JP2003026732A - Fluorinated copolymer, film-forming composition, reflection-preventive membrane, reflection-preventive film and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorinated copolymer whose cured film is excellent in marring resistance, a film-forming composition containing the same, a reflection-preventive membrane, a reflection-preventive film and a display device. SOLUTION: A reflection-preventive membrane excellent in reflection- preventive performance and marring resistance can be obtained by using a fluorinated copolymer represented by formula 1: wherein Rf<1> is a fluorinated alkyl group having a 1-30C straight-chain, branched or alicyclic structure and may have an ether linkage, Rf<2> is a 1-5C perfluoroalkyl group, A is a constituent having at least one reactive group which can participate in a crosslinking reaction, B is an optional constituent, a to d are respectively molar fractions of each constituent and respectively represent values satisfying the relations of 55<=a+b<=95, 5<=a<=90, 5<=b<=70, 5<=c<=45, and 0<=d<=40.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a novel fluorine-containing copolymer, a film-forming composition that can be used as an antireflection film, a paint, a low dielectric constant material effective as an electric / electronic component, and a coating composition formed by coating the composition. The present invention relates to an antireflection film having a low refractive index layer, a polarizing plate using the same, and a liquid crystal display device.

[0003]

2. Description of the Related Art An antireflection film is generally installed on the surface of an optical product or the like so as to reduce the reflectance by using the principle of optical interference in order to prevent the deterioration of contrast and the reflection of an image due to the reflection of external light. In an image display device such as a cathode ray tube display device (CRT), a plasma display panel (PDP) or a liquid crystal display device (LCD) which requires particularly good visibility, it is arranged on the outermost surface of the display surface.

Such an antireflection film can be produced by forming a low refractive index layer having an appropriate thickness on a high refractive index layer. As a low refractive index material, a material having a refractive index as low as possible is desired from the viewpoint of antireflection performance, and at the same time, high scratch resistance is required because it is used on the outermost surface of a display. From the viewpoint of productivity, a material that can be applied by wet coating is preferable.

As a means for lowering the refractive index of a material, it is common to introduce a fluorine atom, for example, Japanese Patent Laid-Open No. 8-923.
No. 23, JP-A Nos. 10-147749 and 10-253.
No. 88, etc., describes the use of an inexpensive curable polymer containing a fluorine-containing olefin as a main component in an antireflection film.

Curable fluorine-containing olefins have long been studied as weather resistant paints, for example, Japanese Patent Application Laid-Open No. 57-3.
No. 4107, No. 61-258852, No. 61-275.
No. 311, No. 62-85740, No. 62-29284.
Many reports such as No. 8 have been made.

Hexafluoropropylene used in the examples of the above publications has lower crystallinity than tetrafluoroethylene and is preferable as a material for the antireflection film low refractive index layer from the viewpoint of refractive index and solubility. is there. However, J. Polymer. Sci. , 4 (6),
481 (1952), The Chemical Society of Japan, 51 (1), 112.
As described in (1980) and the like, the monomer has poor homopolymerizability in a normal solution-type radical polymerization reaction, and can be subjected to alternating copolymerization with a relatively electron-donating monomer such as vinyl ether. , Even in this case up to 50mo
Since only about 1% can be introduced into the polymer, there was a problem for the purpose of sufficiently increasing the fluorine content and lowering the refractive index. On the other hand, octafluoro-1-butene can be introduced in an amount of 60 mol% or more depending on the conditions, but it is also difficult to introduce it in an amount of more than 70 mol%, and there is a problem that the monomer is poor in versatility.

In order to lower the refractive index of the polymer, it is sufficient to lower the composition of the crosslinkable monomer having a high refractive index and increase the copolymerization composition of ethyl vinyl ether or the like having a relatively low refractive index, but there is a limit. Is also disadvantageous in terms of scratch resistance.

On the other hand, in the examples of the above-mentioned publication, there is described a method of increasing the fluorine content by introducing perfluoro (propyl vinyl ether). However, since this monomer also shows the same polymerization reactivity as hexafluoropropylene, when it is copolymerized alone with hexafluoropropylene, the total mole fraction with hexafluoropropylene is not less than 50 mol% in the polymer. Is difficult to introduce. Although the fluorine content can be increased to some extent by introducing perfluoro (propyl vinyl ether), the scratch resistance of the film is remarkably lowered, and there is a problem that the transparency of the film is lowered when the amount thereof is increased.

That is, in the hexafluoropropylene copolymer, it is desired to develop a material having a high fluorine content, a low refractive index, a good solvent solubility and a good coatability, an excellent transparency and an excellent scratch resistance. It was

[0011]

SUMMARY OF THE INVENTION The first object of the present invention is to:
To provide a fluorine-containing copolymer having a high fluorine content and excellent scratch resistance of a cured film, and a film-forming composition containing the same. A low refractive index layer is formed by coating and curing on the refractive index layer to provide an inexpensive antireflection film having sufficient antireflection performance and scratch resistance. Thirdly, the antireflection film is provided. The present invention is to provide an antireflection film in which the above is arranged on a transparent support, and fourthly to provide a display device in which the antireflection film is arranged.

[0012]

The objects of the present invention have been achieved by the inventions 1) to 18) described below. 1) A fluorine-containing copolymer represented by the following general formula 1.

[0013]

[Chemical 2]

In the general formula 1, Rf ¹ represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, which may have an ether bond, and Rf ² has 1 carbon atom. ~ 5 represents a perfluoroalkyl group, A represents a constituent containing at least one reactive group capable of participating in a crosslinking reaction, B represents an arbitrary constituent,
a to d each represent a mole fraction (%) of each constituent component, and 55 ≦ a + b ≦ 95, 5 ≦ a ≦ 90, 5 ≦, respectively.
It represents a value that satisfies the relationship of b ≦ 70, 5 ≦ c ≦ 45, and 0 ≦ d ≦ 40. 2) 1) above fluorine-containing copolymer according to Rf ¹ in the general formula 1 are characterized by being represented by the following general formula 2.

[0015]

[Chemical 3]

In the general formula 2, Rf ³ represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 20 carbon atoms, which may have an ether bond, and p is 0 to 5
Represents an integer, and q represents 0 or 1. 3) The above 1) fluorine-containing copolymer according to Rf ¹ in the general formula 1 are characterized by being represented by the following general formula 3.

[0017]

[Chemical 4]

In the general formula 3, R is a hydrogen atom or has 1 carbon atom.
~ 5 represents an alkyl group containing or not containing a fluorine atom, may have an ether bond, Rf ⁴ is a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 14 carbon atoms. , R and Rf ⁴ may combine with each other to form a ring, and r represents an integer of 0 to 4. 4) The fluorine-containing copolymer as described in any one of 1) to 3) above, wherein c in the general formula 1 is 25 ≦ c ≦ 40. 5) A in the above general formula 1 represents a constituent component of a polymer having a silyl group having a hydrolyzable group, a group having a reactive unsaturated double bond, or a ring-opening polymerization reactive group. 5. The fluorine-containing copolymer as described in any one of 1) to 4) above. 6) The above 1), wherein A in the above general formula 1 represents a constituent component of the polymer represented by the following general formula 4.
~ 5) The fluorocopolymer according to any one of 5).

[0019]

[Chemical 5]

In the general formula 4, L ¹ represents an alkylene group having 1 to 20 carbon atoms, X represents a hydroxyl group or a hydrolyzable group, and s represents 0 or 1. 7) A in the above general formula 1 represents a constituent component of a polymer represented by the following general formula 5, 1) above.
~ 5) The fluorocopolymer according to any one of 5).

[0021]

[Chemical 6]

In the general formula 5, L ² represents a linking group having 1 to 20 carbon atoms, R ¹ represents a hydrogen atom or a methyl group, and t
Represents 0 or 1. 8) The above 1), wherein A in the above general formula 1 represents a constituent component of the polymer represented by the following general formula 6.
~ 5) The fluorocopolymer according to any one of 5).

[0023]

[Chemical 7]

In the general formula 6, L ³ represents a linking group having 1 to 20 carbon atoms, and u represents 0 or 1. 9) The above 1), wherein A in the above general formula 1 represents a constituent component of the polymer represented by the following general formula 7.
~ 5) The fluorocopolymer according to any one of 5).

[0025]

[Chemical 8]

In the general formula 7, L ⁴ represents a linking group having 1 to 20 carbon atoms, R ² and R ³ represent a hydrogen atom or a methyl group, and v represents 0 or 1. 10) The fluorinated copolymer as described in any one of 1) to 5) above, wherein A in the general formula 1 represents a constituent component of the polymer represented by the following general formula 8.

[0027]

[Chemical 9]

In the general formula 8, L ⁵ represents a linking group having 1 to 20 carbon atoms, R ⁴ and R ⁵ represent a hydrogen atom or a methyl group, and w represents 0 or 1. 11) A film-forming composition comprising the fluorocopolymer according to any one of 1) to 10) above. 12) The film-forming composition as described in 11) above, which contains inorganic fine particles. 13) The inorganic fine particles described in 12) above are average particle systems 1 to 5
The above 12) characterized by being 0 nm silica fine particles
The film-forming composition as described above. 14) The above 11) to characterized by containing a curing agent
The film-forming composition as described in any one of 13). 15) The curing agent according to 14) above, which is a compound having a polymerizable vinyl group or a ring-opening polymerizable group, a silicon compound having a hydroxyl group or a hydrolyzable group, or a partial condensate thereof. 14) The film-forming composition as described above. 16) An antireflection film having a low refractive index layer formed by applying and curing the film forming composition as described in any one of 11) to 15) above. However, in the case where the constituent component A in the fluorine-containing copolymer has an epoxy group, the form of the antireflection film formed by coating and curing a film-forming composition containing an epoxy group-containing curing agent and fine particles. Is excluded. 17) An antireflection film comprising the transparent support and the antireflection film according to 16) provided thereon. 18) A display device comprising the antireflection film as described in 17) above.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer represented by the general formula 1 used in the present invention will be described. The copolymer represented by the general formula 1 is a random copolymer of a monomer component represented by M1 or M2 below and a monomer component forming A and B. Each of the constituent components represented by these general formulas may be composed of one type or a plurality of monomers.

