JP5310842B2 - Anti-reflection film forming composition - Google Patents

Abstract

Disclosed is a composition for forming an anti-reflection film, which is capable of providing an anti-reflection film that has high antifouling property, high anti-reflection effect over a wide wavelength range and high mechanical strength, said anti-reflection film having satisfactorily small differences in the anti-reflection effect between different wavelengths over a wide wavelength range. Specifically disclosed is a composition for forming an anti-reflection film, which contains (A) a hydrolyzable metal alkoxide and/or a hydrolysis product thereof, (B) a fluorine-containing polymer that is composed of a structural unit represented by general formula (M) (wherein X1 and X2 may be the same or different and each represents H or F; X3 represents H, F, CH3 or CF3; X4 and X5 may be the same or different and each represents H, F or CH3; Rf1 represents a fluorine-containing alkyl group having 1-40 carbon atoms or an organic group in which from one to three Y3s are bonded to a fluorine-containing alkyl group having an ether bond with 2-100 carbon atoms; Y3 represents a functional group that is reactive with a hydrolyzable metal alkoxide or a monovalent organic group having 1-10 carbon atoms and the reactive group; a represents an integer of 0-3; and b and c may be the same or different and each represents 0 or 1), and (C) a solvent having a boiling point of not less than 70°C and a solubility parameter of 8.0-10.0.

Description

  The present invention relates to a composition for forming an antireflection film.

Currently, with the development of multimedia, various developments have been seen in various display devices (display devices).
Among various types of display devices, in particular, those used outdoors mainly for portable device display devices, it is becoming increasingly important to improve the visibility. Further, even in a large-sized display device, it is demanded by consumers that it is easier to see.
Conventionally, as a means for improving the visibility of a display device, an antireflection film made of a low refractive index material is coated on a substrate of the display device.
As a method of forming the antireflection film, for example, a method of forming a thin film of a fluorine compound by vapor deposition is known.
However, in recent years, there has been a demand for a technique capable of forming an antireflection film for a large display device at a low cost centering on a liquid crystal display device. In the case of the vapor deposition method, it is difficult to form a high-efficiency and uniform antireflection film on a large-area substrate, and it is difficult to reduce the cost because a vacuum apparatus is required.
Under such circumstances, a method of forming an antireflection film by preparing a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent and applying it to the surface of a substrate has been studied. Yes.

In general, when a person uses the display screen, dirt such as dirt, fingerprints, sweat, and cosmetics adheres to the display screen. When the antireflection film is formed, dirt due to the adhesion is easily noticeable and the dirt is difficult to remove.
Therefore, antifouling properties are also required for the antireflection film.

By the way, generally, as a method of forming an antireflection film using a thin film on an optical substrate, there is a method of forming a single layer or a plurality of layers. These are methods that have been practiced for a long time, and generally a thin film is formed by a film forming method such as inorganic vacuum deposition.
When the number of thin film layers is small, it is difficult to obtain an antireflection effect for light having a wavelength range. This is because the refractive index of the thin film is uniquely determined. In order to obtain the antireflection effect in a wide wavelength range, it is necessary to continuously distribute the refractive index of the thin film to obtain a gradient refractive index.
As a method of forming this gradient refractive index profile, for example, a method of laminating a large number of thin films can be considered. This is also a useful method from the viewpoint of suppressing the reflectance from changing depending on the incident angle of light.
However, since the antireflection film basically uses the interference of light to eliminate the reflected light, it is necessary to control the refractive index and film thickness of the material with high precision when forming a thin film. is there. Therefore, as the number of thin films to be stacked increases, problems such as a decrease in productivity and a decrease in mechanical strength increase.
With respect to this problem, Patent Document 1 is formed from an inorganic / organic composite material containing fluorine and has a pseudo multilayer structure (or a tilted structure), thereby providing high antifouling properties and a wide wavelength range. An antireflection film that realizes a high antireflection effect and high mechanical strength has been proposed.
The antireflection film described in Patent Document 1 has a high antifouling property, a high antireflection effect in a wide wavelength range, and a high mechanical strength, but from the viewpoint of keeping the difference in the antireflection effect at different wavelengths small. Still not enough. When the difference in the antireflection effect is not sufficiently small at different wavelengths, there is a problem that reflected light from the display device provided with the antireflection film is colored.

Japanese Patent No. 3912288

The present invention has been made against the background described above, and its purpose is to have high antifouling properties, a high antireflection effect in a wide wavelength range, and high mechanical strength, and in particular, a wide wavelength range. An object of the present invention is to provide a composition for forming an antireflection film from which an antireflection film having a sufficiently small difference in antireflection effect at different wavelengths can be obtained.
Another object of the present invention is to provide an antireflection film having these functions.

［式中、
Ｘ¹およびＸ²は、同じまたは異なり、ＨまたはＦであり、
Ｘ³は、Ｈ、Ｆ、ＣＨ₃またはＣＦ₃であり、
Ｘ⁴およびＸ⁵は、同じまたは異なり、Ｈ、ＦまたはＣＨ₃であり、
Ｒｆ¹は、炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ³が１〜３個結合している有機基であり、
Ｙ³は、加水分解性金属アルコキシドと反応しうる官能基、または当該反応基を有する炭素数１〜１０の１価の有機基であり、
ａは、０〜３の整数であり、
ｂおよびｃは、同じまたは異なり、０または１である。］
で表される構造単位からなる含フッ素重合体、および
（Ｃ）沸点が７０℃以上であり、かつ溶解度パラメータが８．０〜１０.０である溶媒
を含有する反射防止膜形成用組成物を提供する。
これにより、疑似的な多層構造（または傾斜構造）を有し、それによって、高い防汚性、広い波長域での高い反射防止効果、および高い機械的強度を有し、特に、広い波長域にわたって、異なる波長での反射防止効果の差が十分に小さい反射防止膜が得られる。The present invention
(A) hydrolyzable metal alkoxide and / or hydrolyzate thereof,
(B) General formula (M)

[Where:
X ¹ and X ² are the same or different and are H or F;
X ³ is H, F, CH ₃ or CF ₃ ;
X ⁴ and X ⁵ are the same or different and are H, F or CH ₃ ,
Rf ¹ is an organic group in which 1 to 3 Y ³ are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms,
Y ³ is a functional group capable of reacting with a hydrolyzable metal alkoxide, or a C 1-10 monovalent organic group having the reactive group,
a is an integer of 0 to 3,
b and c are the same or different and are 0 or 1. ]
And (C) a composition for forming an antireflective film comprising a solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8.0 to 10.0. provide.
Thereby, it has a pseudo multi-layer structure (or inclined structure), thereby having high antifouling property, high antireflection effect in a wide wavelength range, and high mechanical strength, especially over a wide wavelength range. Thus, an antireflection film having a sufficiently small difference in antireflection effect at different wavelengths can be obtained.

［式中、
Ｘ¹およびＸ²は、同じまたは異なり、ＨまたはＦであり、
Ｘ³は、Ｈ、Ｆ、ＣＨ₃またはＣＦ₃であり、
Ｘ⁴およびＸ⁵は、同じまたは異なり、Ｈ、ＦまたはＣＨ₃であり、
Ｒｆ¹は、炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ³が１〜３個結合している有機基である。
Ｙ³は、加水分解性金属アルコキシド（ｂ）と反応した官能基、または加水分解性金属アルコキシド（ｂ）と反応した反応基を有する炭素数１〜１０の１価の有機基であり、
ａは、０〜３の整数であり、
ｂおよびｃは、同じまたは異なり、０または１である。）
で表される構造単位を含有する含フッ素重合体、および
（Ｃ）沸点が７０℃以上であり、かつ溶解度パラメータが８．０〜１０.０である溶媒
を含有する反射防止膜形成用組成物である。One embodiment of the present invention includes
(A) Hydrolyzable metal alkoxide (a) and / or a hydrolyzate thereof,
(B ′) General formula (M ′)

[Where:
X ¹ and X ² are the same or different and are H or F;
X ³ is H, F, CH ₃ or CF ₃ ;
X ⁴ and X ⁵ are the same or different and are H, F or CH ₃ ,
Rf ¹ is an organic group in which 1 to 3 Y ³ are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms.
Y ³ is a monovalent organic group having 1 to 10 carbon atoms having a functional group reacted with the hydrolyzable metal alkoxide (b) or a reactive group reacted with the hydrolyzable metal alkoxide (b);
a is an integer of 0 to 3,
b and c are the same or different and are 0 or 1. )
And (C) a composition for forming an antireflective film, comprising a solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8.0 to 10.0. It is.

である。The reactive group is preferably a hydroxy group.
The “functional group reacted with the hydrolyzable metal alkoxide (b)” is preferably

It is.

  The hydrolyzable metal alkoxide preferably contains Si as a metal.

The present invention also provides:
Provided is an antireflection film formed by applying the antireflection film-forming composition to a member to prevent reflection, and evaporating the solvent from the applied antireflection film-forming composition. To do.

