selected from the compounds represented by Formulas 1 to 3 above. The R ¹ O-group, R ² O-group, R ⁴ O-group, or R ⁵ O-group included in the above compound is a reaction that reacts with water to generate a silanol group. At this time, not all R ¹ O-groups, R ² O-groups, R ⁴ O-groups, or R ⁵ O-groups need to be hydrolyzed, and only a part thereof may be hydrolyzed, or the degree of hydrolysis. It may be a mixture of others.

In addition, "condensation" means that the silanol groups produced in the "hydrolysis" condensation reaction to generate a Si-O-Si bond. At this time, not all silanol groups need to be condensed, and only a part of them should be understood as a concept including a mixture of condensed substances or mixtures of different condensation degrees.

Although the conditions which perform such a hydrolysis reaction and a condensation reaction are not specifically limited, As an example, it can carry out by the following process.

That is, the hydrolysis reaction and the condensation reaction can be performed by dissolving at least one compound selected from the group consisting of compounds represented by the above formulas (1) to (3) in a suitable solvent and adding water.

At this time, the amount of the compound represented by the formula (2) is 5 to 75% by weight based on the total amount of the compound represented by each of the formulas (1) to (3) as a ratio converted to the hydrolysis / condensation product produced by complete hydrolysis. It is preferable that it is%, It is more preferable that it is 10-70 weight%, It is especially preferable that it is 15-70 weight%. By setting it as such a usage amount, the antireflective film obtained becomes excellent in an elasticity modulus.

Here, it is preferable to use the compound represented by the said Formula (1) and the compound represented by the said Formula (2) as a raw material. Although this does not affect the performance itself of an antireflection film very much, it is requested | required in terms of storage stability of the composition for antireflection film formation mentioned later.

In addition, the "conversion into the hydrolysis / condensation product produced by the complete hydrolysis" means all the R ¹ O-groups, R ² O-groups, and R ⁴ O-groups in each compound represented by Formulas 1 to 3 above. And the weight in terms of R ⁵ O- group hydrolyzed to 100% to become a silanol group and to be completely condensed to a siloxane structure.

When performing a hydrolysis reaction or a condensation reaction, it is preferable to use 0.8-20 mol of water with respect to 1 mol of alkoxyl groups in 1 or more types of compounds chosen from the group which consists of a compound represented by each of the said Formulas 1-3. It is particularly preferred to add 0.8 to 15 moles of water. If the amount of water to be added is less than 0.8 mol, the crack resistance of the antireflection film is inferior, and if it exceeds 20 mol, the surface uniformity of the antireflection film is inferior.

0-100 degreeC is preferable and, as for the temperature at the time of performing a hydrolysis reaction and a condensation reaction, 15-80 degreeC is more preferable. The reaction time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 15 hours, further preferably 30 minutes to 10 hours.

As a solvent which can be used when performing a hydrolysis reaction and a condensation reaction, 1 or more types chosen from the group of an alcohol solvent, a ketone solvent, an amide solvent, an ester solvent, and an aprotic polar solvent is mentioned, for example.

Of these, alcohol solvents and ester solvents are preferable.

Examples of the alcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, and 2-methylbutanol. , sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n- Octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec- tetradecyl alcohol, monoalcohol solvents such as sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2 Polyhydric alcohol solvents such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene And partial ether solvents of polyhydric alcohols such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene in these alcohol solvents Glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether is preferably used.

These alcohol solvents can also be used together 1 type (s) or 2 or more types.

As said ketone solvent, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n- Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone, fencone In addition to acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3, 5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro- (Beta) -diketones, such as 2, 4- heptanedione, etc. are mentioned.

Of these ketone solvents, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone and cyclohexanone are preferably used.

These ketone solvents may be used alone or in combination of two or more.

As said amide solvent, for example, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N -Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like.

Of these amide solvents, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide is preferably used.

These amide solvents can also be used together 1 type (s) or 2 or more types.

As said ester solvent, for example, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-acetic acid Propyl, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, Benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetic acid, ethyl acetoacetic acid, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene acetate Glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol acetate Nomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, acetate dipropylene glycol monomethyl ether, acetate dipropylene glycol monoethyl ether, diacetic acid glycol, methoxytriglycol acetate , Ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid Diethyl and the like.

Of these ester solvents, for example, γ-butyrolactone, ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene acetate monomethyl ether, diethylene glycol monoethyl acetate Ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, acetic acid Dipropylene glycol monoethyl ether is preferably used.

These ester solvents may be used alone or in combination of two or more.

As said aprotic polar solvent, for example, acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, N-methyl-2-pyrrolidone, 1 , 3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, and the like.

Of these aprotic polar solvents, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferably used.