[0030]

[Chemical 10]

[0031]

[Chemical 11]

Rf in the general formula 1¹Is a C1-C30 containing
Represents a fluorine alkyl group, preferably having 1 to 20 carbon atoms,
Particularly preferred is a fluorine-containing alkyl group having 1 to 15 carbon atoms.
is there. This fluorine-containing alkyl group has a straight chain (for example, -CF₂CF
₃, -CH₂(CF₂)_FourH, -CH₂(CF₂)₈CF ₃, -CH₂CH₂(CF₂)_FourH etc.)
Even a branched structure (eg CH (CF₃)₂, CH₂CF (CF₃)₂, CH (CH
₃) CF₂CF₃, CH (CH₃) (CF₂)_FiveCF₂H etc.),
Further, an alicyclic structure (preferably a 5-membered ring or a 6-membered ring, for example,
If perfluorocyclohexyl group, perfluorocyclo
A pentyl group or an alkyl group substituted with these)
It may have an ether bond (eg CH₂OCH₂CF₂CF
₃, CH₂CH₂OCH₂C_FourF₈H, CH₂CH₂OCH₂CH₂C₈F₁₇, CH₂CHF₂OCF₂CF
₂OCF₂CF₂H, etc., preferably as general formula 3 will be described below.
Structure). Rf¹Is perfluoroal
It may be a kill group.

A preferred form of Rf ¹ is synthetic suitability,
From the viewpoint of adhesion to the substrate, the structure represented by the general formula 2 is preferable, and the structure represented by the general formula 3 is particularly preferable.

In the general formula 2, Rf ³ has 1 to 20 carbon atoms.
Fluorine-containing alkyl group (preferably a fluorine-containing alkyl group having 1 to 15 carbon atoms, particularly preferably 2 to 10 carbon atoms).
Is preferably a fluorine-containing alkyl group having a fluorine content of 60% by mass or more, particularly preferably a fluorine content of 70% by mass or more), and a straight chain (for example, Rf ^{1 is} an example). Or a branched (for example, the structure described above as an example of Rf ¹ ) or an alicyclic structure (for example, the structure described above as an example of Rf ¹ ). )
Or may have an ether bond (for example, the structure described above can be mentioned as an example of Rf ¹ ). p
Represents an integer of 0 to 5, more preferably an integer of 0 to 3, and particularly preferably 0 or 1. q represents 0 or 1. The group of Rf ³ may be a perfluoro group.

In the general formula 3, Rf ⁴ has the same meaning as described above for Rf ³ , and R represents a hydrogen atom or an alkyl group containing or not containing a fluorine atom having 1 to 10 carbon atoms (for example, CH. ₃ , CH ₂ CH ₃ , CH ₂ CF
₃ etc.), preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R and Rf ⁴ are bonded to each other to form a ring structure (preferably a 5-membered or 6-membered ring such as perfluorocyclohexyl group, perfluorocyclopentyl group). Group, a perfluorotetrahydrofuryl group, etc.) may be formed.
r represents an integer of 0 to 4, preferably an integer of 0 to 3, and particularly preferably 0 or 1.

Examples of the monomer M1 forming the copolymer represented by the general formula 1 are shown below, but the present invention is not limited thereto.

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

The above-mentioned monomer represented by M1 is, for example,
Macromolecules, 32 (21), 7122 (1999), JP-A-2-721
As described in the above publication, a method of allowing a fluorine-containing alcohol to act on a leaving group-substituted alkyl vinyl ether such as vinyloxyalkyl sulfonate or vinyloxyalkyl chloride in the presence of a base catalyst, International Application Patent Publication No. 9
As described in 2/05135, a method of mixing a fluorine-containing alcohol and vinyl ethers such as butyl vinyl ether in the presence of a catalyst such as palladium to exchange vinyl groups, a fluorine-containing ketone and dibromoethane as described in US Pat. No. 3,420,793. It can be synthesized by a method of reacting in the presence of a potassium fluoride catalyst and then performing a HBr removal reaction with an alkali catalyst.

In the monomer M2 forming the copolymer represented by the general formula 1, Rf ² represents a perfluoroalkyl group having 1 to 5 carbon atoms. From the viewpoint of polymerization reactivity, a perfluoromethyl group or a perfluoroethyl group is preferable,
From the viewpoint of availability, a perfluoromethyl group (M2 represents hexafluoropropylene) is particularly preferable.

A represents a constituent component of a monomer containing at least one reactive group capable of participating in a crosslinking reaction. Examples of the reactive group that can participate in the crosslinking reaction include a silyl group having a hydroxyl group or a hydrolyzable group (eg, alkoxysilyl group, acyloxysilyl group, etc.), a group having a reactive unsaturated double bond ((meth) Acryloyl group, allyl group, vinyloxy group, etc.), ring-opening polymerization reactive group (epoxy group, oxetanyl group, oxazolyl group, etc.), group having active hydrogen atom (eg hydroxyl group, carboxyl group, amino group, carbamoyl group, mercapto group) , Β-ketoester groups, hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups (active halogen atoms, sulfonic acid esters, etc.) that can be substituted by a nucleophile, and the like.

Of these reactive groups, a group having a polymerization activity alone is preferable, and a hydrolyzable silyl group, a group having a reactive unsaturated double bond, and a ring-opening polymerization reactive group are more preferable, and Preferably, a hydrolyzable silyl group,
It is a (meth) acryloyl group, an allyl group, or an epoxy group. General formulas 4 to 8 are mentioned as particularly preferable forms of A.

In the general formula 4, L ¹ represents an alkylene group having 1 to 20 carbon atoms, which may have a substituent (for example, an alkyl group, an alkoxy group, a halogen atom, etc.) and an aliphatic ring. It may have a structure (for example, a cyclohexane ring or the like). An alkylene group having 1 to 5 carbon atoms is preferable, and an ethylene group or a propylene group is particularly preferable. s represents 0 or 1, and is preferably 0 from the viewpoint of polymerization reactivity. X represents a hydroxyl group or a hydrolyzable group (for example, an alkoxy group such as a methoxy group and an ethoxy group, a halogen atom such as chloro and bromo, an acyloxy group such as an acetoxy group and a phenoxy group), and preferably a methoxy group or an ethoxy group. It is a base.
The constituent component represented by the general formula 4 is disclosed in JP-A-48-627.
As described in No. 26, it can be synthesized by a method utilizing a hydrosilylation reaction or the like.

In the general formula 5, L ² represents an alkylene group having 1 to 20 carbon atoms, which may have a substituent (for example, an alkyl group, an alkoxy group, a halogen atom, etc.) and an aliphatic ring. It may have a structure (for example, a cyclohexane ring or the like). An alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 2 to 5 carbon atoms is particularly preferable. t represents 0 or 1, and preferably t is 1. R ¹ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Unsaturation 2 in general formula 5
The heavy bond may be introduced by a method of synthesizing a polymer having a hydroxyl group and then acting an acid halide such as (meth) acrylic acid chloride or an acid anhydride such as (meth) acrylic acid anhydride. It may be formed by a conventional method such as dehydrochlorination after polymerizing a vinyl monomer having a chloropropionate moiety.

In the general formula 6, L ³ and u have the same meanings as L ² and t in the general formula 5, respectively. General formula 5
The allyl group in the constituent component represented by can also be introduced by a method of synthesizing a polymer having a hydroxyl group like the constituent component of the general formula 5 and then allowing allyl halide to act.

In the general formula 7, L ⁴ has the same meaning as L ² in the general formula 5, respectively. v represents 0 or 1. R
² and R ³ each represent a hydrogen atom or a methyl group, preferably a hydrogen atom. The component represented by the general formula 7 is a method of reacting a vinyl ether having a hydroxyl group with an epoxy compound such as epichlorohydrin,
It can be obtained by polymerizing an epoxy group-containing vinyl ether synthesized by a method in which glycidol is allowed to act on butyl vinyl ether in the presence of a catalyst to carry out ether exchange.

L ⁵ , w, R ⁴ and R in the general formula 8
⁵ is L ⁴ , v, R ² and R in the general formula 7, respectively.
It has the same meaning as ³ . The constituent component represented by the general formula 8 is also synthesized in the same manner as the constituent component represented by the general formula 7.

Functional groups other than the particularly preferred examples of the constituent component A described above may be introduced from the monomer stage, or a polymer having a reactive group such as a hydroxyl group may be introduced after the synthesis. .

Preferred examples of the constituent component represented by A in the polymer represented by the general formula 1 are shown below, but the present invention is not limited thereto.