According to the composition for forming an antireflection film of the present invention, it has high antifouling properties, a high antireflection effect in a wide wavelength range, and a high mechanical strength, and in particular, reflection at different wavelengths over a wide wavelength range. An antireflection film having a sufficiently small difference in prevention effect can be obtained.
The antireflection film of the present invention has these functions.

It is a graph which shows the composition ratio (F / Si) with respect to the emission angle measured by the X ray electron molecular spectroscopy (Examples 1-3, Reference Examples 1-3). It is a graph which shows the composition ratio (F / Si) with respect to the emission angle measured by the X ray electron molecular spectroscopy (Example 4, Reference example 4). It is a graph which shows the composition ratio (F / Si) with respect to the emission angle measured by the X ray electron molecular spectroscopy (Example 5). It is a graph which shows the composition ratio (F / Si) with respect to the emission angle measured by the X ray electron molecular spectroscopy (Example 6, Reference example 5). It is a graph which shows the composition ratio (F / Si) with respect to the emission angle measured by the X ray electron molecular spectroscopy (Examples 7-9). It is a chart which shows the reflectance of light with a wavelength of 300 nm-1000 nm.

式中、
Ｘ¹およびＸ²は、同じまたは異なり、Ｈ（水素）またはＦ（フッ素）であり、
Ｘ³は、Ｈ、Ｆ、ＣＨ₃（メチル）またはＣＦ₃（トリフルオロメチル）であり、
Ｘ⁴およびＸ⁵は、同じまたは異なり、Ｈ、ＦまたはＣＨ₃であり、
Ｒｆ¹は、炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ³が１〜３個結合している有機基であり、
Ｙ³は、加水分解性金属アルコキシドと反応しうる官能基、または当該反応基を有する炭素数１〜１０の１価の有機基であり、
ａは、０〜３の整数であり、
ｂおよびｃは、同じまたは異なり、０または１である。］
で表される構造単位からなる含フッ素重合体、および
（Ｃ）沸点が７０℃以上であり、かつ溶解度パラメータが８．０〜１０.０である溶媒
を含有する。
本明細書中、「含フッ素」とは、一部または全部の水素原子がフッ素原子で置換されていること、すなわちフッ化されていることを意味する。
本明細書中、「エーテル結合を有する」とは、単結合の一部または全部がエーテル結合に置き換えられていること（言い換えれば、エーテル結合が挿入されていること）を意味する。
本明細書中、「有機基」とは、炭素を有する基を意味する。本明細書中、特に限定の無い限り、「有機基」の炭素数は、好ましくは、１〜１００である。[Antireflection film forming composition]
The composition for forming an antireflection film of the present invention is
(A) hydrolyzable metal alkoxide and / or hydrolyzate thereof,
(B) General formula (M)

Where
X ¹ and X ² are the same or different and are H (hydrogen) or F (fluorine);
X ³ is H, F, CH ₃ (methyl) or CF ₃ (trifluoromethyl);
X ⁴ and X ⁵ are the same or different and are H, F or CH ₃ ,
Rf ¹ is an organic group in which 1 to 3 Y ³ are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms,
Y ³ is a functional group capable of reacting with a hydrolyzable metal alkoxide, or a C 1-10 monovalent organic group having the reactive group,
a is an integer of 0 to 3,
b and c are the same or different and are 0 or 1. ]
And (C) a solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8.0 to 10.0.
In the present specification, “fluorine-containing” means that some or all of the hydrogen atoms are substituted with fluorine atoms, that is, fluorinated.
In this specification, “having an ether bond” means that part or all of a single bond is replaced with an ether bond (in other words, an ether bond is inserted).
In the present specification, the “organic group” means a group having carbon. In the present specification, unless otherwise specified, the “organic group” preferably has 1 to 100 carbon atoms.

(A) Hydrolyzable metal alkoxide and / or hydrolyzate thereof The antireflection film-forming composition of the present invention contains a hydrolyzable metal alkoxide and / or a hydrolyzate thereof.
The “hydrolyzable metal alkoxide” used in the present invention preferably has at least one alkoxy group. The number of the alkoxy groups is preferably 1 to 12, more preferably 1 to 4.

The “hydrolyzable metal alkoxide” used in the present invention is preferably, for example,
General formula (1):
_{^{R 11 a (R 12 O)}} b M {O-MR 11 g (OR 12) h} f -R 11 d (OR 12) e (1)
[Where:
Each R ¹¹ represents an alkyl group, a methacryloxy group, an acryloxy group, a vinyl group-containing organic group, an aryl group, an amino group, a glycidyl group, an isocyanate group, or a carboxy group-containing organic group,
Each R ¹² represents an alkyl group, an alkoxyalkyl group, or an aryl group, M represents a metal,
a is 0-3, b is 0-4, a + b is 2-4,
d is 1 or 0, e is 1 or 0, d + e is 1,
f is 0-10 (eg, 0-4),
g is 0-3, h is 0-3, and g + h is 1-3.
However, at least one of b, e, and h is 1 or more. ]
It is a hydrolysable metal alkoxide represented by these.

Although it is only for the purpose of facilitating understanding of the general formula (1), general formulas included in the general formula (1) are exemplified below.

The “hydrolyzable metal alkoxide” used in the present invention preferably also has the general formula:
(R ¹¹ ) _n M (OR ¹² ) _m
[Where:
R ¹¹ represents an alkyl group, a methacryloxy group, an acryloxy group, a vinyl group-containing organic group, an aryl group, an amino group, an epoxy group-containing organic group, or an isocyanate group,
R ¹² represents an alkyl group, an alkoxyalkyl group, or an aryl group,
M represents a metal.
m is 2 to 5 (particularly 3 or 4), n is 0 to 2 (particularly 0 or 1), and m + n is 3 to 5 (particularly 4). ]
It is a compound shown by these.
Carbon number of an alkyl group is 1-6, for example.
Carbon number of an aryl group is 6-18, for example.
Carbon number of a vinyl group containing organic group and an epoxy group containing organic group is 2-6, for example.
An example of the vinyl group-containing organic group is a vinyl group.
Examples of the epoxy group-containing organic group include a glycidyl group.
In the alkoxyalkyl group, the alkoxy group has 1 to 6 carbon atoms, for example, and the alkyl group has 1 to 6 carbon atoms, for example.

Examples of M (metal) include silicon (Si), titanium (Ti), aluminum (Al), zirconium (Zr), tin (Sn), iron (Fe), sodium (Na), magnesium (Mg), phosphorus (P), sulfur (S), potassium (K), calcium (Ca), scandium (Sc), vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), rubidium (Rb), strontium (Sr), yttrium (Y), niobium (Nb), molybdenum (Mo), cadmium (Cd), indium (In), antimony (Sb), tellurium (Te), cesium (Cs), barium (Ba), lanthanum (La), ha Nium (Hf), tantalum (Ta), tungsten (W), mercury (Hg), thallium (Tl), lead (Pb), bismuth (Bi), lithium (Li), beryllium (Be), boron (B), Cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), Examples include erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).
Among these, silicon (Si) is particularly preferable from the viewpoints of reactivity, solubility, and stability.

The hydrolyzable metal alkoxide is preferably, for example,
Tetraethoxysilane [Si (OCH ₂ CH ₃ ) ₄ ] (tetrafunctional) (TEOS),
Methyltriethoxysilane [CH ₃ Si (OCH ₂ CH ₃ ) ₃ ] (trifunctional) (MTES),
Dimethyldiethoxysilane [(CH ₃ ) ₂ Si (OCH ₂ CH ₃ ) ₂ ] (bifunctional),
Trimethylethoxysilane _{[(CH 3) 3 SiOCH 2} CH 3] (1 functional), and ethoxy siloxane oligomer _{[(CH 3 CH 2 O)} 3 Si- {O-Si (OCH 2 CH 3) 2} n- (OCH _{2 CH 3)] (n =} 1~4) (6~12 functional)
It is.

As hydrolyzable metal alkoxides, and preferably, for example,
Isocyaninate propyltriethoxysilane [OCNC ₃ H ₆ Si (OCH ₂ CH ₃ ) ₃ ],
Glycidyl triethoxysilane _{[CH 2 OCHC 3 H 6 Si} (OCH 2 CH 3) 3], and aminopropyltriethoxysilane _{[NH 3 C 3 H 6 Si} (OCH 2 CH 3) 3] is.

［式中、Ｒ⁴、Ｒ⁵、Ｒ⁶およびＲ⁷は、同じまたは異なり、水素または炭素数１〜４のアルキル基であり、Ａ¹は、直接結合または２価の有機基であり、Ｍ¹はＳｉ、Ｔｉ、Ａｌ、Ｚｎ、Ｓｎ、Ｆｅなどの金属であり、ｎは１〜３である。
］で示される化合物である。As hydrolyzable metal alkoxides, preferably also, for example, the formula:

[Wherein, R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms, A ¹ is a direct bond or a divalent organic group; ¹ is a metal such as Si, Ti, Al, Zn, Sn, and Fe, and n is 1 to 3.
].