These aprotic polar solvents may be used alone or in combination of two or more.

As for the usage-amount of the solvent at the time of performing a hydrolysis reaction and a condensation reaction, 200-5,000 weight part is preferable with respect to 100 weight part of total amounts of the compound represented by each of the said General formulas 1-3, 300-4,000 weight part more Preferably, 400-3,000 weight part is more preferable. In this amount of use, a hydrolysis / condensation product excellent in coating uniformity of the coating film can be obtained.

In the present invention, (A) when performing a hydrolysis reaction and a condensation reaction of at least one compound selected from the group consisting of compounds represented by the above formulas (1) to (3), the reaction is preferably performed in the presence of a catalyst. Do.

As a catalyst which can be used at this time, an alkali catalyst is preferable.

As such an alkali catalyst, For example, inorganic alkali compounds, such as sodium hydroxide, potassium hydroxide, lithium hydroxide;

Nitrogen-containing aromatic compounds such as pyridine, pyrrole, picoline, N-methylpyrrole, N-ethylpyrrole and N-methylimidazole;

Aminoalcohol compounds such as monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine and triethanolamine;

Compounds having a nitrogen-containing condensed ring structure such as diazabicyclooctane, diazabicyclononane, diazabicycloundecene;

Alkylammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide;

Piperazine, pyrrolidine, piperidine, N-methylmorpholine, N-methyl-Δ ³ -pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N Cyclic amine compounds such as -methyl-4-piperidone and N-methyl-2-piperidone;

Alkylamines such as methylamine, ethylamine, propylamine, butylamine;

Dialkylamines such as N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine;

Trialkylamines such as trimethylamine, triethylamine, tripropylamine;

Tetraalkylammonium hydroxides such as tetraethylammonium hydroxide;

And ammonia.

Of these alkali catalysts, alkylammonium salts, monoalkylamines, dialkylamines, trialkylamines, tetraalkylammonium hydroxides and ammonia are preferred, and monoalkylamines, dialkylamines, trialkylamines, tetraalkylammonium hydroxides are particularly preferred. Roxides and ammonia. The antireflection film of this invention obtained by performing a hydrolysis reaction and a condensation reaction using such an alkali catalyst becomes excellent in adhesiveness to a board | substrate.

These alkali catalysts may be used alone or in combination of two or more.

As the usage-amount of such an alkali catalyst, 1 mole of the total amount of groups represented by R <^1> O- group, R <^2> O- group, R <^4> O- group, and R <^5> O- group in the compound represented by each of the above formulas (1) to (3) 10 mol or less is preferable, 0.00001-10 mol is more preferable, and 0.00005-5 mol is more preferable. If the usage-amount of an alkali catalyst is in the said range, there exists little possibility of precipitation and gelation of the polymer in reaction.

Moreover, other catalysts other than an alkali catalyst can be used together in the range which does not impair the effect of this invention.

As such another catalyst, a metal chelate compound and an acid catalyst are mentioned, for example.

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium and tri-i-propoxy mono (acetylacetonate). Earth) titanium, diethoxy bis (acetylacetonato) titanium, di-n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, mono Toxy tris (acetylacetonato) titanium, mono-n-propoxy tris (acetylacetonato) titanium, mono-i-propoxy tris (acetylacetonato) titanium, tetrakis (acetylacetonato) Titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium, diethoxy bis ( Ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl Setoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i Propoxy-tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium Titanium chelate compounds such as tris (acetylacetonato) mono (ethylacetoacetate) titanium;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, diethoxy bis ( Acetylacetonato) zirconium, di-n-propoxy bis (acetylacetonato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) Zirconium, mono-n-propoxy tris (acetylacetonato) zirconium, mono-i-propoxy tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium, triethoxy mono ( Ethylacetoacetate) zirconium, tri-n-propoxymono (ethylacetoacetate) zirconium, tri-i-propoxymono (ethylacetoacetate) zirconium, diethoxy bis (ethylacetoacetate) zirconium, di-n -Pro Ci-bis (ethylacetoacetate) zirconium, di-i-propoxy bis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, mono-n-propoxy tris (ethylacetoacetate) Zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis Zirconium chelate compounds such as ethylacetoacetate) zirconium and tris (acetylacetonato) mono (ethylacetoacetate) zirconium;

Aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum, and the like, and among these, preferably chelate compounds of titanium or aluminum, particularly preferably chelate compounds of titanium have.

These metal chelate compounds may be used alone or in combination of two or more thereof.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and boric acid;

Acetic acid, propionic acid, butanoic acid, pentanic acid, oxalic acid, maleic acid, methylmalonic acid, butyric acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, formic acid, mal Organic acids such as lonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, hydrolysates of glutaric acid, hydrolysates of maleic anhydride and hydrolysates of phthalic anhydride Can be mentioned. Among these, organic acids are more preferable.