[0055]

[Chemical 19]

[0056]

[Chemical 20]

[0057]

[Chemical 21]

[0058]

[Chemical formula 22]

[0059]

[Chemical formula 23]

[0060]

[Chemical formula 24]

[0061]

[Chemical 25]

[0062]

[Chemical formula 26]

[0063]

[Chemical 27]

[0064]

[Chemical 28]

[0065]

[Chemical 29]

[0066]

[Chemical 30]

[0067]

[Chemical 31]

In the general formula 1, B represents an arbitrary constituent component, and is a constituent component of a monomer copolymerizable with the monomer represented by M1 and M2 and the monomer forming the constituent component represented by A. There is no particular limitation as long as it is, adhesion to a substrate, Tg of a polymer (which contributes to film hardness), solubility in a solvent,
It can be appropriately selected from various viewpoints such as transparency, slipperiness, and dust / fouling resistance.

For example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, vinyl acetate, vinyl propionate,
Examples thereof include vinyl esters such as vinyl butyrate and vinyl cyclohexanecarboxylate, and structural units having a polysiloxane structure (for example, structural components derived from the Wako Pure Chemical Initiator VPS1001).

In the general formula 1, a to d represent the mole fraction (%) of each constituent component, and 55≤a + b≤95, 5≤a≤
90, 5 ≦ b ≦ 70, 5 ≦ c ≦ 45, and 0 ≦ d ≦ 40 are selected.

In order to lower the refractive index of the material, it is desired to increase the mole fraction (%) b of the M2 component, but from the viewpoint of polymerization reactivity, it is 50 to 70 in a general solution type radical polymerization reaction.
It is difficult to introduce more than%, as it is the limit. In the present invention, b is preferably 40% or more,
It is particularly preferably 45% or more.

In the present invention, as a means for lowering the refractive index, the M1 component is introduced in addition to the M2 component. Molar fraction of M1 component
a is preferably in the range of 10 ≦ a ≦ 50%, particularly preferably 20 ≦ a ≦ 40%. The sum of the mole fraction (%) of the M1 component and the mole fraction (%) of the M2 component is preferably in the range of 60 ≦ a + b ≦ 90%, 60
It is particularly preferable that ≦ a + b ≦ 75%.

When the proportion of the polymer unit represented by A is too small, the strength of the cured film becomes weak. In the present invention, the molar fraction (%) of the component A is preferably in the range of 10 ≦ c ≦ 40%, and particularly preferably in the range of 25 ≦ c ≦ 40%.

The molar fraction (%) d of the optional component represented by B is preferably in the range of 0≤d≤20%, particularly preferably in the range of 0≤d≤10%.

Examples of the polymer represented by the general formula 1 of the present invention are shown below, but the present invention is not limited thereto. In Tables 1 and 2, the monomers M1 and M which form the fluorine-containing component of the general formula 1 by polymerization are shown.
2, the constituent component A and the monomer Bm forming the optional constituent component B are described as a combination. The abbreviations in the table represent the following. HFP: Hexafluoropropylene PFB: Perfluoro (1-butene) PFP: Perfluoro (1-pentene) PFN: Perfluoro (1-nonene) EVE: Ethyl vinyl ether CHVE: Cyclohexyl vinyl ether VAc: Vinyl acetate

[0076]

[Table 1]

[0077]

[Table 2]

The polymer represented by the general formula 1 of the present invention can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization and emulsion polymerization. Further, at this time, the synthesis can be performed by a known operation such as batch system, semi-continuous system, continuous system and the like.

The polymerization can be initiated by using a radical initiator, irradiating with light or radiation, and the like. These polymerization methods and methods of initiating the polymerization are described in, for example, Sadaji Tsuruta “Polymer Synthesis Method” revised edition (published by Nikkan Kogyo Shimbun Co., 1971), Takayuki Otsu, and Masayoshi Kinoshita “Experimental Method of Polymer Synthesis”, Kagaku Dojin It is described on pages 124 to 154, published in 1972.

Of the above-mentioned polymerization methods, the solution polymerization method using a radical initiator is particularly preferable. The solvent used in the solution polymerization method, for example, ethyl acetate, butyl acetate, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N
-Dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-
Various organic solvents such as butanol may be used alone or as a mixture of two or more kinds, or as a mixed solvent with water.

The polymerization temperature needs to be set in relation to the molecular weight of the copolymer to be formed, the kind of the initiator and the like, and it can be from 0 ° C. or lower to 100 ° C. or higher. It is preferable to carry out.

The reaction pressure can be appropriately selected, but is usually 1 to 100 kg / cm ² , and particularly preferably 1 to 30 kg / cm ² . The reaction time is about 5 to 30 hours.

A known catalyst may be used in the film-forming composition of the present invention, which may be appropriately mixed with a curing catalyst, a curing agent or the like. The film-forming composition of the present invention comprises a fluoropolymer, a curing catalyst and a solvent. In addition, additives and additives for accelerating the curing and improving the performance for use of the polymer may be contained.

For example, when the polymer of the general formula 1 contains a hydrolyzable silyl group as a curing reactive site, a known acid or base catalyst can be added as a catalyst for the sol-gel reaction, for example, hydrochloric acid, sulfuric acid, Inorganic Bronsted acids such as nitric acid, organic Bronsted acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid, paratoluenesulfonic acid, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, triisopropoxy aluminum, tetrabutoxy Examples thereof include Lewis acids such as zirconium, inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, organic bases such as triethylamine, pyridine and tetramethylethylenediamine, but acid catalysts are particularly preferable, and paratoluene is particularly preferable. Sulfone Organic Bronsted acids or Lewis acids such as dibutyltin dilaurate and the like are preferable.

The amount of these curing catalysts added depends on the kind of catalyst,
Although it varies depending on the difference in the curing reactive site, it is generally 0.1 to 15 relative to the total solid content of the film-forming composition.
The amount is preferably about mass%, more preferably about 0.5 to 5 mass%.

The film-forming composition of the present invention is stable as a composition until a reaction initiation trigger (energy ray, heat) is given. From the viewpoint of storage stability of the film-forming composition, a compound that generates a curing accelerator such as an acid or a base by the action of light may be used. When these compounds are used, the coating can be cured by irradiation with active energy rays.

Examples of the compound that generates an acid by the action of light include, for example, "Organic materials for imaging" p187 to 19 edited by The Society for Organic Electronics Materials (Bunshin Publishing).
8, various examples are described in JP-A No. 10-2826444, and these known compounds can be used.
Specifically, RSO ₃ ⁻ (R represents an alkyl group or an aryl group), AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ or the like as a counter ion, a diazonium salt, an ammonium salt, a phosphonium salt, Various onium salts such as iodonium salts, sulfonium salts, selenonium salts and arsonium salts, organic halides such as trihalomethyl group-substituted oxadiazole derivatives and S-triazine derivatives, organic acid o-nitrobenzyl esters, benzoin esters, Examples thereof include imino esters and disulfone compounds, and preferably
Onium salts, particularly preferably sulfonium salts and iodonium salts. Known compounds can be used as the compound that generates a base by the action of light, and specific examples thereof include nitrobenzyl carbamates and dinitrobenzyl carbamates.

In the present invention, it is particularly preferable to use a compound capable of generating an acid by the action of light. Examples of such compounds include benzoin sulfonate. A sensitizing dye can also be preferably used in combination with a compound which generates an acid or a base by the action of these lights. The addition amount of the compound that accelerates the curing reaction by the action of light of the present invention is preferably 0.1 to 15% by mass, and more preferably 0.5 to 5% by mass based on the total solid content in the film-forming composition. It is% by mass.

Further, a dehydrating agent may be used for the purpose of promoting curing. Examples of the dehydrating agent include carboxylic acid orthoesters (methyl orthoformate, ethyl orthoformate, methyl orthoacetate, etc.), or acid anhydrides (acetic anhydride, etc.).
Etc. can be mentioned.

At this time, organic silicates (tetraethoxysilane, methyltrimethoxysilane, etc., various alkoxysilane hydrolyzed partial condensates) or various silane coupling agents (for example, as described in JP-A-61-258852) are used. (γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, etc.) may be used together as a curing agent. When these curing agents are used, it may be added in an amount of 0.
The addition amount is preferably about 5 to 300 parts by mass, and particularly preferably about 5.0 to 100 parts by mass per 100 parts of the fluorocopolymer.

On the other hand, when the crosslinking reactive site represented by A in the above general formula 1 has an unsaturated double bond capable of radical polymerization (acryloyl group, methacryloyl group, etc.), a radical polymerization initiator may be added. preferable. The radical polymerization initiator may be in the form of a radical which is generated by the action of heat or a radical which is generated by the action of light.

As the compound which initiates radical polymerization by the action of heat, organic or inorganic peroxides, organic azo and diazo compounds can be used. In particular,
Benzoyl peroxide, halogenobenzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, ammonium persulfate, potassium persulfate as inorganic peroxides Examples of the azo compound include 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, and examples of the diazo compound include diazoaminobenzene and p-nitrobenzenediazonium. it can.

When a compound which initiates radical polymerization by the action of light is used, the coating is cured by irradiation with active energy rays. Examples of such photo-radical polymerization initiators include acetophenones, benzoins,
Benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds,
There are disulfide compounds, fluoroamine compounds and aromatic sulfonium compounds. Examples of acetophenones include:
2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenylketone,
1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone is included.
Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. A sensitizing dye can also be preferably used in combination with these photo-radical polymerization initiators.

The amount of the compound that initiates radical polymerization by the action of heat or light may be any amount as long as it initiates the polymerization of carbon-carbon double bonds, but it is generally used in the film-forming composition. The amount is preferably 0.1 to 15% by mass, more preferably 0.5 to 5% by mass, based on the total solid content.