（３−メタクリロキシプロピルトリメトキシシラン）

（３−メタクリロキシプロピルトリエトキシシラン）

（Ｎ−［２−（ビニルベンジルアミノ）エチル］−３−アミノプロピルトリメトキシシラン・塩酸塩）Examples thereof include the following.
CH ₂ = CHSi (OCH ₃ ) ₃ (vinyltrimethoxysilane)
CH ₂ = CHSi (OCH ₂ CH ₃ ) ₃ (vinyltriethoxysilane)

(3-methacryloxypropyltrimethoxysilane)

(3-methacryloxypropyltriethoxysilane)

(N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride)

（チタンメタクリレートトリイソプロポキサイド）The hydrolyzable metal alkoxide is also preferably an alkoxytitanium group-containing monomer, for example.
Examples of the alkoxytitanium group-containing monomer include the following.

(Titanium methacrylate triisopropoxide)

Particularly preferred as the hydrolyzable metal alkoxide is, for example,
Tetraethoxysilane and methyltriethoxysilane.
Such hydrolyzable metal alkoxides can be used alone or in combination of two or more.
The content of the hydrolyzable metal alkoxide and / or the hydrolyzate thereof in the composition for forming an antireflection film of the present invention is preferably 0.1 to 40% by weight, more preferably 0.2 to 20% by weight. is there.

［式中、
Ｘ¹およびＸ²は、同じまたは異なり、ＨまたはＦであり、
Ｘ³は、Ｈ、Ｆ、ＣＨ₃またはＣＦ₃であり、
Ｘ⁴およびＸ⁵は、同じまたは異なり、Ｈ、ＦまたはＣＨ₃であり、
Ｒｆ¹は、炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ³が１〜３個結合している有機基であり、
Ｙ³は、加水分解性金属アルコキシドと反応しうる官能基、または当該反応基を有する炭素数１〜１０の１価の有機基であり、
ａは、０〜３の整数であり、
ｂおよびｃは、同じまたは異なり、０または１である。］
で表される構造単位からなる含フッ素重合体（本明細書中、単に含フッ素重合体Ｂと称する場合がある。）を含有する。(B) Fluoropolymer The composition for forming an antireflection film of the present invention is
General formula (M)

[Where:
X ¹ and X ² are the same or different and are H or F;
X ³ is H, F, CH ₃ or CF ₃ ;
X ⁴ and X ⁵ are the same or different and are H, F or CH ₃ ,
Rf ¹ is an organic group in which 1 to 3 Y ³ are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms,
Y ³ is a functional group capable of reacting with a hydrolyzable metal alkoxide, or a C 1-10 monovalent organic group having the reactive group,
a is an integer of 0 to 3,
b and c are the same or different and are 0 or 1. ]
A fluorine-containing polymer comprising a structural unit represented by the formula (sometimes referred to simply as fluorine-containing polymer B in the present specification).

  The number average molecular weight of the fluoropolymer is preferably 500 to 1,000,000, more preferably 5000 to 50,000.

As the “fluorinated alkyl group having an ether bond having 2 to 100 carbon atoms” for Rf ¹ ,
Formula — (O—Rf ^1a ) _nf —Rf ^1b or — (Rf ^1a —O) _nf —Rf ^1b
(Where
Rf ^1a represents an alkylene chain having 1 to 5 carbon atoms (preferably 1 to 3) which may be substituted with a fluorine atom;
Rf ^1b represents an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3) which may be substituted with a fluorine atom;
nf represents an integer of 1 to 99. )
The fluorine-containing alkyl group which has a C2-C100 ether bond represented by these is mentioned.
However, Rf ¹ does not have a —O—O— part.
Preferred examples of the “functional group capable of reacting with a hydrolyzable metal alkoxide” for Y ³ include a hydroxy group, a glycidyl group, an amino group, an alkoxy group, a carboxy group, and an isocyanate group. Of these, more preferred are, for example, a hydroxy group and a carboxy group, and still more preferred is, for example, a hydroxy group.

CX ⁴ X ⁵ , CO, and O in the general formula (1) are present in the order described in the formula.

［式中の記号は前記と同意義を表す。］
で表される構造単位である。The structural unit represented by the general formula (1) is preferably, for example,
General formula (1)

[The symbols in the formula are as defined above. ]
Is a structural unit represented by

  The fluorinated polymer B can be produced by, for example, a known method such as the method described in International Publication WO95 / 33782 pamphlet, or a method analogous thereto.

  From the viewpoint of obtaining an antireflection film with little reflection, the fluorine content in the fluoropolymer B is preferably high, preferably 15% by weight or more, more preferably 30% by weight or more.

  The content of the fluoropolymer B in the composition for forming an antireflection film of the present invention is preferably 0.1 to 40% by weight, more preferably 0.2 to 20% by weight.

In the composition for forming an antireflection film of the present invention, the hydrolyzable metal alkoxide or the hydrolyzate thereof may be bonded to Rf ^{1 of the} fluoropolymer B.

(C) Solvent The composition for forming an antireflection film of the present invention has a boiling point of 70 ° C. or higher and a solubility parameter of 8.0 to 10.0 (sometimes referred to as solvent C in the present specification). Contain).
By using such a solvent, an antireflection film having a sufficiently small difference in antireflection effect at different wavelengths can be obtained.
Here, the solubility parameter means a quantity defined by (H / V) ^1/2 when the heat of molar evaporation of the liquid is H and the molar volume is V, and is also called an SP value. There are various literature values regarding the SP value of the solvent. Here, the values of Charles M. Hansen, Ind. Eng. Chem. Prod. Res. Dev., 1969, 8 (1), pp 2-11 were referred to. . This value is also cited, for example, in Table 3-10 of “Basic Science of Coating” by Yuji Harasaki, Kashiwa Shoten (1977), p. 65. The SP value can also be obtained by calculation, for example, by the method described in RT Fedors, Polymer Engineering and Science, (14), 147 (1974). Regarding the SP value not described in the previous document, the value was determined by calculation according to the method of this document.
When the SP value is higher than 10.0, the compatibility with the hydrolyzable metal alkoxide and / or the hydrolyzate thereof is improved, and the entire system is made uniform, so that the inclined structure is difficult to occur. On the other hand, when the SP value is less than 8.0, the solubility of the fluorine-containing polymer is remarkably lowered, so that a uniform solution cannot be obtained.
When the boiling point is lower than 70 ° C., the solvent is volatilized before the inclined structure is formed, and as a result, a sufficient inclined structure cannot be obtained. In addition, since the volatility is high, a large amount of bubbles are generated when the coating film is formed, and the coating film becomes cloudy. The boiling point of the solvent is preferably 160 ° C. or less from the viewpoint of preventing the solvent from remaining excessively in the antireflection film formed from the composition for forming an antireflection film of the present invention.
Examples of such a solvent include butyl acetate (boiling point: 126 ° C., SP value 8.46), ethylbenzene (boiling point: 136 ° C., SP value 8.80), xylene (boiling point: 139 ° C., SP value 8.80). ), Methyl amyl ketone (boiling point: 152 ° C., SP value 8.55), ethyl acetate (boiling point: 77 ° C., SP value 9.10), benzene (boiling point: 80 ° C., SP value 9.15), toluene (boiling point) : 110 ° C., SP value 8.91), trichlorethylene (boiling point: 87 ° C., SP value 9.28), methyl ethyl ketone (boiling point: 79 ° C., SP value 9.27), methyl isobutyl ketone (boiling point: 116 ° C., SP value) 8.57). Of these, ester solvents such as butyl acetate and ethyl acetate, and ketone solvents such as methyl amyl ketone, methyl isobutyl ketone, and methyl ethyl ketone are preferable from the viewpoint of solubility. Of these, methyl isobutyl ketone is most preferred.
The content of the solvent in the composition for forming an antireflection film of the present invention is preferably 50 to 99% by weight, more preferably 70 to 99% by weight.
The composition for forming an antireflection film of the present invention may contain a solvent other than the solvent C as long as the effects of the present invention are not impaired.
The content of the solvent other than the solvent C in the composition for forming an antireflection film of the present invention is preferably 35 parts by weight or less with respect to 100 parts by weight of the solvent C.