These acid catalysts may be used alone or in combination of two or more.

When using other catalysts other than such an alkali catalyst together, 50 weight part or less is preferable with respect to 100 weight part of alkali catalysts, and 30 weight part or less is more preferable.

The antireflection film of the present invention contains a hydrolysis / condensation product of at least one compound selected from the group consisting of compounds represented by the above formulas (1) to (3). It is preferable to carry out in the presence of an alkali catalyst as described above.

However, it is also effective to mix and use a hydrolysis / condensation product obtained using a catalyst other than an alkali catalyst in the range which does not impair the effect of this invention with the hydrolysis / condensation product obtained in the presence of the said alkali catalyst.

As catalysts other than the alkali catalyst which can be used here, the metal chelate compound and acid catalyst which were illustrated as another catalyst which can be used together with the above-mentioned alkali catalyst are mentioned.

Preferred ranges of the use ratio of the compound represented by each of the formulas (1) to (3) and the solvents that can be used when performing a hydrolysis reaction or a condensation reaction using these catalysts are the same as in the case of the reaction in the presence of the alkali catalyst described above. Do.

In addition, the preferable usage-amount of these catalysts is the same as the preferable usage-amount of the alkali catalyst mentioned above.

In the case of using a hydrolysis / condensation product obtained by using a catalyst other than the alkali catalyst with the hydrolysis / condensation product obtained in the presence of the alkali catalyst, the amount of use thereof is 30% by weight based on the total amount of the hydrolysis / condensation product. The following is preferable and 20 weight% or less is more preferable. When this value exceeds 30 weight%, the refractive index of a coating film may become larger than a predetermined value, and a desired effect may not be exhibited.

The antireflection film of the present invention is an antireflection film formed between the transparent substrate and the transparent conductive electrode as described above, and has a refractive index of 1.33 or less at a wavelength of 633 nm.

In addition, as long as the anti-reflection film of the present invention has the above refractive index and practical heat resistance, the raw material and the formation method may be used, but for example, at least one member selected from the group consisting of compounds represented by the above formulas (1) to (3). It may be to contain.

Next, the formation method of the anti-reflective film of this invention is demonstrated.

Although the formation method of the anti-reflective film of this invention is not specifically limited, For example, it can follow the method of performing the following processes sequentially.

(1) preparing a composition for forming an antireflection film containing a hydrolysis / condensation product and a solvent of at least one compound selected from the group consisting of the above compounds.

② Process of apply | coating the said anti-reflective film formation composition on a transparent substrate.

③ process of removing solvent.

Moreover, you may add the process of heating as needed. In addition, this heating process may be performed after process (3), and may be performed simultaneously with process (3).

Moreover, depending on the objective, an electron beam or an ultraviolet-ray can also be irradiated after said (3) solvent removal.

The antireflection film-forming composition contains at least one hydrolysis / condensation product and a solvent selected from the group consisting of compounds represented by the formulas (1), (2) and (3). Moreover, you may contain another component in the range which does not impair the effect of this invention.

Examples of such other components include colloidal silica, colloidal alumina, organic polymers, surfactants, silane coupling agents, and the like.

The colloidal silica or colloidal alumina may be added to improve the hardness of the antireflection film.

Colloidal silica is, for example, a dispersion in which high purity silicic anhydride is dispersed in the hydrophilic organic solvent, preferably an average particle diameter of 5 to 30 µm, more preferably 10 to 20 µm, and a solid content concentration of about 10 to 40. It is weight%. As such colloidal silica, For example, Nissan Chemical Industries, Ltd. methanol silica sol and isopropanol silica sol; The Shokubai Kasei Kogyo Co., Ltd. make, Oscal etc. are mentioned.

As colloidal alumina, Nissan Chemical Industries, Ltd. alumina sol 520, 100, 200; Alumina clear sol, Alumina sol 10, 132 by Kawaken Fine Chemical Co., Ltd. is mentioned.

Examples of the organic polymer include a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, and a polyquinol. Saline, a polyoxadiazole, a fluoropolymer, the compound which has a polyalkylene oxide structure, etc. are mentioned.

These may be used individually by 1 type or in combination of 2 or more types.

The amount of the colloidal silica and the colloidal alumina is preferably 20 parts by weight or less, more preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total amount (in terms of complete hydrolysis / condensation product) of the compounds represented by Formulas 1 to 3, respectively. Addition is more preferable.