When the compound represented by the general formula 1 has a radical-polymerizable unsaturated double bond, it cures without using any other curing agent. Preferred examples include polyfunctional unsaturated monomers capable of reacting with these unsaturated bonds (for example, (meth) acrylate monomers derived from polyhydric alcohols such as dipentaerythritol hexa (meth) acrylate). it can.

When these curing agents are added, the amount of addition is preferably about 0.5 to 300 parts by weight per 100 parts by weight of the above-mentioned fluorine-containing copolymer, and particularly, the fluorine-containing copolymer 10
The amount added is preferably about 5.0 to 100 parts by mass per 0 parts by mass.

When the cross-linking reactive site represented by A in the above general formula 1 has a cationically polymerizable group (epoxy group, oxetanyl group, oxazolyl group, vinyloxy group, etc.), the hydrolyzable silyl group is used as a curing catalyst. The acid catalyst and the photo-acid generator described as the group curing catalyst can be added. The preferable range of these addition amounts is also the same as the range described above as the curing catalyst for the hydrolyzable silyl group.

At this time, it is not necessary to use other curing agent in combination, but a curing agent can be appropriately added. As a curing agent, a polyfunctional compound capable of reacting with these cationically polymerizable groups (for example, polybasic acid such as pyromellitic acid, trimellitic acid, phthalic acid, maleic acid, succinic acid, etc. A compound having a plurality of) are preferred.

When these curing agents are added, the amount of addition is preferably about 0.5 to 300 parts by mass per 100 parts by mass of the above-mentioned fluorine-containing copolymer, and particularly, the fluorine-containing copolymer 10
The amount added is preferably about 5.0 to 100 parts by mass per 0 parts by mass.

When the curing reactive site is a group having active hydrogen such as a hydroxyl group, it is preferable to add a curing agent. Examples of such a curing agent include polyisocyanate type, aminoplast, polybasic acid or its anhydride. You can list things.

As the polyisocyanate system, polyisocyanate compounds such as m-xylylene diisocyanate, toluene-2,4-diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate,
Silyl isocyanate compounds such as methylsilyl triisocyanate, partial condensation products of these isocyanate compounds, multimers, adducts with polyhydric alcohols, low molecular weight polyester film, etc., blocked isocyanate groups with a blocking agent such as phenol Examples thereof include polyisocyanate compounds.

As the aminoplast, melamines, guanamines, ureas and the like are used. Among them, methylol melamine at least partially etherified with one or more lower alcohols such as methanol, ethanol, propanol and butanol (eg hexamethyl etherified methylol melamine, hexabutyl etherified methylol melamine, methyl butyl mixed etherified methylol). Preferred examples include melamine, methyl etherified methylol melamine, butyl etherified methylol melamine, etc.), or condensates thereof.

Examples of the polybasic acid or its anhydride include aromatic polyvalent carboxylic acids such as pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid and phthalic anhydride, or their anhydrides. Examples thereof include aliphatic polycarboxylic acids such as maleic acid, maleic anhydride, succinic acid, and succinic anhydride, and anhydrides thereof.

In the present invention, the blending amount of each component can be appropriately selected, but the above fluorine-containing copolymer 10
The amount of the curing agent is preferably about 0.5 to 300 parts by weight per 0 parts by weight, and particularly preferably about 5.0 to 100 parts by weight per 100 parts by weight of the fluorocopolymer. Further, the compound represented by the general formula 1 of the present invention and these curing agents may be partially condensed beforehand.

In order to accelerate the curing reaction together with the above-mentioned curing agent, a curing-accelerating catalyst can be appropriately used if necessary. Examples of these include the above-mentioned base or acid catalysts as the curing catalyst for the hydrolyzable silyl group, and as described above, compounds which generate these catalysts by the action of light can also be preferably used.
The preferable range of these addition amounts is also the same as the range described above as the curing catalyst for the hydrolyzable silyl group.

When the curing reactive site is an acid anhydride group or a group which can be substituted by a nucleophilic species, a compound having a plurality of nucleophilic groups such as amino group and hydroxyl group in one molecule is used as a curing agent. It is preferable. At this time, the curing catalyst may or may not be added, but when added, the various acid and base catalysts described above in the case where A is a hydrolyzable silyl group can be used in similar addition amounts. . The preferable blending amount of the curing agent is the same as the range described above for the case where A is a group having active hydrogen.

When the copolymer of the present invention is used together with a curing agent as described above, it is general to select a curing agent that forms a bond with the site represented by A in the general formula 1. As long as there is no problem in compatibility, the bond formation between the copolymer and the curing agent is not always necessary, and various combinations can be made. For example, the functional group in the copolymer may be selected from the viewpoint of adhesion to the substrate, and the curing agent may be selected from the viewpoint of film hardness. Even if a direct bond is not formed, the cross-linking network formed by the above-mentioned copolymer and the cross-linking network formed by the curing agent form a so-called IPN structure. It can be preferably selected from the viewpoint of application and the like.

For example, as a combination of polymer-functional group / hardener functional group, epoxy group / acryl group, epoxy group / alkoxysilyl group, epoxy group / oxetanyl group, acryl group / epoxy group, acryl group / alkoxysilyl group,
Alkoxysilyl group / epoxy group, alkoxysilyl group /
Acrylic group, hydroxyl group / acrylic group, hydroxyl group / epoxy group,
Various combinations such as hydroxyl group / alkoxysilyl group are possible.

The film-forming composition of the present invention is usually prepared by dissolving the copolymer represented by the general formula 1 in a suitable solvent. At this time, the concentration of the copolymer is appropriately selected according to the application, but is generally about 0.01 to 60% by mass,
Preferably 0.5 to 50% by mass, particularly preferably 1% to
It is about 20% by mass.

The solvent is not particularly limited as long as the composition containing the copolymer represented by the general formula 1 can be uniformly dissolved or dispersed without causing precipitation, and two or more kinds of solvents are used in combination. You can also do it. Preferred examples include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,
4-dioxane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.

Fine particles such as silica and magnesium fluoride may be added to the composition for forming a film of the present invention in order to further improve the film strength or coating property, and it is preferable to add silica fine particles. The average particle size of the fine particles is 5 to
A film having a thickness of 50 nm is used, but preferably 5 to 30.
nm, and particularly preferably a particle size of 8 to 20 n.
m. Such silica fine particles are, for example, I.
In accordance with the method described in M. Thomas, Appl.Opt. You can In addition, commercially available products are Snowtex IPA-ST and MEK-S manufactured by Nissan Chemical Industries, Ltd.
T, Nippon Aerosil Co., Ltd. AEROSIL300, AEROSIL130, AEROSIL50, etc. can also be used. However, in the present invention, when the component A in the fluorine-containing copolymer of the general formula 1 has an epoxy group, a film forming composition containing an epoxy group-containing curing agent and fine particles is applied and cured. The form of the formed antireflection film is excluded.

The amount of the fine particles added is in the range of 5 to 95 mass% of the total solids after the coating film is cured, preferably 10 to 70.
%, Particularly preferably 20 to 60% by mass.

Others Additives such as various silane coupling agents, surfactants, thickeners, leveling agents, and slip agents may be appropriately added to the film-forming composition of the present invention.

The film is cured by drying at room temperature or by 3
It is carried out by heating at a temperature of about 0 to 200 ° C. for about 1 minute to 100 hours. When the film-forming composition of the present invention contains a compound that releases a curing accelerator by the action of light, a high pressure mercury lamp or the like is used to emit light corresponding to the absorption wavelength of the curing accelerator or the sensitizing dye. Curing is performed by irradiation. At this time, heating may be performed at a temperature of about 30 to 200 ° C. for about 1 minute to 10 hours after the light irradiation.

The film forming composition of the present invention can be applied to various substrates such as glass, plastic, metal, ceramics, wood and paper. Further, its application is not particularly limited, and it is an application utilizing the physical properties unique to the fluoropolymer such as weather resistance, water repellency, chemical resistance, antifouling property, low friction property, non-adhesiveness (for example, building material application , Coatings for automobile glass, coatings for cooking equipment, etc., and applications that take advantage of the low dielectric constant characteristics of fluoropolymers (for example, "electronic materials,
As described in "March 1998, p. 22", etc., it can be used for various applications such as use as an organic insulating film). Especially, it is preferably used as an antireflection film by taking advantage of its low refractive index property. be able to.

The antireflection film of the present invention is produced by coating the above film-forming composition as a low refractive index layer film forming material on a support and then curing it, and this antireflection film is formed only in the low refractive index layer. It may have a single-layer structure composed of, or may have a multi-layer structure in which a medium / high / low refractive index layer, a hard coat layer and the like are laminated. This antireflection film may be disposed in the image display device after forming the antireflection film in advance,
Alternatively, they may be directly formed (on the spot) and arranged on an image display device or the like. In the present invention, when the functional group of the copolymer is an epoxy group, the form of the antireflection film formed by applying and curing a film-forming composition containing a curing agent and fine particles containing an epoxy group. Is excluded.

The antireflection film of the invention will be described in more detail below. [Layer Structure of Antireflection Film] In a preferred embodiment of the present invention, in the antireflection film, the low refractive index layer containing the fluorine-containing copolymer represented by the general formula 1 has a higher refractive index than that. It is formed on the high refractive index layer and is formed of two or more layers. A typical layer structure of the antireflection film of the present invention will be described with reference to FIG.