［式中、Ｒ⁴、Ｒ⁵、Ｒ⁶およびＲ⁷は、同じまたは異なり、水素または炭素数１〜４のアルキル基であり、Ａ¹は、直接結合または２価の有機基であり、Ｍ¹はＳｉ、Ｔｉ、Ａｌ、Ｚｎ、Ｓｎ、Ｆｅなどの金属であり、ｎは１〜３である。］
で示される化合物であってよい。
具体的には（ａ）としては、アルコキシシリル基含有モノマーまたはアルコキシチタン基含有モノマーが挙げられる。
アルコキシシリル基含有モノマーとして、例えば、以下のものが例示される。ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ （ビニルトリメトキシシラン）
ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₂ＣＨ₃）₃ （ビニルトリエトキシシラン）

（３−メタクリロキシプロピルトリメトキシシラン）

（３−メタクリロキシプロピルトリエトキシシラン）

（Ｎ−［２−（ビニルベンジルアミノ）エチル］−３−アミノプロピルトリメトキシシラン・塩酸塩）
モノマー（ａ）と共重合可能なモノマー（ｂ）の具体例としては、
（１）メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル、ｔｅｒｔ−ブチルビニルエーテル、ｎ−ペンチルビニルエーテル、ｎ−ヘキシルビニルエーテル、ｎ−オクチルビニルエーテル、ｎ−ドデシルビニルエーテル、ラウリルビニルエーテル、セチルビニルエーテル、２−エチルヘキシルビニルエーテル、エチレングリコールブチルビニルエーテル、ジエチレングリコールモノビニルエーテル、トリエチレングリコールメチルビニルエーテル、シクロヘキシルビニルエーテルなどのアルキルビニルエーテル類もしくはシクロアルキルビニルエーテル類；
（２）酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、バーサチック酸ビニル、ステアリン酸ビニル、安息香酸などのカルボン酸ビニルエステル類；
（３）エチレン、プロピレン、イソブテンなどのα−オレフィン類；
（４）スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ジイソプロペニルベンゼン、ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン、１，１−ジフェニルエチレン、ｐ−メトキシスチレン、Ｎ，Ｎ−ジメチル−ｐ−アミノスチレン、Ｎ，Ｎ−ジエチル−ｐ−アミノスチレン、ビニルピリジン、ビニルイミダゾールなどのビニル芳香族化合物；
（５）（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸などのカルボキシ基含有化合物；
（６）メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレートなどのアルキル（メタ）アクリレート類；
（７）ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートなどのヒドロキシアルキル（メタ）アクリレート類；
（８）フェノキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレートなどのフェノキシアルキル（メタ）アクリレート類；
（９）メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、プロポキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、メトキシブチル（メタ）アクリレートなどのアルコキシアルキル（メタ）アクリレート類；
（１０）ポリエチレングリコールモノ（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレートなどのポリエチレングリコール（メタ）アクリレート類；
（１１）ポリプロピレングリコールモノ（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、エトキシポリプロピレングリコール（メタ）アクリレート、ノニルフェノキシポリプロピレングリコール（メタ）アクリレートなどのポリプロピレングリコール（メタ）アクリレート類；
（１２）シクロヘキシル（メタ）アクリレート、４−ブチルシクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタジエニル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレートなどのシクロアルキル（メタ）アクリレート類；
（１３）アクリロイルモルフォリン、ジアセトン（メタ）アクリルアミド、イソブトキシメチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリルアミド、ジエチルアミノエチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ｔｅｒｔ−オクチル（メタ）アクリルアミド、７−アミノ−３，７−ジメチルオクチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミドなどの（メタ）アクリルアミド類；
（１４）クロトン酸メチル、クロトン酸エチル、クロトン酸プロピル、クロトン酸ブチル、ケイ皮酸メチル、ケイ皮酸エチル、ケイ皮酸プロピル、ケイ皮酸ブチル、イタコン酸ジメチル、イタコン酸ジエチル、マレイン酸ジメチル、マレイン酸ジエチル、フマル酸ジメチル、フマル酸ジエチルなどの不飽和カルボン酸エステル類；
（１５）（メタ）アクリロニトリル、α−クロロアクリロニトリル、α−クロロメチルアクリロニトリル、α−メトキシアクリロニトリル、α−エトキシアクリロニトリル、クロトン酸ニトリル、ケイ皮酸ニトリル、イタコン酸ジニトリル、マレイン酸ジニトリル、フマル酸ジニトリルなどの不飽和ニトリル類；
（１６）２−ヒドロキシエチルビニルエーテル、２−ヒドロキシプロピルビニルエーテル、３−ヒドロキシプロピルビニルエーテル、３−ヒドロキシブチルビニルエーテル、４−ヒドロキシブチルビニルエーテル、５−ヒドロキシペンチルビニルエーテル、６−ヒドロキシヘキシルビニルエーテルなどの水酸基含有ビニルエーテル類；
（１７）２−ヒドロキシエチルアリルエーテル、４−ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテルなどの水酸基含有アリルエーテル類；
（１８）Ｎ−ビニル−２−ピロリドン、Ｎ−ビニル−２−カプロラクタムなどのＮ−ビニルラクタム類；
（１９）ナイロン６，６６，６１０，１２共重合体などの可溶性ナイロン共重合体類などを挙げることができる。
中でも、上記の単量体化合物のうち、アルキルビニルエーテル類、シクロアルキルビニルエーテル類、またはカルボン酸ビニルエステル類やメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレートが好適に使用され、単独で、または２種以上を併用することができる。
数平均分子量５００以上の非フッ素オレフィン系重合体には、この他、三次元的に分岐した多分岐化合物で、規則性のあるハイパーブランチ（ｈｙｐｅｒ−ｂｒａｎｃｈｅｄ）構造を有する化合物（通称、「デンドリマー」）であってもよい。
即ち、１分子中に少なくとも４個の末端官能基を有し、且つ５個以上の末端官能基由来の活性水素を有する多官能化合物（ａ）と、活性水素と反応可能な官能基を有するビニル基含有化合物とを、多官能化合物（ａ）が有する活性水素含有末端官能基由来の活性水素の少なくとも１個にビニル基を導入し、且つ全活性水素の９５％以下にビニル基を導入するように反応させてなり、コア部位、分岐部位、枝部位、および末端部位から構成され、該末端部位としてビニル基およびビニル基以外の活性水素含有官能基を有するビニル基含有デンドリマーであってよい。
例えば、多官能化合物（ａ）が、下記式（ｉ）または（ｉｉ）で示されるポリアミノ系デンドリマーであってよい。

さらに、ポリアミノ系デンドリマーとしては、上記式（ｉ）または（ｉｉ）で示した、ブチレンジアミン系デンドリマーとアクリロニトリルを反応させ、末端のニトリル基をアミンに還元する反応を１ステップとし、この反応を繰り返すことにより得られるプロピレンイミン系デンドリマー（ＷＯ９３／１４１４７，ＵＳ５５３００９２，特公平７−３３０６３１）や、アンモニアやエチレンジアミンにメチルアクリレートをマイケル付加し、更にエステルアミド交換反応により末端に二級アミノ基を導入する反応を１ステップとし、必要に応じてこのステップを繰り返すことにより得られる下記構造式（ｉｖ）で示したアミドアミン系デンドリマー（ＷＯ８４／０２７０５，特公平６−７０１３２）またはその中間生成物、また下記式（ｉｉｉ）、下記式（ｖ）で示される構造を有する化合物などを挙げることができる。

当該密着性向上剤の量は、（Ａ）加水分解性金属アルコキシドおよび／またはその加水分解物１００重量部に対して、好ましくは０．１〜５００重量部、より好ましくは１〜５０重量部である。(D) Other components The antireflection film-forming composition of the present invention may contain an adhesion improver, if desired.
The surface free energy of the adhesion accelerator (gamma] s) is, 10 mJ / m ² or more, for example 15 mJ / m ² or more, and particularly preferably 20 mJ / m ² or more.
Examples of the adhesion improver include polymethacrylic acid; PMAA (molecular weight 55000) γs = 71.0 mJ / m ² , methyl methacrylate / methacryloxypropyltrimethoxysilane copolymer; P (MMA-TMSM) ( = 9/1 mol ratio; molecular weight 100000) γs = 37.6 mJ / m ^{2 and the} like.
Preferably, the adhesion improver is a non-fluorinated olefin polymer having a number average molecular weight of 500 or more, for example, 1000 or more.
The non-fluorinated olefin-based polymer includes (a) a monomer having a carbon-carbon double bond and a metal alkoxide group (hereinafter referred to as “monomer (a)”), (b) other copolymerizable with this monomer (a). It can be obtained by reacting a monomer compound (hereinafter referred to as “monomer (b)”).
The non-fluorinated olefin polymer may be a homopolymer of monomer (a), a homopolymer of monomer (b), or a copolymer of monomer (a) and monomer (b). Alternatively, it may be a mixture of a monomer (a) homopolymer and a monomer (b) homopolymer.
Component (a) has the general formula:

[Wherein, R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms, A ¹ is a direct bond or a divalent organic group; ¹ is a metal such as Si, Ti, Al, Zn, Sn, and Fe, and n is 1 to 3. ]
It may be a compound shown by these.
Specifically, (a) includes an alkoxysilyl group-containing monomer or an alkoxytitanium group-containing monomer.
Examples of the alkoxysilyl group-containing monomer include the following. CH ₂ = CHSi (OCH ₃ ) ₃ (vinyltrimethoxysilane)
CH ₂ = CHSi (OCH ₂ CH ₃ ) ₃ (vinyltriethoxysilane)

(3-methacryloxypropyltrimethoxysilane)

(3-methacryloxypropyltriethoxysilane)