The said organic polymer can be added in order to adjust the refractive index of the antireflection film obtained. As such an organic polymer, the compound, polyoxyethylene polyoxypropylene block copolymer, etc. which have a polyalkylene oxide structure are mentioned.

Examples of the compound having a polyalkylene oxide structure include a compound having a polymethylene oxide structure, a compound having a polyethylene oxide structure, a compound having a polypropylene oxide structure, a compound having a polytetramethylene oxide structure, and a polybutylene oxide The compound which has a structure, etc. are mentioned.

Examples of the compound having a polymethylene oxide structure include polymethylene oxide having a molecular weight of 500 to 100,000;

Examples of the compound having a polyethylene oxide structure include polyethylene oxide having a molecular weight of 500 to 100,000;

Examples of the compound having a polypropylene oxide structure include polypropylene oxide having a molecular weight of 500 to 100,000;

Examples of the compound having a polytetramethylene oxide structure include polytetramethylene oxide having a molecular weight of 500 to 100,000;

Examples of the compound having a polybutylene oxide structure include polybutylene oxide having a molecular weight of 500 to 100,000.

As said polyoxyethylene polyoxypropylene block copolymer, the compound which has the following block structure is mentioned.

-(A) _j- (B) _k-

-(A) _j- (B) _k- (A) _l-

Wherein, A is -CH ₂ CH ₂ group represented by O-, B represents a group represented by _{-CH 2 CH (CH 3) O-} , j is 1 to 90, k is 10 to 99, l is 0 To 90.

In these, the compound which has a polyethylene oxide structure, the compound which has a polypropylene oxide structure, and a polyoxyethylene polyoxypropylene block copolymer are mentioned as a preferable example.

These can also use together 1 type (s) or 2 or more types.

The use amount of the organic polymer is preferably 30 parts by weight or less, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the total amount (in terms of complete hydrolysis / condensation product) of the compounds represented by the formulas (1) to (3).

The said surfactant can be added in order to improve the applicability | paintability at the time of apply | coating the composition for antireflection film formation on a transparent substrate.

Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, fluorine surfactants, silicone surfactants, polyalkylene oxide surfactants, and poly (meth) acrylates. And rate surfactants. Of these, fluorine-based surfactants and silicone-based surfactants are preferable.

As a commercial item of the said fluorine-type surfactant, Megapack F142D, F172, F173, F183 (above, Dai Nippon Ink Chemical Co., Ltd. make), FTOP EF301, 303, 352 (made by Shin-Kaida Kasei Co., Ltd. product) ), Flowride FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Supron S-382, SC-101, SC-102, SC-103, SC-104, SC-105 Fluorine-type surfactant marketed by names, such as SC-106 (made by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (made by Yusho Co., Ltd.), and NBX-15 (neos Co., Ltd.) are mentioned. Can be. Among these, megapack F172, BM-1000, BM-1100, and NBX-15 are especially preferable.

Moreover, as said silicone type surfactant, SH7PA, SH21PA, SH30PA, ST94PA (all are the Toray Dow Corning Silicone Co., Ltd. product) etc. can be used, for example.

These can also use together 1 type (s) or 2 or more types.

The amount of the surfactant used is preferably 10 parts by weight or less, more preferably 0.0001 to 10 parts by weight based on 100 parts by weight of the total amount (in terms of complete hydrolysis / condensation product) of the compounds represented by Formulas 1 to 3. .

The said silane coupling agent can be added in order to improve the adhesiveness of the anti-reflection film of this invention and a transparent substrate.

Examples of such silane coupling agents include 3-glycidyloxypropyl trimethoxysilane, 3-aminoglycidyloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-glycidyl. Oxypropylmethyl dimethoxysilane, 1-methacryloxypropylmethyl dimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl tri Ethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl dimethoxysilane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyl tri Ethylenetriamine, N-triethoxysilylpropyl triethylenetriamine, 1 0-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triadecane, 9-trimethoxysilyl-3,6-diazanyl acetate, 9-triethoxysilyl-3, 6-diazanyl acetate, etc. are mentioned.

These can also use together 1 type (s) or 2 or more types.

The amount of the silane coupling agent used is preferably 10 parts by weight or less, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount (in terms of complete hydrolysis / condensation product) of the compounds represented by the formulas (1) to (3). .

The solvent which may be contained in the antireflection film-forming composition is not particularly limited as long as the compound represented by each of Chemical Formulas 1 to 3 and other additives optionally added are uniformly dissolved or dispersed. For example, 1 or more types chosen from the group of alcohol solvent, a ketone solvent, an amide solvent, an ester solvent, and an aprotic polar solvent are mentioned.