FIG. 1 is a schematic sectional view showing a preferred layer structure of the antireflection film. The embodiment shown in FIG. 1A has a layer structure in which a transparent support 4, a hard coat layer 3, a high refractive index layer 2, and a low refractive index layer 1 are arranged in this order. As in (a),
In the antireflection film having the high refractive index layer 2 and the low refractive index layer 1, as described in JP-A-59-50401, the high refractive index layer is represented by the following formula (I) Preferably satisfy the following formula (II).

[0119]

[Equation 1]

Where m is a positive integer (generally 1, 2 or 3), n ₁ is the refractive index of the high refractive index layer, and d ₁ is the layer thickness (nm) of the high refractive index layer. Is.

[0121]

[Equation 2]

Where n is a positive odd number (generally 1),
n ₂ is the refractive index of the low refractive index layer, and d ₂ is the layer thickness (nm) of the low refractive index layer. Refractive index n ₁ of high refractive index layer
Is generally at least 0.05 higher than a transparent film,
The refractive index n ₂ of the low refractive index layer is generally at least 0.1 lower than that of the high refractive index layer and at least 0.05 lower than that of the transparent film. The refractive index can be obtained by measurement using an Abbe refractometer or estimation from the reflectance of light from the layer surface. In the present invention, the terms low refractive index, medium refractive index (described later), and high refractive index mean the relationship between the relative magnitudes of the refractive indexes between the constituent layers of the antireflection film.

The refractive index n ₁ of the high refractive index layer is generally 1.5.
It is in the range of 0 to 2.50, preferably 1.57 to 2.40, and particularly preferably 1.60 to 2.2.

The refractive index n ₂ of the low refractive index layer is generally 1.20.
To 1.49, more preferably 1.20 to 1.45, and particularly preferably 1.20 to 1.43.

The film thickness (d ₁ ) of the high refractive index layer and the film thickness (d ₂ ) of the low refractive index layer are generally in the range of 50 to 400 nm, preferably 50 to 200 nm, and more preferably 50 to 200 nm. Particularly preferably, it is in the range of 150 nm.

Another preferred embodiment shown in FIG. 1 (b) is
The transparent support 4, the hard coat layer 3, the medium refractive index layer 5, the high refractive index layer 2, and the low refractive index layer 1 are laminated in this order. As in (b), an antireflection film having a medium refractive index layer 5, a high refractive index layer 2 and a low refractive index layer 1 is disclosed in JP-A-59-5.
As described in JP-A-0401, it is preferable that the medium refractive index layer satisfies the following formula (III), the high refractive index layer satisfies the following formula (IV), and the low refractive index layer satisfies the following formula (V). .

[0127]

[Equation 3]

Where h is a positive integer (generally 1, 2 or 3), n ₃ is the refractive index of the medium refractive index layer, and d ₃ is the layer thickness (nm) of the medium refractive index layer. Is.

[0129]

[Equation 4]

Where j is a positive integer (generally 1, 2 or 3), n ₄ is the refractive index of the high refractive index layer, and d ₄ is the layer thickness (nm) of the high refractive index layer. Is.

[0131]

[Equation 5]

Where k is a positive odd number (generally 1),
n ₅ is the refractive index of the low refractive index layer, and d ₅ is the layer thickness (nm) of the low refractive index layer.

The refractive index n ₃ of the medium refractive index layer is generally 1.5.
The refractive index n of the high refractive index layer is in the range of 0 to 1.70.
₄ is generally in the range 1.70 to 2.50. The preferable refractive index n ₅ of the low refractive index layer is the same as the range described for n ₂ .

The medium refractive index layer (d ₃ ), the high refractive index layer (d ₄ ), and the low refractive index layer (d ₅ ) preferably have a thickness of generally 50 to 4
00 nm, more preferably 50 to 200 nm, particularly preferably 50 to 120 nm.

The hard coat layer preferably has a refractive index of 1.60 or less, and the medium refractive index layer (n ₃ ) is the high refractive index layer (n 3
A refractive index intermediate between ₄ ) and the hard coat layer is preferable. The film thickness of the hard coat layer is preferably in the range of 1 μm to 100 μm, preferably 5 to 20 μm, particularly preferably 5 to
This is the case of 10 μm.

In the formulas (I) to (V), λ is the wavelength of visible light, and when used as an antireflection layer in the visible region, λ is a value in the range of 380 to 680 nm. Is also effective for ultraviolet rays and infrared rays in the visible region. The high refractive index, the medium refractive index, and the low refractive index described here mean high and low relative refractive indexes between layers. For example, the medium refractive index layer is produced by a method of changing the content of the high refractive index inorganic fine particles added to the high refractive index layer. In the antireflection film of the present invention having the above layer structure, at least the improved low refractive index layer containing the fluorine-containing copolymer represented by the general formula 1 according to the present invention is used.

[Low Refractive Index Layer] The low refractive index layer is shown in FIG.
As shown in (b), it is arranged on the upper layer of the high refractive index layer. The upper side of the low refractive index layer is the surface of the antireflection film. The refractive index and the film thickness of the low refractive index layer are as described above. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test under a load of 1 kg.

[High / Medium Refractive Index Layer] When the antireflection film of the present invention takes the form of a multilayer film, generally, the low refractive index layer is
It is used together with at least one layer having a higher refractive index than the low refractive index layer (that is, the high refractive index layer and the medium refractive index layer described above).

Examples of the organic material for forming the layer having a higher refractive index than the low refractive index layer include thermoplastic films (eg, polystyrene, polystyrene copolymers, polycarbonate, aromatic rings other than polystyrene, heterocycles, and fats). Polymer having cyclic cyclic group, or polymer having halogen group other than fluorine); Thermal low refractive index layer forming composition (eg,
A coating composition having a curing agent such as a melamine coating, a phenol coating, or an epoxy coating); a urethane-forming composition (eg, a combination of an alicyclic or aromatic isocyanate and a polyol); and a radical-polymerizable composition (above-mentioned. Examples thereof include a composition containing a modified film or a prepolymer capable of radical curing by introducing a double bond into a compound (polymer or the like). A material having a high film forming property is preferable. Inorganic fine particles dispersed in an organic material can also be used for the layer having a higher refractive index than the above. As the organic material used in the above, since the inorganic fine particles generally have a high refractive index, a material having a lower refractive index than the organic material used alone can be used. As such materials, in addition to the organic materials described above, vinyl-based copolymers including acrylics, polyesters, alkyd coatings, fibrin-based polymers, urethane coatings and various curing agents for curing these, curability Examples thereof include various organic materials such as a composition having a functional group, which are transparent and can stably disperse the inorganic fine particles.

Further, an organically substituted silicon compound can be included therein. These silicon compounds are compounds represented by the following general formula, or hydrolysis products thereof. : R ^a mR ^b n SiZ (4-mn) (where R ^a
And R ^b each represents an alkyl group, an alkenyl group, an aryl group, or a hydrocarbon group substituted with halogen, epoxy, amino, mercapto, methacryloyl or cyano, and Z is an alkoxyl group, an alkoxyalkoxyl group, a halogen atom to It represents a hydrolyzable group selected from an acyloxy group, and under the condition that m + n is 1 or 2, m and n are 0, 1 or 2, respectively. )

Preferred inorganic compounds of the inorganic fine particles dispersed in these are oxides of metal elements such as aluminum, titanium, zirconium and antimony. These compounds are commercially available in particulate form, ie as powders or colloidal dispersions in water and / or other solvents. These are further mixed and dispersed in the above organic material or organosilicon compound before use.

As a material for forming a layer having a refractive index higher than the above, an inorganic material (eg, an alkoxide of various elements, a salt of an organic acid, etc.) which is film-forming and can be dispersed in a solvent or is itself liquid. Examples thereof include a coordination compound (eg, chelate compound) and an inorganic polymer) bonded to the coordination compound. Preferable examples thereof include titanium tetraethoxide, titanium tetra-i-propoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, titanium tetra-sec-butoxide and titanium tetra-t.
ert-butoxide, aluminum triethoxide, aluminum tri-i-propoxide, aluminum tributoxide, antimony triethoxide, antimony tributoxide, zirconium tetraethoxide, zirconium tetra-i-propoxide, zirconium tetra-
Metal alcoholate compounds such as n-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide and zirconium tetra-tert-butoxide; diisopropoxytitanium bis (acetylacetonate), dibutoxytitanium bis (acetylacetoacetate). ), Diethoxytitanium bis (acetylacetonate), bis (acetylacetone zirconium), aluminum acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-i-propoxide monomethylacetoacetate and tri-n-. Chelate compounds such as butoxide zirconium monoethylacetoacetate; and inorganic polymers containing carbon zirconyl ammonium or zirconium as a main component Etc. can be mentioned. In addition to the above-mentioned compounds, various alkyl silicates or their hydrolysates, finely divided silica, particularly silica gel dispersed in a colloidal form, can be used as a compound which has a relatively low refractive index and can be used in combination with the above compound. .

The refractive index of the high refractive index layer is as described above for the film thickness. The haze of the high refractive index layer is preferably 5% or less, more preferably 3% or less, and 1
Most preferably, it is at most%. The specific strength of the high refractive index layer is preferably H or more, more preferably 2H or more, and more preferably 3H in terms of pencil hardness under a load of 1 kg.
The above is most preferable.

The refractive index of the medium refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.50 to 1.70. It is particularly preferable to use inorganic fine particles and a polymer in the high refractive index layer and to form the medium refractive index layer by adjusting the refractive index to be lower than that of the high refractive index layer. The haze of the medium refractive index layer is preferably 3% or less.