(N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride)
As a specific example of the monomer (b) copolymerizable with the monomer (a),
(1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, Alkyl vinyl ethers or cycloalkyl vinyl ethers such as lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, ethylene glycol butyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol methyl vinyl ether, cyclohexyl vinyl ether;
(2) Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl stearate, benzoic acid;
(3) α-olefins such as ethylene, propylene and isobutene;
(4) Styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chloro Vinyl aromatic compounds such as styrene, 1,1-diphenylethylene, p-methoxystyrene, N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, vinylpyridine, vinylimidazole;
(5) Carboxy group-containing compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid;
(6) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth ) Acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) ) Acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (Meth) acrylates, alkyl such isostearyl (meth) acrylate (meth) acrylates;
(7) Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate;
(8) Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
(9) Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate;
(10) Polyethylene glycol (meth) acrylates such as polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and nonylphenoxypolyethylene glycol (meth) acrylate Kind;
(11) Polypropylene glycol (meth) acrylates such as polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate;
(12) Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate , Cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and tricyclodecanyl (meth) acrylate;
(13) Acryloylmorpholine, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, tert-octyl (meth) (Meth) acrylamides such as acrylamide, 7-amino-3,7-dimethyloctyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide;
(14) Methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate, diethyl itaconate, dimethyl maleate , Unsaturated carboxylic acid esters such as diethyl maleate, dimethyl fumarate, diethyl fumarate;
(15) (Meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, etc. Of unsaturated nitriles;
(16) Hydroxyl-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 3-hydroxypropyl vinyl ether, 3-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether ;
(17) Hydroxyl-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether;
(18) N-vinyl lactams such as N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam;
(19) Soluble nylon copolymers such as nylon 6,66,610,12 copolymer and the like can be mentioned.
Among them, among the above monomer compounds, alkyl vinyl ethers, cycloalkyl vinyl ethers, or carboxylic acid vinyl esters, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate Are preferably used and can be used alone or in combination of two or more.
In addition to this, non-fluorinated olefin polymers having a number average molecular weight of 500 or more include a three-dimensionally branched multi-branched compound having a regular hyper-branched structure (commonly referred to as “dendrimer”). ).
That is, a polyfunctional compound (a) having at least 4 terminal functional groups in one molecule and having active hydrogen derived from 5 or more terminal functional groups, and vinyl having a functional group capable of reacting with active hydrogen A vinyl group is introduced into at least one active hydrogen derived from an active hydrogen-containing terminal functional group of the polyfunctional compound (a), and a vinyl group is introduced into 95% or less of the total active hydrogen. And a vinyl group-containing dendrimer having a core part, a branch part, a branch part, and a terminal part, and having a vinyl group and an active hydrogen-containing functional group other than the vinyl group as the terminal part.
For example, the polyfunctional compound (a) may be a polyamino dendrimer represented by the following formula (i) or (ii).

Further, as the polyamino dendrimer, the reaction in which butylene diamine dendrimer and acrylonitrile shown in the above formula (i) or (ii) are reacted and the terminal nitrile group is reduced to amine is made one step, and this reaction is repeated. Propyleneimine dendrimer (WO93 / 14147, US5530092, JP-B-7-330631) obtained by this, Michael addition of methyl acrylate to ammonia or ethylenediamine, and further introducing a secondary amino group at the terminal by ester amide exchange reaction The amidoamine dendrimer (WO84 / 02705, Japanese Patent Publication No. 6-70132) represented by the following structural formula (iv) or an intermediate product thereof obtained by repeating this step as necessary, and the following formula ( i i), and the like compounds having a structure represented by the following formula (v).

The amount of the adhesion improver is preferably 0.1 to 500 parts by weight, more preferably 1 to 50 parts by weight with respect to (A) 100 parts by weight of the hydrolyzable metal alkoxide and / or hydrolyzate thereof. is there.

The composition for forming an antireflection film of the present invention may contain various other additives as desired.
Examples of such additives include leveling agents, viscosity modifiers, light stabilizers, moisture absorbers, pigments, dyes, reinforcing agents, and the like.
The antireflection film-forming composition of the present invention can also contain inorganic compound fine particles for the purpose of increasing the hardness of the cured product.
The inorganic compound fine particles are not particularly limited, but compounds having a refractive index of 1.5 or less are preferable.
Specifically, magnesium fluoride (refractive index 1.38), silicon oxide (refractive index 1.46), aluminum fluoride (refractive index 1.33-1.39), calcium fluoride (refractive index 1.44) Fine particles such as lithium fluoride (refractive index 1.36 to 1.37), sodium fluoride (refractive index 1.32 to 1.34), thorium fluoride (refractive index 1.45 to 1.50) are desirable. .
Further, conductive or semiconductive fine particles made of CuS, CdS, Ag, or the like are also desirable.
The particle size of the inorganic compound fine particles is desirably sufficiently smaller than the wavelength of visible light in order to ensure the transparency of the low refractive index material. Specifically, it is preferably 100 nm or less, particularly 50 nm or less.
When using inorganic compound fine particles, it should be used in the form of an organic sol dispersed in advance in an organic dispersion medium in order not to lower the dispersion stability in the composition and the adhesion in the low refractive index material. Is desirable.
Furthermore, in order to improve the dispersion stability of the inorganic compound fine particles and the adhesion in the low refractive index material in the composition, the surface of the inorganic fine particle compound is modified in advance using various coupling agents. Can do.
Examples of various coupling agents include organically substituted silicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony or mixtures thereof; salts of organic acids; coordination compounds bonded to coordination compounds, and the like. .

In the composition for forming an antireflection film of the present invention, the above-mentioned other components may be dissolved or dispersed in the solvent, but in order to form a uniform thin film, a comparison is required. A uniform solution is preferable in that film formation is possible at a low temperature.
Such a liquid can be prepared by mixing the said component by a conventional method.

［式中、
Ｘ¹およびＸ²は、同じまたは異なり、ＨまたはＦであり、
Ｘ³は、Ｈ、Ｆ、ＣＨ₃またはＣＦ₃であり、
Ｘ⁴およびＸ⁵は、同じまたは異なり、Ｈ、ＦまたはＣＨ₃であり、
Ｒｆ¹は、炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ³が１〜３個結合している有機基である。
Ｙ³は、加水分解性金属アルコキシド（ｂ）と反応した官能基、または加水分解性金属アルコキシド（ｂ）と反応した反応基を有する炭素数１〜１０の１価の有機基であり、
ａは、０〜３の整数であり、
ｂおよびｃは、同じまたは異なり、０または１である。）
で表される構造単位を含有する含フッ素重合体となっていることが好ましい。
当該含フッ素重合体は、一般式（Ｍ）で表される構造単位および一般式（Ｍ’）で表される構造単位からなる。一般式（Ｍ）で表される構造単位および一般式（Ｍ’）で表される構造単位のモル比は、通常１０：９０〜９０：１０であり、好ましくは、２０：８０〜８０：２０である。
好ましくは、このような含フッ素重合体は、単離されて、加水分解性金属アルコキシド（ｂ）とは異なる加水分解性金属アルコキシド（本明細書中、加水分解性金属アルコキシド（ａ）と称する場合がある。）、および沸点が７０℃以上であり、かつ溶解度パラメータが８．０〜１０.０である溶媒と混合される。
すなわち、
（Ａ）加水分解性金属アルコキシド（ａ）および／またはその加水分解物、
（Ｂ）一般式（Ｍ’）

［式中、
Ｘ¹およびＸ²は、同じまたは異なり、ＨまたはＦであり、
Ｘ³は、Ｈ、Ｆ、ＣＨ₃またはＣＦ₃であり、
Ｘ⁴およびＸ⁵は、同じまたは異なり、Ｈ、ＦまたはＣＨ₃であり、
Ｒｆ¹は、炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ³が１〜３個結合している有機基である。
Ｙ³は、加水分解性金属アルコキシド（ｂ）と反応した官能基、または加水分解性金属アルコキシド（ｂ）と反応した反応基を有する炭素数１〜１０の１価の有機基であり、
ａは、０〜３の整数であり、
ｂおよびｃは、同じまたは異なり、０または１である。）
で表される構造単位を含有する含フッ素重合体、および
（Ｃ）沸点が７０℃以上であり、かつ溶解度パラメータが８．０〜１０.０である溶媒
を含有する反射防止膜形成用組成物は、本発明の反射防止膜形成用組成物の一態様である。When the hydrolyzable metal alkoxide is a combination of two or more kinds, hydrolyzable metal alkoxides of several kinds (eg, one kind) (in the present specification, hydrolyzable metal alkoxide (b) and May be reacted with a part of the functional group capable of reacting with the hydrolyzable metal alkoxide in the fluoropolymer to give a compound of the general formula (M ′)