As the alcohol solvent, for example, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, 3-methoxybutanol, 2,6-dimethyl Monoalcohols such as heptanol-4, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2 Polyhydric alcohols such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene And partial etherification solvents of polyhydric alcohols such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

Examples of the ketone solvents include methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone and ethyl-n-butyl ketone , Methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, phencone, etc. , Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5- Nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2, (Beta) -diketones, such as 4-heptanedione, etc. are mentioned.

These ketone solvents may be used alone or in combination of two or more.

As said amide solvent, for example, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N -Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like.

These amide solvents can also be used together 1 type (s) or 2 or more types.

As said ester solvent, for example, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-acetic acid Propyl, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, Benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetic acid, ethyl acetoacetic acid, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene acetate Glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol acetate Nomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, acetate dipropylene glycol monomethyl ether, acetate dipropylene glycol monoethyl ether, diacetic acid glycol, methoxytriglycol acetate , Ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid Diethyl and the like.

These ester solvents may be used alone or in combination of two or more.

As said aprotic polar solvent, for example, acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, N-methyl-2-pyrrolidone, 1 , 3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, and the like.

These solvents can also use together 1 type (s) or 2 or more types.

The amount of the solvent used may be used in an amount such that the total content of components other than the solvent in the total amount of the antireflective film-forming composition is preferably 1 to 30% by weight, more preferably 2 to 25% by weight.

As a solvent, when a solvent is used in the above-mentioned hydrolysis reaction and condensation reaction, the solvent can also be used as it is as a solvent of the composition for antireflection film formation, and can also be substituted by the said solvent by the method normally performed. It may also be a mixture of both.

In addition, when the alcohol having a boiling point of 100 ° C. or less is present in the composition for forming an antireflection film in excess of 20% by weight, problems may arise in terms of coating uniformity of the coating film, and therefore the content thereof is preferably 20% by weight or less, particularly It is preferable to remove by distillation etc. so that it may become 5 weight% or less. Alcohol below boiling point 100 degreeC may arise at the time of the hydrolysis reaction and condensation reaction mentioned above.

Moreover, the composition obtained as mentioned above can remove the foreign material in a composition by filtering with a filter made from Teflon (trademark) agent, polyethylene agent, polypropylene, etc. which are about 0.05-5 micrometers in diameter, and can obtain a favorable coating film. Can be.

Next, the above-described antireflection film-forming composition is applied onto the transparent substrate.

As a transparent substrate which can be used here, besides glass, resin substrates, such as a polycarbonate, polyester, aromatic polyamide, polyimide amide, polyether sulfone, the ring-opening polymer of cyclic olefin, and its hydrogenated substance, are mentioned.

Depending on the purpose, these substrates may be subjected to appropriate treatments such as chemical treatment, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, and the like.

In coating, for example, suitable coating means such as spin coating, dipping, roll coating, spraying, bar coating, or the like can be used.

It is preferable that the coating film thickness at this time is about 0.005-2 micrometers as a film thickness after solvent removal. In addition, when a thick film thickness is desired, it is also possible to repeat the application | coating process several times and thicken it. At this time, the coating film of about 0.01-4 micrometers in 2 coatings and about 0.015-6 micrometers in 3 coatings may be formed.

The solvent is then removed. The solvent removal step can be carried out by a suitable method such as being allowed to stand at room temperature for a predetermined time, and can also replace the solvent removal step by a heating step described later.

The heating step can be optionally performed as necessary.

The heating step is preferably carried out by heating at a temperature of 80 to 400 ° C, more preferably 100 to 350 ° C, preferably 2 to 240 minutes, more preferably 5 to 120 minutes.

As the heating method, for example, a hot plate, an oven, a furnace, or the like can be used, and the heating can be performed under conditions such as air, nitrogen, argon, vacuum, or low oxygen concentration.

By performing such heat processing, the antireflection film of this invention becomes a more solid thing. It is assumed that at least one selected from the compounds represented by the above formulas (1) to (3) contained in the antireflection film of the present invention is due to the glassy or macromolecular polymer.

At the time of the said electron beam irradiation, it can carry out by the exposure amount of 100-20,000 J / m <^2> using the 0.1-10 keV electron beam.

In addition, at the time of the said ultraviolet irradiation, it can carry out by the exposure amount of 100-200000 J / m < ² > using 150-300 nm ultraviolet-rays.

It is preferable that the film thickness of the antireflection film of this invention is 10-500 nm from the point which can obtain the low reflection laminated film.

After forming the antireflection film of this invention on a transparent substrate as mentioned above, it can be set as the laminated body of this invention by further forming a transparent conductive electrode on the upper part of an antireflection film.

As a transparent conductive electrode which can be used here, zinc oxide, tin oxide, indium oxide, tin dope indium oxide, an indium oxide zinc oxide composite etc. are mentioned, for example.

