JP2000329903A - Agent for antireflection film and production of antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to obtain an antireflection film having a good adhesion property to a treating base material and high transparent by a simple method which is excellent in terms of a treatment cost, a treating time and the laboriousness of the treatment. SOLUTION: This agent is for the high-refractive index layer formable antireflection film containing 100 pts.wt. energy ray polymerizable material and an organic solvent dispersion type colloidal titanium oxide of 5 to 100 nm in average particle size at 5 to 300 pts.wt. in terms of TiO2 of the weight of this energy ray polymerizable material. The agent is for the low-refractive index layer formable antireflection film formed by hydrolysis decomposition of a solution prepared by dissolving a specific fluorine-containing silane coupling agent in an organic solvent. Further, these are used in the process for producing the antireflection film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agent for an antireflection film for producing an antireflection film and a method for producing the antireflection film. The present invention relates to an antireflection film agent having a rate layer forming property and a method for producing an antireflection film using the same, to obtain an antireflection film having excellent transparency, adhesion, antireflection ability, processing cost, and processing time.

[0002]

2. Description of the Related Art As display terminals for viewing information such as cathode ray tubes and liquid crystal monitors have become widespread, reflection of external light in a use environment causes various problems such as eyestrain and reduced visual acuity. There has been a demand for a display terminal for information viewing which has a small number of items.

Conventionally, in order to solve such a problem, an antireflection film is directly applied to a display terminal for information viewing. Such an antireflection film has a high refractive index layer whose thickness is controlled and a low refractive index layer. It was common to use the interference effect of incident light due to the stacking of the refractive index layers.

The antireflection film is formed by laminating a high-refractive index metal compound and a low-refractive index metal compound having a strictly controlled refractive index by a vacuum deposition method or a sputtering method while alternately controlling the film thickness. That is what has been achieved.

However, in this method, it is necessary to use an expensive vacuum evaporation apparatus or a sputtering apparatus to manufacture a product provided with an antireflection film, and it takes too much processing time and processing cost. It was difficult to adapt to the ends.

There is also a problem that it cannot be applied to an information viewing display terminal having a property that it is difficult to directly laminate by a vapor deposition method or a sputtering method.

Further, when an inorganic material such as a high-refractive index metal or metal oxide is formed on a resin base material to be subjected to antireflection treatment by a method such as vapor deposition or sputtering, both materials are derived from different kinds of substances, and are adhered to each other. There was also a problem that the property was not sufficient and it was easy to peel off.

Japanese Unexamined Patent Publication No. 5-2101 discloses a method for producing an antireflection film by such means, but it is disadvantageous in terms of processing complexity, time and cost as described above. . Japanese Patent Application Laid-Open No. 7-72305 describes a method of forming a low refractive index layer by coating and drying. However, the low-refractive-index layer in this invention has low film strength and is inferior in durability, and the high-refractive-index metal layer is also formed by a vapor deposition method, which complicates processing, inefficient mass production, and increases processing cost. Inadequate in terms.

Further, as a component of a high refractive index layer, JP-A-2-
No. 113027, JP-A-3-54226, JP-A-3-54
JP-A-21638 and JP-A-3-41110 disclose reactive resins containing a large amount of sulfur. However, when such products are used, it is necessary to use special raw materials. There is a problem because the cost is increased, and there is also an adverse effect on the environment that sulfur oxides are released into the atmosphere upon disposal or incineration after use. Furthermore, in order to change the refractive index of the resin, it is necessary to change the molecular structure, and it is difficult to finely adjust the refractive index.

On the other hand, in the prior art, the formation of the low refractive index layer is generally achieved by vapor deposition / sputtering of a fluorine atom-containing metal such as magnesium fluoride, silicon metal or silicon oxide. At present, a method advantageous in terms of processing time and processing cost for the entire film has not been put to practical use.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a simple method which is excellent in terms of processing cost, processing time and no complicated processing, and has good adhesion to a processing substrate. An object of the present invention is to provide an antireflection film agent capable of obtaining a highly transparent antireflection film and a method for producing an antireflection film using the same.

[0012]

In order to solve the above-mentioned problems, the agent for forming an antireflection film having a high refractive index layer according to the present invention comprises, as essential components, 100 parts by weight of an energy ray polymerizable material, TiO ₂ for energy ray polymerizable material
5 to 300 parts by weight in terms of average particle diameter 5 to 100 nm
Wherein the organic solvent-dispersed colloidal titanium oxide is contained.