[Where:
X ¹ and X ² are the same or different and are H or F;
X ³ is H, F, CH ₃ or CF ₃ ;
X ⁴ and X ⁵ are the same or different and are H, F or CH ₃ ,
Rf ¹ is an organic group in which 1 to 3 Y ³ are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms.
Y ³ is a monovalent organic group having 1 to 10 carbon atoms having a functional group reacted with the hydrolyzable metal alkoxide (b) or a reactive group reacted with the hydrolyzable metal alkoxide (b);
a is an integer of 0 to 3,
b and c are the same or different and are 0 or 1. )
It is preferable that it is a fluorine-containing polymer containing the structural unit represented by these.
The fluoropolymer includes a structural unit represented by the general formula (M) and a structural unit represented by the general formula (M ′). The molar ratio of the structural unit represented by the general formula (M) and the structural unit represented by the general formula (M ′) is usually 10:90 to 90:10, preferably 20:80 to 80:20. It is.
Preferably, such a fluorine-containing polymer is isolated and is different from the hydrolyzable metal alkoxide (b) (referred to herein as the hydrolyzable metal alkoxide (a)). And a solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8.0 to 10.0.
That is,
(A) Hydrolyzable metal alkoxide (a) and / or a hydrolyzate thereof,
(B) General formula (M ′)

[Where:
X ¹ and X ² are the same or different and are H or F;
X ³ is H, F, CH ₃ or CF ₃ ;
X ⁴ and X ⁵ are the same or different and are H, F or CH ₃ ,
Rf ¹ is an organic group in which 1 to 3 Y ³ are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms.
Y ³ is a monovalent organic group having 1 to 10 carbon atoms having a functional group reacted with the hydrolyzable metal alkoxide (b) or a reactive group reacted with the hydrolyzable metal alkoxide (b);
a is an integer of 0 to 3,
b and c are the same or different and are 0 or 1. )
And (C) a composition for forming an antireflective film, comprising a solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8.0 to 10.0. These are one aspect | mode of the composition for anti-reflective film formation of this invention.

  The terms and symbols used for the composition for forming an antireflection film have the same meanings as the terms and symbols described in detail above unless otherwise specified.

である。The functional group in the “functional group reacted with hydrolyzable metal alkoxide (b)” and the “functional group reacted with hydrolyzable metal alkoxide (b)” is preferably a carboxy group.
The “functional group reacted with the hydrolyzable metal alkoxide (b)” is preferably

It is.

Among the hydrolyzable metal alkoxides described above, examples of the hydrolyzable metal alkoxide (a) include:
Tetraethoxysilane [Si (OCH ₂ CH ₃ ) ₄ ] (tetrafunctional),
Methyltriethoxysilane [CH ₃ Si (OCH ₂ CH ₃ ) ₃ ] (trifunctional),
Dimethyldiethoxysilane [(CH ₃ ) ₂ Si (OCH ₂ CH ₃ ) ₂ ] (bifunctional),
Trimethylethoxysilane _{[(CH 3) 3 SiOCH 2} CH 3] (1 functional), and ethoxy siloxane oligomer _{[(CH 3 CH 2 O)} 3 Si- {O-Si (OCH 2 CH 3) 2} n- (OCH _{2 CH 3)] (n =} 1~4) , such as (6-12 functional), hydrolyzable metal alkoxide containing Si as metal is preferably used.
On the other hand, among the hydrolyzable metal alkoxides, examples of the hydrolyzable metal alkoxide (b) include:
Isocyaninate propyltriethoxysilane [OCNC ₃ H ₆ Si (OCH ₂ CH ₃ ) ₃ ],
Glycidyl triethoxysilane _{[CH 2 OCHC 3 H 6 Si} (OCH 2 CH 3) 3], and aminopropyltriethoxysilane _{[NH 3 C 3 H 6 Si} (OCH 2 CH 3) 3] , such as, Si as the metal A hydrolyzable metal alkoxide containing is preferably used.

[Antireflection film]
The antireflection film of the present invention can be formed by applying the composition for forming an antireflection film of the present invention to a member to which the antireflection film of the present invention is applied and evaporating the solvent.
As a result, a gradient of refractive index due to the composition gradient of the film is generated in the film thickness direction, and an antireflection film having a sufficiently small difference in antireflection effect at different wavelengths can be obtained.
The coating method is not particularly limited as long as the film thickness can be controlled, and a known coating method can be employed.
Specifically, for example, from a method such as a roll coating method, a gravure coating method, a micro gravure coating method, a flow coating method, a bar coating method, a spray coating method, a die coating method, a spin coating method, and a dip coating method, a substrate Can be selected in consideration of the type, shape, productivity, and controllability of the film thickness.
The evaporation of the solvent is preferably carried out in the atmosphere at room temperature from the viewpoint of obtaining an antireflection film having a sufficiently small difference in the antireflection effect at different wavelengths, but for the purpose of promoting the evaporation of the solvent, the present invention Heating, decompression, or the like may be performed within a range that does not impair the effect.

Examples of the member to which the antireflection film of the present invention is applied include prisms, lens sheets, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, rear projection display screens, optical components such as optical fibers and optical couplers;
Transparent protective plates such as glass for show windows, glass for showcases, advertising covers, photo stand covers, etc .;
Protection plates such as CRT, liquid crystal display, plasma display, rear projection display;
Optical recording media represented by magneto-optical disks, read-only optical disks such as CD / LD / DVD, phase transition optical disks such as PD, hologram recording, etc .;
Photolithography-related members during semiconductor manufacturing, such as photoresists, photomasks, pellicles, and reticles;
Examples include protective covers for light emitters such as halogen lamps, fluorescent lamps, and incandescent lamps.
In particular, it can be suitably applied to the antireflection for large displays used in digital signage.

  EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

The measurement methods employed in this specification are summarized below.
(1) Measurement of average molecular weight By gel permeation chromatography (GPC), using GPC HLC-8020 manufactured by Tosoh Corporation, one column manufactured by Shodex (one GPC KF-801 and one GPC KF-802) The weight average molecular weight and the number average molecular weight were calculated from data measured by flowing tetrahydrofuran (THF) at a flow rate of 1 ml / min as a solvent using two GPC KF-806Ms connected in series.
(2) Fluorine content 10 mg of sample was burned by the oxygen flask combustion method, the decomposition gas was absorbed in 20 ml of deionized water, and the fluorine ion concentration in the absorption liquid was determined by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion). ) To determine by weight (% by weight).
(3) Refractive index (n _D )
The measurement was performed using an Abbe refractometer manufactured by Atago Optical Instruments Co., Ltd. at 25 ° C. using sodium D line (589 nm) as a light source.
(4) Glass transition temperature (Tg)
Using DSC (Differential Scanning Calorimeter: SEIKO, RTG220), the temperature range from -50 ° C to 200 ° C is raised (first run)-lowered-raised (second run) under the condition of 10 ° C / min. The intermediate point of the endothermic curve in the second run was defined as Tg (° C.).
(5) IR analysis It measured at room temperature with the Fourier transform infrared spectrophotometer 1760X by Perkin Elmer.
(6) Film thickness Measured with a spectroscopic ellipsometer EC400 manufactured by JA Woollam Japan.
WVASE32 was used as analysis software.

  The functional group-containing fluorine-containing allyl ether polymers (a) to (c) shown below were synthesized.

を２６．８ｇと、［Ｈ（ＣＦ₂ＣＦ₂）₃ＣＯＯ］₂−の８．０重量％パーフルオロヘキサン溶液を２０．1ｇ入れ、充分に窒素置換を行ったのち、窒素気流下２０℃で２４時間撹拌を行ったところ、高粘度の固体が生成した。
得られた固体をジエチルエーテルに溶解させたものをヘキサンに注ぎ、分離、真空乾燥させ、無色透明な重合体１８．８ｇを得た。
この重合体をＢＲＵＫＥＲ社製のＮＭＲ測定装置を用いて¹⁹Ｆ−ＮＭＲ分析（測定条件：２８２ＭＨｚ（トリクロロフルオロメタン：０ｐｐｍ））、¹Ｈ−ＮＭＲ分析（測定条件：３００ＭＨｚ（テトラメチルシラン＝０ｐｐｍ）を行い、ＩＲ分析（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製フーリエ変換赤外分光光度計１７６０Ｘで室温にて測定）により分析したところ、上記含フッ素アリルエーテルの構造単位のみからなり側鎖末端にヒドロキシ基を有する含フッ素重合体であった。また、数平均分子量は３１０００、重量平均分子量は７８０００であった。
Ｔｇ＝３２℃、フッ素含有率（重量％）＝６０、屈折率＝１．３６であった。Synthesis Example 1 (Synthesis of fluorinated allyl ether polymer (a) (PAEH-1) having a hydroxyl group)
In a 100 ml glass four-necked flask equipped with a stirrer thermometer, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol):

And 28.1 g of [H (CF ₂ CF ₂ ) ₃ COO] ₂ -in an 8.0 wt% perfluorohexane solution, and after sufficiently purging with nitrogen, the reaction was carried out at 20 ° C. under a nitrogen stream. After stirring for 24 hours, a highly viscous solid was produced.
A solution obtained by dissolving the obtained solid in diethyl ether was poured into hexane, separated and dried under vacuum to obtain 18.8 g of a colorless and transparent polymer.
This polymer was subjected to ¹⁹ F-NMR analysis (measurement conditions: 282 MHz (trichlorofluoromethane: 0 ppm)) and ¹ H-NMR analysis (measurement conditions: 300 MHz (tetramethylsilane = 0 ppm) using an NMR measuring apparatus manufactured by BRUKER. And analyzed by IR analysis (measured at room temperature with a Fourier transform infrared spectrophotometer 1760X manufactured by Perkin Elmer). As a result, the fluorine-containing fluorine-containing allyl ether structural unit alone and having a hydroxy group at the end of the side chain The polymer had a number average molecular weight of 31,000 and a weight average molecular weight of 78,000.
Tg = 32 ° C., fluorine content (% by weight) = 60, and refractive index = 1.36.