As a method of forming such a transparent conductive electrode, a sputtering method, a vacuum deposition method, an ion plating method, a coating method, a plating method, etc. are mentioned, for example.

30-500 nm is preferable and, as for the preferable thickness of a transparent conductive electrode, 50-400 nm is more preferable.

Next, the display element of this invention is demonstrated.

The display element of this invention has said laminated body on the surface of an observer side, and is excellent in screen brightness compared with the conventionally known display element.

The display element of the present invention may be, for example, a liquid crystal display element, an electroluminescent display element, a plasma display element, a field emission display element or an electrophoretic display element.

As described above, the antireflection film of the present invention has two characteristics of low refractive index and practical heat resistance, and the laminate having the antireflection film of the present invention between the transparent substrate and the transparent conductive electrode includes a liquid crystal display element and an electroluminescence. It contributes to the brightness improvement of display elements, such as a display element, a plasma display element, a field emission display element, or an electrophoretic display element.

<Example>

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following description shows the embodiment of this invention generally, and there is no reason in particular, and this invention is not limited by this description.

In addition, the part and% in an Example and a comparative example represent a weight part and weight%, respectively, unless there is particular notice.

In addition, various evaluation followed the following method.

Weight average molecular weight (Mw)

It measured by the gel permeation chromatography (GPC) method by the following conditions.

Sample: Prepared by using tetrahydrofuran as a solvent and dissolving 1 g of hydrolysis condensate in 100 cc of tetrahydrofuran.

Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical, USA was used.

Apparatus: high temperature high speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters, Inc.

Column: Showa Denko Co., Ltd. make SHODEX A-80M (length 50cm)

Measuring temperature: 40 ℃

Flow rate: 1 cc / min

Heat resistance

The antireflection film-forming composition was applied onto the glass substrate by using a spin coating method, heated at 90 ° C. for 3 minutes on a hot plate to remove the solvent, and then heated at 250 ° C. for 3 minutes to reflect a film thickness of 100 nm. The glass substrate in which the prevention film was formed was obtained. The obtained glass substrate with an antireflection film was heated at 350 ° C. under nitrogen for 5 hours, and the change in the film thickness of the coating film before and after heating was measured. When the absolute value of the film thickness change at this time is 5% or less, it is evaluated that heat resistance is favorable.

Refractive index

The anti-reflective film-forming composition was applied onto the silicon substrate using a spin coating method, heated at 90 ° C. for 3 minutes on a hot plate to remove the solvent, and then heated at 250 ° C. for 3 minutes to reflect a film thickness of 100 nm. The silicon substrate in which the prevention film was formed was obtained. The refractive index of this coating film was measured using the spectroscopic ellipsometer of 633 nm wavelength. When the refractive index is 1.33 or less, the result is evaluated to be good.

Reflectance measurement

The composition was coated on the glass substrate by spin coating to form an antireflection film-forming composition, heated at 90 ° C. for 3 minutes on a hot plate to remove the solvent, and then heated at 250 ° C. for 3 minutes to obtain a film thickness of 100 nm. The glass substrate in which the antireflective film of was formed was obtained. A 50 nm-thick tin-doped indium oxide was formed on the antireflective film on this glass substrate using the sputtering method, and the laminated body was formed.

A 633 nm lithium-neon laser was incident orthogonally on the tin-doped indium oxide film surface with respect to this laminated body, and the laser beam intensity emitted from the glass surface was measured, and the intensity change from incident light was computed. When the absolute value of the change rate of this laser beam intensity is 1% or less, the reflectance result can be said to be favorable.

Synthesis Example 1

In a quartz separable flask, 276.01 g of methyltrimethoxysilane as a compound represented by the formula (1), 86.14 g of tetramethoxysilane as the compound represented by the formula (2) and 0.0092 g of tetrakis (acetylacetonato) titanium as a catalyst After dissolving in 101 g of propylene glycol monoethyl ether, the mixture was stirred with a three-one motor and the solution temperature was stabilized at 55 ° C. Then, a mixed solution of 225.52 g of ion-exchanged water and 263.00 g of propylene glycol monoethyl ether was added to the solution over 1 hour. Then, after reacting at 55 degreeC for 4 hours, 48.12 g of acetylacetone were added, and also it was made to react for 30 minutes, and the reaction liquid was cooled to room temperature. 227g of the solution containing methanol and water was evaporated and removed from reaction liquid at 50 degreeC, and reaction liquid (1) was obtained.

The weight average molecular weight of the hydrolysis / condensation product thus obtained was 1,230.

In addition, in the synthesis example 1, the usage-amount converted into the complete hydrolysis / condensation product of the compound (tetramethoxysilane) represented by General formula (2) is a complete hydrolysis / condensation product of each compound represented by General formula (1) It corresponds to 20.1% by weight based on the total amount used.