In the agent for an antireflection film capable of forming a high refractive index layer according to the present invention, the energy ray-polymerizable material is (1)
It may be composed of a cation polymerizable organic substance and (2) an energy ray-sensitive cation polymerization initiator, or the energy ray polymerizable material may be composed of (1) a cation polymerizable organic substance, and (2) An energy ray-sensitive cationic polymerization initiator, (3) a radically polymerizable organic substance,
(4) It may be composed of an energy ray-sensitive radical polymerization initiator. Further, in the energy ray polymerizable material, (1) a cationic polymerizable organic substance and (3)
The weight ratio with the radical polymerizable organic substance (1) :( 3) is
Preferably it is 10-100: 0-90.

The low-refractive-index layer-forming antireflection film agent of the present invention comprises, as an essential component, an organic solvent represented by the following formula: (Wherein, R ¹ is a straight-chain or branched carbon atom having 1 to 3 carbon atoms.
R ² is a fluorine-containing hydrocarbon group having 1 to 16 carbon atoms which may be straight-chain or branched; R ³ is an alkyl group having 1 to ³ carbon atoms; R ¹ , R ² , R 3 ³
May be the same or different, and the number of fluorine atoms in all R ² is 3
M is a number of 1 to 3, n is a number of 1 to 3,
And m + n ≦ 4) in which a solution in which a fluorine-containing silane coupling agent is dissolved is subjected to hydrolysis treatment.

Further, the method for producing an antireflection film according to the present invention comprises the steps of: a) applying an agent for forming an antireflection film having a high refractive index layer to the surface of the antireflection member; A step of irradiating the surface of the anti-reflective body coated with the agent for anti-reflection film with energy rays to cure the coated material to form a high refractive index layer; c) a low refractive index layer on the high refractive index layer A step of applying a layer-forming anti-reflection film agent; and d) a step of curing the coating material coated with the low-refractive-index layer-forming anti-reflection film agent to form a low-refractive-index layer. , Consisting of:

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The organic solvent-dispersed colloidal titanium oxide used in the antireflection film-forming agent of the present invention for forming a high refractive index layer is obtained by dispersing titanium oxide particles in an organic solvent.

The organic solvent used here is not particularly limited, but examples thereof include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol and isopropanol, benzene, and the like. BTX solvents such as toluene and xylene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, cellosolve solvents such as ethylene glycol monobutyl ether, methyl acetate,
Ester solvents such as ethyl acetate, carbitol solvents,
And the like. These organic solvents can be used as one kind or a mixture of two or more kinds, and preferably an organic solvent having a boiling point of 200 ° C. or less is preferable. It is desirable that the content be not more than weight%.

The content of titanium oxide in the organic solvent is arbitrary. T in terms of the ratio with the energy ray polymerizable material described later
iO ₂ content is not limited particularly since it is within the desired range, preferably from 1 to 60 wt% TiO
₂ is preferable.

If the content of TiO ₂ is too small, it becomes difficult to form a high refractive index layer, and if it is too large, it becomes difficult to obtain a stable dispersion.

The average particle size of TiO ₂ dispersed in the organic solvent is 5 to 100 nm, more preferably, 7 to 70 nm. When the average particle size is less than 5 mm, stable colloidal state cannot be maintained, and the stability of the compounded energy ray polymerizable composition is deteriorated. Conversely 100mm
If it exceeds, the transparency of the cured film is deteriorated, and the transparency which is a feature of the present invention becomes inappropriate.

The organic solvent-dispersed colloidal titanium oxide used in the present invention requires that the titanium oxide particles be dispersed in an organic solvent in a colloidal state, and is used as a dispersion. 3000rpm
It is preferable to use a stable dispersion in which the sediment is 5% by weight or less of the TiO ₂ content by centrifugation at 30 minutes.

Such an organic solvent-dispersed colloidal titanium oxide cannot be obtained simply by dispersing TiO ₂ powder in the aforementioned organic solvent. When a dispersion of TiO ₂ powder is used, the dispersed particles greatly deviate from the above-mentioned particle size range, so that an antireflection film having excellent transparency cannot be obtained.