[Other Layers] The antireflection film may be further provided with a hard coat layer, a moisture-proof layer, an antistatic layer, an undercoat layer and a protective layer. The hard coat layer is provided to impart scratch resistance to the transparent support. The hard coat layer also has a function of enhancing the adhesion between the transparent support and the layer above it. The hard coat layer can be formed using an acrylic polymer, a urethane polymer, an epoxy polymer, a silicon polymer or a silica compound. Pigments may be added to the hard coat layer. The acrylic polymer is preferably synthesized by a polymerization reaction of a polyfunctional acrylate monomer (eg, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of urethane-based polymers include melamine polyurethane. As the silicon-based polymer, a cohydrolyzate of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy, methacryl) is preferably used. Two or more kinds of polymers may be used in combination. Colloidal silica is preferably used as the silica-based compound. The strength of the hard coat layer has a pencil hardness under a load of 1 kg, preferably H or more, more preferably 2H or more, and 3
Most preferably, it is H or more. In addition to the hard coat layer, an adhesive layer, a shield layer, a slip layer and an antistatic layer may be provided on the transparent support. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Transparent Support] The antireflection film preferably has a transparent support except when the antireflection film is directly provided on the CRT image display surface or the lens surface. As the transparent support, a plastic film is preferable to a glass plate. Examples of plastic film materials include cellulose ester (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, nitrocellulose), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate). , Poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethene Includes tacrylate and polyetherketone. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred. The light transmittance of the transparent support is preferably 80% or more, more preferably 86% or more. The haze of the transparent support is
It is preferably 2.0% or less, more preferably 1.0% or less. The refractive index of the transparent support is 1.
It is preferably 4 to 1.7. An infrared absorber or an ultraviolet absorber may be added to the transparent support. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass. Particles of an inert inorganic compound may be added to the transparent support as a slip agent. Examples of inorganic compounds include SiO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ ,
Includes talc and kaolin. The transparent support may be surface-treated. Examples of surface treatment include chemical treatment,
Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Laser treatment, mixed acid treatment and ozone oxidation treatment are included. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferable, and glow discharge treatment and ultraviolet treatment are more preferable.

[Formation of Antireflection Film] When the antireflection film has a single layer or a multilayer structure as described above, each layer is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, It can be formed by coating by a wire bar coating method, a gravure coating method or an extrusion coating method (described in US Pat. No. 2,681,294). Two or more layers may be applied simultaneously.
For the simultaneous coating method, see US Pat. No. 2,761,791.
No. 2941898, 3508947, 35
No. 26528, Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

The lower the reflectance of the antireflection film, the better.
Specifically, the average reflectance in the wavelength region of 450 to 650 nm is preferably 2% or less, more preferably 1% or less, and most preferably 0.7% or less. The haze of the antireflection film (when it does not have the following antiglare function) is preferably 3% or less, and 1%.
It is more preferably at most 0.5%, most preferably at most 0.5%. The strength of the antireflection film has a pencil hardness under a load of 1 kg, preferably H or more, more preferably 2H or more, and most preferably 3H or more.

In the antireflection film of the present invention, the surface may have an antiglare function (that is, a function of scattering incident light on the surface and preventing the scenery around the film from being transferred to the film surface). The formation of fine irregularities may be any conventionally known method, for example, fine irregularities are formed on the surface of a transparent film, and an antireflection film (eg,
It can be obtained by forming a low refractive index layer or the like). Inorganic or organic fine particles (particle size: 50 nm to 2 μ
m) may be added in a small amount (0.1 to 50% by mass) to the low refractive index layer, the high refractive index layer, the medium refractive index layer or the hard coat layer. Alternatively, as described in JP-A Nos. 2000-329905 and 275404, fine irregularities may be formed by embossing after forming the low refractive index layer.

In an antireflection film composed of two layers, a low refractive index layer and a high refractive index layer, it is preferable to add particles of an organic or inorganic compound to the high refractive index layer. For example, silica particles or TiO ₂ Particles, crosslinked acrylic particles,
Crosslinked styrene particles, melamine film particles, benzoguanamine film particles, etc. are preferably used. In this case, the average particle size is preferably 1.0 to 10.0 μm, and 1.5 to 7.
0 μm is more preferable. The shape of the particles may be either spherical or amorphous. Two or more different particles may be used in combination. The coating amount of the particles is preferably 10 to 1000 mg / m ² , more preferably 30 to 1000 mg / m ² .
It is 100 mg / m ² . The film thickness of the high refractive index layer is 2
It is preferable that silica particles having a particle size larger than one-third occupy 40 to 100% of the entire silica particles. The particle size distribution can be measured by the Coulter counter method, the centrifugal sedimentation method or the like, but the distribution is considered in terms of the particle number distribution. The film thickness of the high refractive index layer is preferably 1 to 10 μm, and 1.2 to 6 μm
Is more preferable.

When the antireflection film has the antiglare function as described above, the haze of the antireflection film is preferably 3 to 30%, more preferably 5 to 20%, and further preferably 7 to 20%. Is most preferred.

The antireflection film is formed of a liquid crystal display (LCD),
It is applied to an image display device such as a plasma display panel (PDP), an electroluminescence display (ELD) or a cathode ray tube display device (CRT). The antireflection film is arranged so that the high refractive index layer is on the image display surface side of the image display device. When the antireflection film has a transparent support, the transparent support side is bonded to the image display surface of the image display device. In the image display device having such an antireflection film, reflection of incident light is prevented, and visibility is significantly improved. The liquid crystal display (LCD) provided with the antireflection film of the present invention includes, for example, a pair of substrates having transparent electrodes, a liquid crystal cell made of nematic liquid crystal enclosed between the substrates, and polarized light arranged on both sides of the liquid crystal cell. A mode in which the antireflection film of the present invention is provided on the surface of at least one of the polarizing plates can be mentioned. Further, the antireflection film can be used for a case cover, an optical lens, an eyeglass lens, a window shield, a light cover and a helmet shield.

[0153]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. In the following Examples and Synthesis Examples,% means mass% unless otherwise specified. In the following synthesis examples, the refractive index of a polymer is a value measured by an Abbe refractometer (manufactured by Atago Co., Ltd.) at a temperature of 20 ° C.

<Synthesis example>Synthesis Example 1; Synthesis of P-19 1) Synthesis of M1- (5) 84 g of 1H, 1H-perfluorooctanol and sulfur
Mix 17 g of tetra-n-butylammonium hydrogen hydride
Place 33.8 g of sodium hydroxide in 50 ml
Add an aqueous solution of sodium hydroxide dissolved in water at room temperature for 3
Stir for 0 minutes. In addition, chloroethyl vinyl ether
89.8 g and 90 ml of toluene were added, and the mixture was stirred at 80 ° C for 5
The mixture was heated and stirred for an hour. Ethyl acetate was added to the reaction solution and washed with water,
Extract the organic layer, dry over magnesium sulfate, and dissolve under reduced pressure.
The medium was distilled off. Furthermore, by producing by vacuum distillation
The target product M1- (5) was obtained (boiling point 79.5-80 ° C, 8
00 Pa).

2) Synthesis of P-19: 180 ml of ethyl acetate and M1- (5) 3 in an autoclave (made by Withstanding Pressure Glass Industry Co., Ltd.) with a stirrer made of glass with an internal capacity of 1 L.
1.9 g and γ-trimethoxysilylpropyl vinyl ether (monomer component corresponding to constituent component A-1, synthesized according to the method described in JP-A-48-62726) 21.
0 g and 1.29 g of dilauroyl peroxide were charged, the system was degassed and replaced with nitrogen gas. Further, 25.4 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure at the time when the temperature inside the autoclave reached 65 ° C. was 2.05 kg / cm ² . The temperature is maintained, stirring is continued for 20 hours, and the pressure is 0.
When the temperature reached 95 kg / cm ² , the heating was stopped and the mixture was allowed to cool.
When the internal temperature had dropped to room temperature, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out.
After concentration, the polymer was dissolved in a small amount of ethyl acetate and reprecipitated with n-hexane. The polymer obtained is treated twice more
Remaining monomer was completely removed by reprecipitation with n-hexane. P-19 was obtained by drying the polymer under reduced pressure. The polymer yield was 45 g. Elemental analysis and NM analysis of the composition of the obtained polymer
When performed using R, M1- (5) / HFP / A-
It was 1 = 20/50/30 (molar ratio). The content of the cross-linking reactive group (alkoxysilyl group) in the polymer is 1.
It is 3 mmol / g. The refractive index of the polymer is 1.3.
It was 8.

[0156]Synthesis Example 2; Synthesis of P-6 1) Synthesis of M1- (1) 100g of 1H, 1H-perfluoropentanol and sulfuric acid
20 g of tetra-n-butylammonium hydrogen was mixed
By the way, 69 g of sodium hydroxide was added to 100 ml of water.
Sodium hydroxide aqueous solution dissolved in was added at room temperature for 30 minutes
It was stirred for a while. Furthermore, 1 of chloroethyl vinyl ether
Add 83.8 g and 150 ml of toluene, and add 5 at 80 ° C.
The mixture was heated and stirred for an hour. Ethyl acetate was added to the reaction solution and washed with water,
Extract the organic layer, dry over magnesium sulfate, and dissolve under reduced pressure.
The medium was distilled off. Furthermore, by producing by vacuum distillation
100 g of the target fluorine-containing vinyl ether compound was obtained.
(Boiling point 73 to 76 ° C., 1064 Pa).