を２５．０ｇと、［Ｈ（ＣＦ₂ＣＦ₂）₃ＣＯＯ］₂−の８．０重量％パーフルオロヘキサン溶液を１４．８ｇ入れ、充分に窒素置換を行ったのち、窒素気流下２０℃で２４時間撹拌を行ったところ、高粘度の固体が生成した。得られた固体をアセトンに溶解させたものをパーフルオロヘキサンに注ぎ、分離、真空乾燥させ、無色透明な重合体２２．４ｇを得た。この重合体を¹⁹Ｆ−ＮＭＲ、¹Ｈ−ＮＭＲ分析、ＩＲ分析により分析したところ、上記含フッ素アリルエーテルの構造単位のみからなり側鎖末端にカルボキシ基を有する含フッ素重合体であった。
また、数平均分子量は７２５００、重量平均分子量は２０３０００であった。
Ｔｇ＝３８℃、フッ素含有率（重量％）＝５２、屈折率＝１．３８であった。Synthesis Example 2 (Synthesis of fluorinated allyl ether homopolymer (b) (PAEC-0) having a COOH group)
In a 100 ml glass four-necked flask equipped with a stirrer and a thermometer, add 6H, 6H-perfluoro-2-methyl-3-oxa-5-hexenoic acid:

25.0 g and 14.8 g of an 8.0 wt% perfluorohexane solution of [H (CF ₂ CF ₂ ) ₃ COO] ₂ − were added and thoroughly purged with nitrogen, and then at 20 ° C. under a nitrogen stream. After stirring for 24 hours, a highly viscous solid was produced. A solution obtained by dissolving the obtained solid in acetone was poured into perfluorohexane, separated and vacuum dried to obtain 22.4 g of a colorless and transparent polymer. When this polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, it was a fluorine-containing polymer comprising only the structural unit of the fluorine-containing allyl ether and having a carboxy group at the end of the side chain.
The number average molecular weight was 72500, and the weight average molecular weight was 203000.
Tg = 38 ° C., fluorine content (% by weight) = 52, and refractive index = 1.38.

を２５．０ｇと、［Ｈ（ＣＦ₂ＣＦ₂）₃ＣＯＯ］₂−の８．０重量％パーフルオロヘキサン溶液を１５．1ｇ入れ、充分に窒素置換を行ったのち、窒素気流下２０℃で２４時間撹拌を行ったところ、高粘度の固体が生成した。得られた固体をアセトンに溶解させたものをパーフルオロヘキサンに注ぎ、分離、真空乾燥させ、無色透明な重合体１８．２ｇを得た。この重合体を¹⁹Ｆ−ＮＭＲ、¹Ｈ−ＮＭＲ分析、ＩＲ分析により分析したところ、上記含フッ素アリルエーテルの構造単位のみからなり側鎖末端にカルボキシ基を有する含フッ素重合体であった。
また、数平均分子量は２８０００、重量平均分子量は７００００であった。
Ｔｇ＝１３℃、フッ素含有率（重量％）＝５８、屈折率＝１．３５であった。Synthesis Example 3 (Synthesis of homopolymer (c) (PAEC-1) of fluorine-containing allyl ether (AEC-1) having a COOH group)
In a 100 ml glass four-necked flask equipped with a stirrer and a thermometer, 9H, 9H-perfluoro-2,5-dimethyl-3,6-dioxa-8-nonenoic acid:

25.0 g and 15.1 g of an 8.0 wt% perfluorohexane solution of [H (CF ₂ CF ₂ ) ₃ COO] ₂ − were added and sufficiently purged with nitrogen, and then at 20 ° C. under a nitrogen stream. After stirring for 24 hours, a highly viscous solid was produced. A solution obtained by dissolving the obtained solid in acetone was poured into perfluorohexane, separated and vacuum-dried to obtain 18.2 g of a colorless and transparent polymer. When this polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, it was a fluorine-containing polymer comprising only the structural unit of the fluorine-containing allyl ether and having a carboxy group at the end of the side chain.
The number average molecular weight was 28,000 and the weight average molecular weight was 70000.
Tg = 13 ° C., fluorine content (% by weight) = 58, refractive index = 1.35.

Synthesis Example 4 Synthesis of ARSi25 (synthesis of terminal-modified PAEH-1)
PAEH-1 10 g (24.5 mmol MW78000), MIBK 100 g, and dibutyltin dilaurate 2.3 mg (170 ppm) were added to a 300 ml four-necked glass flask, and then dissolved at 50 ° C. in a nitrogen atmosphere. Thereafter, 3.02 g (12 mmol 0.5 eq) of 3-triethoxysilylpropyl isocyanate was added dropwise over 2 minutes. After dropping, the mixture was stirred at 50 ° C. for 35.5 hours, 7.8 mg of 600 ppm of Sn catalyst was dropped, and then stirred for 12 hours, and the completion of the reaction was confirmed by disappearance of the isocyanate-derived peak (2274 cm ⁻¹ ) in the IR spectrum. did. ¹⁹ F-NMR was used for product identification and modification rate calculations. The peak at -138.7 ppm was assigned to CF before modification, and the peak at -137.6 ppm was assigned to CF after modification. As a result, the denaturation rate was 25%. This is hereinafter referred to as “ARSi25”. That is, it is a polymer in which 25 mol% of the side chain terminal OH groups of PAEH-1 are substituted with triethoxysilyl groups. The refractive index of ARSi25 alone was 1.37. The ARSi25 solution used in this example was the same as that obtained in this synthesis example. That is, the solvent is methyl isobutyl ketone (MIBK) and the concentration is 10% by weight.

＜ＡＲＳｉ２５の構造式（ランダムコポリマー）＞

（ｐ：ｑ＝２５：７５（モル比））The reaction scheme and the structural formula of ARSi25 are shown below.
<Reaction scheme>

<Structural formula of ARSi25 (random copolymer)>

(P: q = 25: 75 (molar ratio))

Synthesis Example 5 Preparation of inorganic component liquid (hydrolyzable metal alkoxide liquid) TEOS (tetraethoxysilane) 2.08 g, MTES (methyltriethoxysilane) 2.08 g, EtOH 2.40 g, H ₂ O 1.17 g, 1NHCl 0.28 g was weighed in order, stirred well, and then allowed to stand overnight (inorganic component liquid 1).
4.16 g of TEOS, 2.40 g of EtOH, 1.17 g of H ₂ O, 0.28 g of 1N HCl were weighed in order and stirred well, and then allowed to stand overnight (inorganic component liquid 2).

Examples 1-3, Reference Examples 1-3
A film formed from a composition containing a solvent having a boiling point of 70 ° C. or higher and an SP value of 8.0 to 10.0, and a solvent having a boiling point of 70 ° C. or higher and an SP value of 10.0 or higher In order to compare the characteristics of the films formed from the compositions, the films of Examples 1 to 3 and Reference Examples 1 to 3 were prepared from the following compositions A to F (Table 1).
The ARSi25 solution obtained in Synthesis Example 4 was added to the inorganic component liquid whose concentration was adjusted with a solvent, so that the total solid content concentration and the polymer / SiO ₂ ratio were as shown in the following table.
In addition, methyl isobutyl ketone (MIBK) used as a solvent has a boiling point of 116 ° C. and an SP value of 8.57, while ethanol (EtOH) has a boiling point of 78 ° C. and an SP value of 12.97.

  The specific mixing amount (composition) is shown in the following table.

After mixing each component with the above composition and stirring well, the substrate was immediately coated. A silicon wafer was used as the substrate, and the film forming conditions were spin-coated (basic conditions: 2000 rpm, 25 s) and then dried at 70 ° C. for 2 minutes to obtain the films of Examples 1 to 3 and Reference Examples 1 to 3. .
The spin coating conditions were slightly changed so that the film thickness after drying of each film was about 150 nm.
The film thickness was a value measured with a spectroscopic ellipsometer.

Test Example 1 (Measurement of surface orientation)
The surface orientation (composition gradient) of the films of Examples 1 to 3 and Reference Examples 1 to 3 was evaluated.
X-ray photoelectron spectroscopy (ESCA) was used for composition gradient evaluation. ESCA 3400 manufactured by Shimadzu Corporation was used as ESCA. The composition change with respect to the depth was evaluated by the emission angle dependency evaluation.
In this measuring method, since the detection depth changes by tilting the sample film, the element ratio changes when there is a composition change. The information includes a depth of about 2 nm at an emission angle of 15 ° and a depth of about 10 nm at 90 °. The element ratio of F (fluorine) characteristic of the organic material (polymer component) and Si (silicon) characteristic of the inorganic material was calculated as F / Si and used as an index of the composition gradient. When there is a composition gradient of the film, F / Si changes in correlation with the emission angle, and in the case of a uniform film, F / Si shows a substantially constant value.
FIG. 1 shows the measurement results of the emission angle by ESCA for each film. The value of the theoretical composition ratio F / Si in each composition is shown in the following table.