Such an organic solvent-dispersed colloidal titanium oxide usable in the present invention is disclosed, for example, in JP-A-6-29.
It can be obtained by a method of dropping a titanium alkoxide into a strong acid as disclosed in JP-A-8533, or by replacing the water content of an aqueous titania sol with a solvent as described in JP-B-2820251. In addition, a general commercial product can be used as it is, and a product commercially available under a trade name such as Optrake (manufactured by Catalyst Chemicals, Inc.) can also be used.

The agent for forming a high refractive index layer of the present invention for an antireflection film is used in an amount of 100 parts by weight of the energy ray polymerizable material.
The organic solvent-dispersible colloidal titanium oxide of the aforementioned particle diameter 5 to 100 nm, those containing 5 to 300 parts by weight in terms of TiO _2.

If the amount of the colloidal titanium oxide is less than the above range, the refractive index is insufficient, and a high refractive index layer cannot be provided. Preferably, the amount is such that the refractive index is 1.60 or more. Further, if the amount is more than the above range, the refractive index is increased, but the hardness as a cured film is insufficient, and the transparency is further reduced, which is unsuitable.

The energy ray-polymerizable material used in the antireflection film forming agent having a high refractive index layer according to the present invention comprises (1) a cationic polymerizable organic substance and (2) an energy ray-sensitive cationic polymerization initiator. Or (3) a radically polymerizable organic substance and (4) an energy ray-sensitive radical polymerization initiator in addition to the above (1) and (2).

The (1) cationically polymerizable organic substance that can be used for the energy ray polymerizable material includes, for example, epoxy compounds, cyclic ether compounds, oxetane compounds,
Examples thereof include a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, and a vinyl compound, and one or more of these can be used. Among them, epoxy compounds that are easily available and convenient to handle are suitable. As such an epoxy compound, an aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin and the like are suitable.

Specific examples of the aromatic epoxy resin include a polyhydric phenol having at least one aromatic ring or a polyglycidyl ether of an alkylene oxide adduct thereof, such as bisphenol A and bisphenol F, and furthermore an alkylene oxide. Glycidyl ether, epoxy novolak resin, epoxidized fluorene resin, epoxidized carbazole resin and the like.

Specific examples of the alicyclic epoxy resin are obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a compound containing cyclohexene or cyclopentene ring with an oxidizing agent. And a compound having a vinylcyclohexane oxide structure obtained by epoxidizing a compound having a cyclohexene oxide structure, a compound having a cyclopentene oxide structure, or a compound having a vinylcyclohexane structure with an oxidizing agent.
For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-
Epoxycyclohexyl carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxy Cyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methyl Cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide 4 - vinyl epoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexyl methyl) adipate, 3,4-epoxy-6-methylcyclohexyl carboxylate, methylene bis (3,
4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, epoxyhexahydrophthalate And di-2-ethylhexyl acid.

Specific examples of the aliphatic epoxy resin include a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, a polyglycidyl ester of an aliphatic long-chain polybasic acid, and an aliphatic long-chain unsaturated hydrocarbon. And glycidyl acrylate or glycidyl methacrylate homopolymer, glycidyl acrylate or glycidyl methacrylate copolymer, and the like. Representative compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, dipentaerthry Glycidyl ethers of polyhydric alcohols such as tall hexaglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Further, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol and glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids can be mentioned. Can be Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy stearin Octyl acid, butyl epoxystearate, epoxidized linseed oil, epoxidized polybutadiene, and the like.

(1) Specific examples of cationically polymerizable organic substances other than epoxy compounds include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-methyl-3-hydroxymethyloxetane, Oxetane compounds such as 3-ethyl-3-hydroxymethyloxetane and 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene; oxofuran compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; trioxane; Acetal compounds such as 1,3-dioxolan, 1,3,6-trioxanecyclooctane, β-propiolactone, ε-
Cyclic lactone compounds such as caprolactone, ethylene sulfide, thiirane compounds such as thioepichlorohydrin,
Thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthiethane, cyclic thioether compounds such as tetrahydrothiophene derivatives, ethylene glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3, 4-dihydropyran-2
-Carboxylate), vinyl compounds such as triethylene glycol divinyl ether, spiro orthoester compounds obtained by reacting epoxy compounds with lactones, ethylenically unsaturated compounds such as vinylcyclohexene, isobutylene, polybutadiene, and derivatives of the above compounds. Can be

In the present invention, (1) one or more compounds of the above-mentioned cationically polymerizable substances can be blended and used as the cationically polymerizable organic substance.