2) Synthesis of 2-glycidyloxyethyl vinyl ether (A-37) When 500 g of hydroxyethyl vinyl ether and 50 g of tetra-n-butylammonium hydrogen sulfate were mixed, 340 g of sodium hydroxide was dissolved in 380 ml of water. The sodium hydroxide aqueous solution was added over 30 minutes and the mixture was further stirred for 1 hour at room temperature. Further, 78.8 g of chloromethyloxirane was added, and the mixture was stirred at 60 ° C. for 2 hours. Ethyl acetate was added to the reaction solution, which was washed with water, the organic layer was extracted, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Further, 530 g of 2-glycidyloxyethyl vinyl ether (A-37) was obtained by distillation under reduced pressure (boiling point 65 ° C., 532 Pa).

3) Synthesis of P-6 In a stainless steel autoclave with a stirrer (manufactured by Pressure Resistant Glass Industry Co., Ltd.) having an internal capacity of 100 ml, 25 ml of ethyl acetate, and 7.84 g of M1- (1), 2-glycidyloxyethyl vinyl ether ( A-37) (5.61 g) and dilauroyl peroxide (0.34 g) were charged, and the system was degassed and replaced with nitrogen gas. Hexafluoropropylene (HFP)
9.74 g was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure at the time when the temperature inside the autoclave reached 65 ° C. was 5.4 kg / cm ² . Hold the temperature
The stirring was continued for 8 hours, and when the pressure reached 3.2 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature had dropped to room temperature, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out. After concentration, the polymer was dissolved in a small amount of ethyl acetate and reprecipitated with n-hexane.
The resulting polymer was reprecipitated twice with n-hexane to completely remove the residual monomer. P-6 was obtained by drying this polymer under reduced pressure. The polymer yield was 8.7 g. The composition of the obtained polymer was analyzed by elemental analysis and NMR.
FP / 2- (1H, 1H, 5H-perfluoropentanyloxy)
Ethyl vinyl ether (M1- (1)) / 2-glycidyloxyethyl vinyl ether (A-37) = 50/2
The copolymer was 0/30 (molar ratio). The refractive index of the polymer was 1.396.

[0159]Synthesis Example 3; Synthesis of P-4 Stainless steel autoclave with a content of 100 ml
(Pressure-resistant glass industry company made 25 ml of ethyl acetate, and M
10 g of 1- (1), 4-hydroxybutyl vinyl ether
(A-34) 2.56 g, dilauroyl peroxide 0.2
1 g was charged, the system was degassed and replaced with nitrogen gas. It
Hexafluoropropylene (HFP) 9.92 g
It was introduced into the autoclave and heated to 65 ° C. Oh
The pressure at the time when the temperature inside the tclave reached 65 ° C was 6.
7 kg / cm^TwoMet. Hold the temperature and stir for 8 hours
Continue, the pressure is 4.5kg / cm^TwoWhen it reaches
I left it to cool. Unreacted when the internal temperature dropped to room temperature
Discharge the monomer, open the autoclave and let the reaction liquid
Took out. After concentrating the polymer in a small amount of ethyl acetate
It was dissolved and reprecipitated with a large excess of methanol. Got
The precipitated polymer should be reprecipitated twice with methanol.
The residual monomer was completely removed by. The polymer
Was dried under reduced pressure to obtain P-4. polymer
The yield was 8.7g. Composition analysis of the obtained polymer
Was carried out using elemental analysis and NMR.
/ 2- (1H, 1H, 5H-perfluoropentanyloxy) eth
Ruvinyl ether (M1- (1)) / 4-hydroxybutane
Chill vinyl ether (A-34) = 50/30/20
It was a (molar ratio) copolymer. Also the refractive index of the polymer
Was 1.385.

[0160]Synthesis Example 4; Synthesis of P-16 10 g of P-4 obtained above was added to 50 ml of ethyl acetate.
Dissolve and under ice cooling 1.87 g of triethylamine and
Luganox 1010 (Ciba Geigy polymerization inhibitor)
0.1 g was added. Further stirring under stirring
Solution of 1.68 g of sodium hydroxide diluted with 10 ml of ethyl acetate
The mixture was added dropwise, and the reaction solution was stirred at room temperature for 5 hours. The reaction solution is water
After washing and extracting the organic layer, it is dried with magnesium sulfate.
And concentrated under reduced pressure. Furthermore, a small amount of the obtained polymer
Dissolve in ethyl acetate and add to a large amount of hexane to reprecipitate.
went. The polymer obtained by repeating the reprecipitation operation twice
Was dried under reduced pressure to obtain P-16. Poly
The mer yield was 6 g. NMR solution of the obtained polymer
As a result of the analysis, the hydroxyl group of P-4 was almost completely repaired with an acrylic group.
I found it was decorated. The refractive index of the polymer is
It was 1.389.

The other fluorine-containing copolymer of the present invention is also synthesized in the same manner as in the above-mentioned synthesis example.

[0162]Synthesis of comparative compounds 1-4 By the same operation as in Synthesis Example 2, the copolymer component and the charging composition were changed.
By changing, Comparative Compounds 1 to 4 were obtained. Obtained
Comparative polymer 1 has a refractive index of 1.42.
1, comparative compound 2 is 1.413, comparative compound 3 is 1.4
25 and comparative compound 4 were 1.417.

[0163]

[Chemical 32]

[0164]

[Chemical 33]

[0165]Synthesis of comparative compound 5 (JP-A-8-9232)
Compound described in Example 5 of JP-A-3) 143 g of hexafluoropropylene (HFP), ethi
50g of ruvinyl ether (EVE) and hydroxy
Using 20 g of butyl vinyl ether (HBVE)
Polymerization was carried out in the same manner as described above to synthesize Comparative Compound 5.
It was Elemental analysis and NM analysis of the composition of the obtained polymer
When using R, HFP / EVE / HBVE =
It was 50/40/10 (molar ratio). Also of polymer
The refractive index was 1.385.

[0166]

[Chemical 34]

[0167]Synthesis of comparative compound 6 (JP-A-10-147)
749 gazette, compound described in Example 5) 10 g of the above comparative compound 1 and γ-triethoxysilyl
Rupropyl isocyanate 1g, dibutyltin dilaure
1 mg of sodium acetate in 50 g of methyl ethyl ketone and nitrogen
By stirring at 20 ° C. for 12 hours in a gas atmosphere,
A comparative compound in which part of the hydroxyl groups was modified to alkoxysilyl groups
A MEK solution of the product 6 was obtained. Solids refractive index is 1.394
there were.

[0168]

[Chemical 35]

[0169]Synthesis of comparative compound 7 For the hydroxyl group-containing polymer in the same manner as in Synthesis Example 4 above.
Compare by reacting acrylic acid chloride
Compound 7 was synthesized. The refractive index of the polymer is 1.403
there were.

[0170]

[Chemical 36]

<Example 1; Evaluation of cured film> The copolymer of the present invention (P-5, 30) and Comparative Compounds 1 to 4 were dissolved in methyl isobutyl ketone to a concentration of 30% by mass, 5% by mass of photo-acid generator UVI6990 (manufactured by Union Carbide Japan Co., Ltd.) with respect to the copolymer.
The added liquid was prepared. The coating composition was applied onto a glass substrate and dried, then irradiated with ultraviolet rays at an energy of 500 mj / cm ² and further heated at 120 ° C. for 10 minutes to form a coating having a thickness of about 20 μm. The hardness of the film was measured using a micro hardness meter (manufactured by Fisher Instruments Co., Ltd .: Fisher Scope H100VP-HCU). At this time, a quadrangular pyramid indenter made of diamond (tip facing angle; 136 °) was used, and the indentation depth under an appropriate test load was measured within a range where the indentation depth did not exceed 1 μm. The universal hardness value is expressed as the test load divided by the surface area calculated from the geometry of the indentation produced by the test load. Table 3 shows the universal hardness value (HU) of each film and the refractive index of the cured film (measured with an Abbe refractometer (manufactured by Atago Co., Ltd.) at a temperature of 20 ° C.).

[0172]

[Table 3]

It is understood that the fluorine-containing copolymers P-5 and P-30 of the present invention are superior to Comparative Compounds 1 to 4 from the viewpoint of achieving both high hardness and low refractive index. That is,
The copolymer of the present invention is superior in hardness to the comparative compound 1 in which ethyl vinyl ether is copolymerized, and the refractive index of the copolymer of the present invention is lower. It turns out to be excellent. On the other hand, it can be seen that Comparative Compounds 3 and 4 obtained by copolymerizing perfluoro (propyl vinyl ether) are significantly inferior.

Example 2 Evaluation of Antireflection Film>Preparation of coating liquid for low refractive index layer Mix the components shown in Table 4 below and add to methyl ethyl ketone.
A coating liquid for a low refractive index layer having a solid content of 5% was prepared by dissolving.
The values in parentheses in Table 4 represent parts by mass of the solid content of each component.
In the table, colloidal silica is ME manufactured by Nissan Chemical Industries, Ltd.
Represents K-ST. Cymel 303 is Mitsui Cytec
Represents a methylolated melamine manufactured by Co., Ltd. Takenate
What is D110 is an isocyanate type manufactured by Takeda Pharmaceutical Co., Ltd.
Represents a curing agent. DPHA is dipenta manufactured by Nippon Kayaku Co., Ltd.
Represents erythritol hexaacrylate. OXT22
1 represents a bifunctional oxetane curing agent manufactured by Toagosei Co., Ltd.
You TEOS sol is 10 g of tetraethoxysilane
2.26 g of 0.01N hydrochloric acid was added and stirred for 5 hours
Represents a sol solution prepared by SiNCO is γ-triethoxy
Comparative compound 6 representing silylpropyl isocyanate
In the same manner as above, the fluorocopolymer was previously reacted.
Used. UVI6990 is Union Carbide Japan
Photo acid generator manufactured by K.K. IRG 907 is Chiva Gaigi
-Represents a photo radical polymerization initiator manufactured by Co., Ltd. DETX is the day
This represents a photosensitizer manufactured by Kayaku.