Example 4, Reference Example 4
Contains a film formed from a composition containing a solvent having a boiling point of 70 ° C. or higher and an SP value of 8.0 to 10.0, and a solvent having a boiling point of 70 ° C. or lower and an SP value of 10.0 or higher. In order to compare the performance of the films formed from the compositions, the films of Example 4 and Reference Example 4 were prepared from the following compositions G and H.
A polymer solution in which PAEC-0, a polymer, is dissolved in a solvent is added to the inorganic component liquid whose concentration is adjusted with a solvent, and the total solid content concentration and polymer / SiO ₂ ratio are as shown in the following table. I did it. Methyl ethyl ketone (MEK) used as the solvent has a boiling point of 79 ° C. and an SP value of 9.27, and methanol (MeOH) has a boiling point of 65 ° C. and an SP value of 14.28.
In the same manner as in Example 1 and the like, films of Example 4 and Reference Example 4 were prepared from the compositions G and H, respectively.

Specific mixing amounts are shown in the following table. The PAEC-0 polymer solution used was 10% by weight.

Test Example 2 (Measurement of surface orientation)
The films of Example 4 and Reference Example 4 obtained as described above were evaluated for the composition change in the depth direction by ESCA in the same manner as in Test Example 1.
The results are shown in FIG. 2. Note that the theoretical F / Si is the same and is 1.46.

Example 5
In order to compare the properties of films formed at different drying temperatures, the film of Example 5 was prepared from the following composition I.
A composition I was prepared in the same manner as in Example 1 except that the drying conditions of the film were Condition 1 (room temperature) and Condition 2 (70 ° C., 2 minutes), and then a film was prepared. .

The specific mixing amount (composition) is shown in the following table. The concentration of the polymer solution of PAEC-1 used is 10% by weight.

Test Example 3 (Measurement of surface orientation)
Two types of films of Example 5 dried under different conditions (condition 1 (room temperature) and condition 2 (70 ° C., 2 minutes)) were subjected to composition change in the depth direction by ESCA as in Test Example 1. Was evaluated. The results are shown in FIG.

Comparative Test Example 1 (Example using a solvent having a boiling point of 70 ° C. or lower and an SP value of 8.0 or lower)
A film is produced in the same manner as in Examples 1 to 3 except that hexane (boiling point 69 ° C., SP value 7.24) is used instead of MIBK (boiling point 116 ° C., SP value 8.57) as a solvent. However, when other components were mixed with hexane, polymer precipitation occurred and a coating film could not be obtained.

Comparative Test Example 2 (Example using a solvent having a boiling point of 70 ° C. or higher and an SP value of 8.0 or lower)
A film is produced in the same manner as in Examples 1 to 3 except that heptane (boiling point 98 ° C., SP value 7.4) is used instead of MIBK (boiling point 116 ° C., SP value 8.57) as a solvent. However, when other components were mixed with heptane, polymer precipitation occurred and a coating film could not be obtained.

Comparative Test Example 3 (Example using a solvent having a boiling point of 70 ° C. or less and an SP value in the range of 8.0 to 10.0)
A film was produced in the same manner as in Examples 1 to 3, except that acetone (boiling point 56.5 ° C., SP value 9.77) was used instead of MIBK (boiling point 116 ° C., SP value 8.57) as a solvent. However, all the coating films became cloudy and a uniform film was not obtained.

Example 6 and Reference Example 5
(Comparison between using a solvent having a boiling point of 70 ° C. or higher and an SP value of 8.0 to 10.0 and a solvent having a boiling point of 70 ° C. or higher and an SP value of 10.0 or higher)
A polymer solution in which PAEC-1 as a polymer is dissolved in a solvent is added to an inorganic component liquid whose concentration is adjusted with a solvent, and the total solid content concentration and polymer / SiO ₂ ratio are as shown in the following table. I did it. The ethyl acetate used as solvent has a boiling point of 77 ° C. and an SP value of 9.1, and ethyl cellosolve has a boiling point of 135 ° C. and an SP value of 11.43.
In the same manner as in Example 1 and the like, films of Example 6 and Reference Example 5 were prepared from the compositions J and K, respectively.

  Specific mixing amounts are shown in the following table. The polymer solution of PAEC-1 used was 10% by weight.

Test Example 4 (Measurement of surface orientation)
The films of Example 6 and Reference Example 5 obtained as described above were evaluated for the composition change in the depth direction by ESCA in the same manner as in Test Example 1. The results are shown in FIG.
The theoretical F / Si is the same and is 1.85.

Examples 7-9
(Example when using a solvent having a boiling point of 70 ° C. or higher and an SP value in the range of 8.0 to 10.0)
A polymer solution in which PAEC-0, a polymer, is dissolved in a solvent is added to the inorganic component liquid whose concentration is adjusted with a solvent, and the total solid content concentration and polymer / SiO ₂ ratio are as shown in the following table. I did it. The butyl acetate used as solvent has a boiling point of 126 ° C. and an SP value of 8.46.
In the same manner as in Example 1 above, films of Examples 7 to 9 were prepared from the compositions L to N, respectively.

Specific mixing amounts are shown in the following table. The PAEC-0 polymer solution used was 10% by weight.

Test Example 5 (Measurement of surface orientation)
The films of Examples 7 to 9 obtained as described above were evaluated for the composition change in the depth direction by ESCA in the same manner as in Test Example 1. The results are shown in FIG.
The theoretical F / Si is shown in the following table.

Test Example 6 (Reflectance measurement)
After mixing with the composition of Example 3 (Composition C) and stirring well, the substrate was immediately coated. The substrate was TAC, and the film forming conditions were bar-coated and then dried at 70 ° C. for 2 minutes. The film thickness was adjusted to about 200 nm.

Using the obtained coating film as a sample, the transmittance of light having a wavelength of 400 nm to 700 nm was measured using a spectrophotometer “U-3410 type” with an integrating sphere having a diameter of 60 mm (manufactured by Hitachi, Ltd.). Moreover, it set to the visible ultraviolet spectrometer equipped with the acrylic board 5 degree regular reflection unit, and the reflectance was measured about the light of wavelength 300nm-1000nm.
The results are shown in FIG.

According to the composition for forming an antireflection film of the present invention, it has high antifouling properties, a high antireflection effect in a wide wavelength range, and a high mechanical strength, and in particular, reflection at different wavelengths over a wide wavelength range. An antireflection film having a sufficiently small difference in prevention effect can be obtained.
The antireflection film of the present invention formed from the composition for forming an antireflection film of the present invention can be used for antireflection of various members.

Claims (6)

(A) hydrolyzable metal alkoxide and / or hydrolyzate thereof,
(B) General formula (M)

[Where:
X ¹ and X ² are the same or different and are H or F;
X ³ is H, F, CH ₃ or CF ₃ ;
X ⁴ and X ⁵ are the same or different and are H, F or CH ₃ ,
Rf ¹ is an organic group in which 1 to 3 Y ³ are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms.
Y ³ is a functional group capable of reacting with a hydrolyzable metal alkoxide, or a C 1-10 monovalent organic group having the reactive group,
a is an integer of 0 to 3,
b and c are the same or different and are 0 or 1. )
And (C) a composition for forming an antireflection film comprising a solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8.0 to 10.0. (A) Hydrolyzable metal alkoxide (a) and / or a hydrolyzate thereof,
(B ′) General formula (M ′)

[Where:
X ¹ and X ² are the same or different and are H or F;
X ³ is H, F, CH ₃ or CF ₃ ;
X ⁴ and X ⁵ are the same or different and are H, F or CH ₃ ,
Rf ¹ is an organic group in which 1 to 3 Y ³ are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms.
Y ³ is a monovalent organic group having 1 to 10 carbon atoms having a functional group reacted with the hydrolyzable metal alkoxide (b) or a reactive group reacted with the hydrolyzable metal alkoxide (b);
a is an integer of 0 to 3,
b and c are the same or different and are 0 or 1. )
And (C) a composition for forming an antireflective film, comprising a solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8.0 to 10.0. .   The composition for forming an antireflection film according to claim 1, wherein the reactive group is a hydroxy group.   3. The antireflection film-forming material according to claim 1, wherein each of the hydrolyzable metal alkoxide, the hydrolyzable metal alkoxide (a), and the hydrolyzable metal alkoxide (b) contains Si as a metal. Composition. The functional group reacted with the hydrolyzable metal alkoxide (b)

The composition for forming an antireflection film according to claim 2. Applying the antireflection film-forming composition according to claim 1 or 2 to a member to prevent reflection, and evaporating the solvent from the applied antireflection film-forming composition. Antireflection film to be formed.

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