Synthesis Example 2

In a quartz separable flask, 205.50 g of methyltrimethoxysilane as a compound represented by the formula (1) and 85.51 g of tetramethoxysilane as the compound represented by the formula (2) were dissolved in 426 g of propylene glycol monoethyl ether. Stirred by motor and stabilized at 50 ° C solution temperature. Subsequently, 182 g of ion-exchanged water in which 0.63 g of maleic acid was dissolved as a catalyst was added to the solution over 1 hour. Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. 360 g of the solution containing methanol was removed from the reaction liquid at 50 degreeC, and reaction liquid (2) was obtained.

The weight average molecular weight of the hydrolysis / condensation product thus obtained was 1,400.

In addition, in the synthesis example 2, the usage-amount converted into the complete hydrolysis / condensation product of the compound (tetramethoxysilane) represented by general formula (2) is a complete hydrolysis / condensation product of the compound represented by each of general formula (1)-(3) It corresponds to 24.8% by weight based on the total amount used.

Synthesis Example 3

370 g of distilled ethanol, 200 g of distilled propylene glycol monopropyl ether, 160 g of ion-exchanged water and 90 g of a 10% aqueous solution of methylamine were added to the quartz separable flask and stirred uniformly. To this solution was added a mixture of 136 g of methyltrimethoxysilane as the compound represented by the formula (1) and 209 g of tetraethoxysilane as the compound represented by the formula (2). The solution was reacted for 2 hours while maintaining the temperature at 52 ° C. 300 g of propylene glycol monopropyl ether was added to the solution, and then concentrated using a 50 ° C. evaporator until it reached 10% (completely hydrolyzed / condensed product), followed by 10% propylene of acetic acid. 10 g of glycol monopropyl ether solution was added to the reaction solution 3.

The weight average molecular weight of the hydrolysis / condensation product thus obtained was 904,000.

In addition, in the synthesis example 3, the usage-amount converted into the complete hydrolysis / condensation product of the compound (tetraethoxysilane) represented by general formula (2) is a complete hydrolysis / condensation product of the compound represented by each of general formulas (1) It corresponds to 47.3 weight% with respect to the total used amount.

Synthesis Example 4

Into a quartz separable flask, 428 g of distilled ethanol, 215 g of ion-exchanged water, and 15.6 g of a 25% aqueous solution of tetramethylammonium hydroxide were added as a catalyst and stirred uniformly. To this solution was added a mixture of 40.8 g of methyltrimethoxysilane as the compound represented by the formula (1) and 61.4 g of tetraethoxysilane as the compound represented by the formula (2). The solution was reacted for 2 hours while maintaining the solution at 57 ° C. 300 g of propylene glycol monopropyl ether was added to the solution, and the solution was then concentrated using an evaporator at 50 ° C until it became 10% (complete hydrolysis / condensation product conversion), and then 10% of maleic acid. 20 g of propylene glycol monopropyl ether solution was added to obtain a reaction solution ④.

The weight average molecular weight of the hydrolysis / condensation product thus obtained was 1,600,000.

In addition, in the synthesis example 4, the usage-amount converted into the complete hydrolysis / condensation product of the compound (tetraethoxysilane) represented by general formula (2) is a complete hydrolysis / condensation product of the compound represented by each of general formula (1)-(3) It is equivalent to 46.8% by weight based on the total amount of use.

Synthesis Example 5

Into a quartz separable flask, 428 g of distilled ethanol, 215 g of ion-exchanged water, and 15.6 g of a 25% aqueous solution of tetramethylammonium hydroxide were added as a catalyst and stirred uniformly. To this solution is added a mixture of 40.8 g of methyltrimethoxysilane as the compound represented by the formula (1), 61.4 g of tetraethoxysilane as the compound represented by the formula (2) and 2.4 g of hexaethoxydisiloxane as the compound represented by the formula (3). It was. The solution was reacted for 2 hours while maintaining the solution at 57 ° C. 300 g of propylene glycol monopropyl ether was added to this solution, and then, the solution was concentrated using an evaporator at 50 ° C until it became 10% (in terms of complete hydrolysis condensate), and then 10% of maleic acid was added. 20 g of a propylene glycol monopropyl ether solution was added to obtain a reaction solution ⑤.

The weight average molecular weight of the hydrolysis / condensation product thus obtained was 1,650,000.

In addition, in the synthesis example 5, the usage-amount converted into the complete hydrolysis / condensation product of the compound (tetraethoxysilane) represented by general formula (2) is a complete hydrolysis / condensation product of the compound represented by each of general formula (1)-(3) It is equivalent to 45.8% by weight based on the total amount of use.