[0175]

[Table 4]

[0176]Preparation of coating liquid for the first layer (hard coat layer) Dipentaerythritol pentaacrylate and dipenta
A mixture of erythritol hexaacrylate (DPHA
(Trade name), manufactured by Nippon Kayaku Co., Ltd., 125 g and ureta
Acrylate oligomer (UV-6300B (product
Name), manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 125 g, 439
g in industrial denatured ethanol. The resulting solution
A photopolymerization initiator (IRGACURE 907 (trade name),
7.5 g of Bar Geigy and a photosensitizer (Kayakyu)
A-DETX (trade name), manufactured by Nippon Kayaku Co., Ltd., 5.0 g
Was added to a solution of 49 g in methyl ethyl ketone.
It was After stirring the mixture, fill the 1 micron mesh
And filtered through a filter to prepare a hard coat layer coating solution.

[0177]Preparation of titanium dioxide dispersion Fine particles of titanium dioxide having a core / shell structure (TTO-55
B (trade name), Ishihara Sangyo Co., Ltd. 30 parts by mass, Anio
Diacrylate monomer (PM21 (trade name), JP
4.5 parts by weight of Kayaku Co., Ltd., cationic methacrylic acid
Monomer (DMAEA (trade name), manufactured by Kojin Co., Ltd.)
0.3 parts by mass and methyl ethyl ketone 65.2 parts by mass
Dispersed with a sand grinder to remove titanium dioxide content.
A powder was prepared.

[0178]Preparation of coating liquid for second layer (medium refractive index layer) 151.9 g of cyclohexanone and methyl ethyl keto
Photopolymerization initiator (Irgacure 907
(Trade name), manufactured by Ciba-Geigy) 0.14 g and light
Sensitizer (Kayacure-DETX (trade name), Nippon Kayaku
(Manufactured by K.K.) 0.04 g was dissolved. Furthermore, the above
6.1 g of tan dispersion and dipentaerythritol pen
Taacrylate and dipentaerythritol hexaacrylate
Rate mixture (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 2.4
g, and stirred at room temperature for 30 minutes, then 1 micron of membrane was added.
Filter with a filter of the filter and apply the coating liquid for medium refractive index layer.
Prepared.

[0179]Preparation of third layer (high refractive index layer) coating liquid 152.8 g of cyclohexanone and methyl ethyl keto
Photopolymerization initiator (Irgacure 907
(Trade name), manufactured by Ciba-Geigy) 0.06 g and light
Sensitizer (Kayacure-DETX (trade name), Nippon Kayaku
0.02 g (manufactured by K.K.) was dissolved. In addition, titanium dioxide
Dispersion 13.13 g and dipentaerythritol pe
Acrylate and dipentaerythritol hexaac
Relate mixture (DPHA (trade name), Nippon Kayaku)
0.76 g was added and stirred at room temperature for 30 minutes.
Then, filter with a 1 micron mesh filter to obtain a high
A coating liquid for the refractive index layer was prepared.

[0180]Making anti-reflection film 80 micron thick triacetyl cellulose film
(TAC-TD80U (trade name), Fuji Photo Film
Co., Ltd.) with a gelatin undercoat layer
On top of the coating layer, apply the coating solution for the above hard coat layer
And then dried at 120 ° C. Next, nitrogen atmosphere
7. The coating layer is cured by irradiating it with ultraviolet rays in an ambient atmosphere to obtain a thickness of 7.
A 5 micron hard coat layer was formed. Then, above
Apply the coating liquid for the medium refractive index layer onto the hard coat layer with bar coating.
Applied and dried at 120 ° C, then nitrogen atmosphere
Irradiate lower ultraviolet light to cure the coating layer, and
Folding rate: 1.72, thickness: 81 nm) was formed. Continued
The coating solution for the high refractive index layer above the medium refractive index layer.
Coated with a coater, dried at 120 ° C, and then exposed to UV light.
The coating layer is cured by irradiation, and the high refractive index layer (refractive index: 1.
92, thickness: 53 nm) was formed. Further, Table 4 above
Coating liquid for low refractive index layer shown in (invention Ln1 to Ln15
And Comparative Examples Ln 18, 19, 22 to 24) have a high refractive index.
Coating on the layer using a bar coater to a thickness of 85 nm
Then, after irradiating it with ultraviolet rays in a nitrogen atmosphere, it is 10
After drying for a minute, a low refractive index layer was formed. Similarly, Table 4 above
The coating liquid for the low refractive index layer shown in
And Comparative Example Ln20, 21) on the high refractive index layer by bar coating.
Coating it to a thickness of 85 nm, and at 120 ° C for 1
It was dried for 0 minutes to form a low refractive index layer.

[0181]Evaluation of coating film performance A film coated with the first to fourth layers thus obtained
The following performances are described for the bright Examples 1 to 17 and Comparative Examples 1 to 7).
An evaluation was carried out.

(1) 380 to 7 using an average reflectance spectrophotometer (manufactured by JASCO Corporation)
The spectral reflectance at an incident angle of 5 ° was measured in the wavelength region of 80 nm. The specular average reflectance of 450 to 650 nm was used for the results.

(2) Evaluation of Pencil Hardness The antireflection film was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then the pencil hardness was evaluated according to JIS K 5400.

(3) Scratch resistance test The surface of the film was measured with steel wool # 0000 to obtain 200 g.
After rubbing once under the load of, the scratching level was confirmed. The judgment was based on the following criteria. No scratches: ○ Fine scratches: △ Scratches are significant: ×

(4) Adhesion Evaluation Cross-cut-Cellotape (registered trademark) peel test according to JIS K5
It carried out according to 400. The number (x) that remained in the 100-divided grid without peeling was expressed in the form of x / 100.

The results obtained are shown in Table 5.

[0187]

[Table 5]

As is clear from this example, the antireflection film of the present invention has a very low surface reflectance in a wide wavelength range, a sufficiently strong film strength, and an excellent adhesion to a substrate. You can see that On the other hand, in some comparative examples, the reflectance is lowered to some extent, but it is found that the film strength and the adhesion to the substrate are inferior.

[0189]Display device with anti-reflection film installed
Success Antireflection of Examples 1 to 17 and Comparative Examples 1 to 7 prepared above
Personal film obtained from NEC Corporation
Computer PC9821NS / 340W LCD screen
Paste on the spray surface, make a surface device sample,
Visually evaluate the degree of scenery reflection due to the surface reflection
It was Installation of the antireflection film of Examples 1 to 17 of the present invention
The display device is comfortable because there is almost no reflection of the surrounding scenery.
It showed visibility and had sufficient surface strength.
On the other hand, a display device provided with the films of Comparative Examples 1 to 7
Is the surface strength although the surrounding reflection can be reduced to some extent
It was inferior to

[0190]

The film-forming composition containing the polymer of the present invention forms a film having a low refractive index and excellent strength.
Furthermore, an antireflection film using this film-forming composition as a material for a low refractive index layer has high antireflection performance and excellent scratch resistance. A polarizing plate and a liquid crystal display device using this antireflection film have an excellent effect that reflection of external light is sufficiently prevented and also scratch resistance is high.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a layer structure when an antireflection film of the present invention is a composite film, (a) is a four-layer structure, and (b) is a five-layer structure.
An example of the layer structure is shown.

[Explanation of symbols]

1 Low refractive index layer 2 High refractive index layer 3 hard coat layer 4 transparent support 5 Middle refractive index layer

Continued front page    F term (reference) 2K009 AA05 AA06 AA15 BB28 CC03                       CC09 CC24 CC26 CC35 CC42                       EE03                 4J100 AC21Q AC22Q AE03S AE09P                       AE09R BA02P BA77R BB13P                       BB17P BB18P BC04P BC53P                       BC54R CA05 CA06 JA00

Claims (5)

[Claims] 1. A fluorinated copolymer represented by the following general formula 1. [Chemical 1] In Formula 1, Rf ¹ represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, which may have an ether bond, and Rf ² has 1 to 5 carbon atoms. Represents a perfluoroalkyl group, A represents a constituent containing at least one reactive group capable of participating in a crosslinking reaction, B represents an arbitrary constituent, and a to d each represent a mole fraction of each constituent. Indicates the rate (%), 5 for each
5 ≦ a + b ≦ 95, 5 ≦ a ≦ 90, 5 ≦ b ≦ 70, 5 ≦
It represents a value that satisfies the relationship of c ≦ 45 and 0 ≦ d ≦ 40. 2. A film-forming composition comprising the fluorine-containing copolymer according to claim 1. 3. An antireflection film having a low refractive index layer containing the fluorine-containing copolymer according to claim 1. 4. An antireflection film having the antireflection film according to claim 3 provided on a transparent support. 5. A display device comprising the antireflection film according to claim 4.