<Example 1>

The reaction solution 3 obtained in Synthesis Example 3 was filtered with a filter made of Teflon (registered trademark) having a pore diameter of 0.2 μm to prepare a composition for forming an antireflection film.

It evaluated according to the above-mentioned evaluation method using this composition for antireflection film formation. The results are shown in Table 1.

The refractive index of the anti-reflection film formed here was 1.27, and the absolute value of the film thickness change rate of the heat resistance test was 1.5%, indicating excellent heat resistance.

Moreover, in the reflectance evaluation of the laminated body formed here, the absolute value of the laser beam intensity change was 0.3%, and showed the outstanding antireflection performance.

<Examples 2 to 8>

In Example 1, it evaluated similarly to Example 1 except having used the reaction liquid of Table 1 or the mixture of reaction liquid instead of reaction liquid ③. The evaluation results are shown in Table 1 together.

Comparative Example 1

In Example 1, tin-doped indium oxide was formed directly on the glass substrate, without performing the anti-reflective film formation process using reaction liquid (3).

When the reflectance of this laminated film was measured, the antireflection performance was lowered to 1.6%.

Comparative Example 2

In Example 1, it evaluated substantially the same as Example 1 except having used Cytop (fluorine-containing organic polymer) by Asahi Glass Co., Ltd. instead of reaction liquid ③.

The refractive index of the antireflection film formed here was 1.34, which showed a refractive index exceeding 1.33. The absolute value of the film thickness change in the heat resistance test of the antireflection film was found to be inferior in practical heat resistance at 7.2%.

In addition, in the reflectance evaluation of the laminated body formed here, the absolute value of the laser beam intensity change was 1.1%, and it was inferior to antireflection ability.

Raw material of composition for antireflection film formation Evaluation of antireflection film Evaluation reflectance (%) of laminate Heat resistance (%) Refractive index Example 1 Reaction solution ③ 1.5 1.27 0.3 Example 2 Reaction liquid ④ 1.3 1.26 0.2 Example 3 Reaction solution③ 30g + reaction solution① 3g 1.2 1.29 0.5 Example 4 Reaction solution③ 30g + reaction solution② 2g 1.2 1.28 0.4 Example 5 Reaction solution④ 30g + reaction solution① 3g 1.1 1.28 0.4 Example 6 Reaction solution④ 30g + reaction solution② 2g 1.1 1.27 0.3 Example 7 Reaction solution ⑤ 1.2 1.25 0.2 Example 8 Reaction solution③ 30g + reaction solution① 10g 1.2 1.32 0.9 Comparative Example 1 none - - 1.6 Comparative Example 2 Asahi Glass Co., Ltd. production Saitop 7.2 1.34 1.1

According to the present invention, an antireflection film having excellent low refractive index and heat resistance formed between a transparent substrate and a transparent conductive electrode, and the antireflection film between the transparent substrate and the transparent conductive electrode, which are suitable for use for improving the brightness of various display elements, are provided. There is provided a laminate having and a display element comprising the laminate.

The display element which has an antireflection film and a laminated body of this invention is excellent in screen brightness.

Claims (6)

An antireflection film formed between a transparent substrate and a transparent conductive electrode, wherein the antireflection film has a refractive index of 1.33 or less at a wavelength of 633 nm. The antireflection film according to claim 1, wherein the antireflection film contains a hydrolysis / condensation product of at least one compound selected from the group consisting of compounds represented by the following formulas (1), (2) and (3). <Formula 1> R _a Si (OR ¹ ) _4-a In the formula, R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, and a is 1 or 2. <Formula 2> Si (OR ² ) ₄ In the formula, R ² represents a monovalent organic group. <Formula 3> R ³ _b (R ⁴ O) _3-b Si- (R ⁷ ) _d -Si (OR ⁵ ) _3-c R ⁶ _c In the formula, R ³ to R ⁶ are the same or different and each represents a monovalent organic group, and R ⁷ is an oxygen atom, a phenylene group or a group represented by-(CH ₂ ) _n- , where n is 1 to 6 B and c are the same or different and are integers from 0 to 2, and d is 0 or 1. The antireflection film according to claim 2, wherein the hydrolysis and condensation of at least one compound selected from the group consisting of compounds represented by the above formulas (1) to (3) is performed in the presence of an alkali catalyst. The laminated body which has an anti-reflective film in any one of Claims 1-3 between a transparent substrate and a transparent conductive electrode. The display element provided with the laminated body of Claim 4. The display element according to claim 5, wherein the display element is a liquid crystal display element, an electroluminescent display element, a plasma display element, a field emission display element or an electrophoretic display element.