Although not limited thereto, preferred among (1) cationically polymerizable organic substances are alicyclic epoxy resins having at least two or more epoxy groups per molecule, bisphenol A Epoxy resin, bisphenol F epoxy resin, epoxidized fluorene resin, and epoxidized carbazole resin.

The (2) energy ray-sensitive cationic polymerization initiator which can be used for the energy ray polymerizable material is a compound capable of releasing a substance which initiates cationic polymerization by irradiation with energy rays. A double salt that is an onium salt that releases a Lewis acid upon irradiation, or a derivative thereof. Representative examples of such compounds include salts of cations and anions represented by the general formula [A] ^{t +} [B] ^t- .

Here, the cation At ⁺ is preferably onium, and its structure can be represented by, for example, [(R ¹¹ ) _a Z] ^{t +} .

Further, R ¹¹ is an organic group having 1 to 60 carbon atoms and which may contain any number of atoms other than carbon. a is an integer of 1 to 5. In a number of R ¹¹ are each independently, it may be the same or different. Also, at least one
One is preferably an organic group having an aromatic ring as described above. Z is S, N, Se, Te, P, As, Sb,
An atom or atomic group selected from the group consisting of Bi, O, I, Br, Cl, F, and N = N. Also, cation A
^{When the} valence of Z in ^{t +} is z, it is necessary that the relationship t = az is satisfied.

Further, the anion ^{B t-is} preferably a halide complex, and its structure, for example, can be represented by _[LX ^{b] t-.}

Here, L is a metal or metalloid which is the central atom of the halide complex,
B, P, As, Sb, Fe, Sn, Bi, Al, Ca,
In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is halogen. b is an integer of 3 to 7. Further, when the valence of L in the anion B ^t− is p, it is necessary that the relationship t = bp holds.

Specific examples of the anion [LX _b ] ^{t- in} the above general formula include tetrafluoroborate (BF ₄ ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoro Arsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like.

As the anion B ^t− , _one having a structure represented by [LX _b-1 (OH)] ^t− can also be preferably used.
L, X and b are the same as above. Other anions that can be used include perchlorate ion (ClO
₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO
₃ ) ⁻ , fluorosulfonic acid ion (FSO ₃ ) ⁻ , toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion and the like.

Further, as ^t- anion ^B, it is possible to also use preferably tetrakis (pentafluorophenyl) borate.

In the present invention, it is particularly effective to use an aromatic onium salt among such onium salts.
Among them, JP-A-50-151997 and JP-A-50-1
Aromatic halonium salts described in JP-A-58680, and VIA aromatics described in JP-A-50-151997, JP-A-52-30899, JP-A-56-55420, JP-A-55-125105 and the like. Group onium salt, JP-A-50
A VA-group aromatic onium salt described in JP-A-1558698;
JP-A-56-8428, JP-A-56-149402
And oxosulfoxonium salts described in JP-A-57-192429, aromatic diazonium salts described in JP-A-49-17040, and thiobrillium salts described in U.S. Pat. No. 4,139,655 are preferred. Other preferable examples include an iron / allene complex and an aluminum complex / photolytic silicon compound-based initiator.

Among these aromatic onium salts, particularly preferred are those as cations Or (Wherein, R represents a hydrogen atom, a halogen atom, or a hydrocarbon group optionally containing an oxygen atom or a halogen atom, or an alkoxy group optionally having a substituent, and Ar represents one or more hydrogen atoms. And a compound represented by the formula: (tolylcumyl) iodonium, bis (tertiarybutylphenyl) iodonium, triphenylsulfonium and the like. For example, 4,4 '
-Bis (di (β-hydroxyethoxy) phenylsulfonio) phenylsulfide-bis-hexafluorophosphate, 4- (4-benzoyl-phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4, 4′-bis (di (β-
Hydroxyethoxy) phenylsulfonio) phenylsulfide-bis-hexafluorophosphate, 4,
4′-bis (di (β-hydroxyethoxy) phenylsulfonio) phenylsulfide-bis-hexafluoroantimonate, 4,4′-bis (difluorophenylsulfonio) phenylsulfide-bis-hexafluorophosphate, 4,4 '-Bis (difluorophenylsulfonio) phenylsulfide-bis-hexafluoroantimonate, 4,4'-bis (phenylsulfonio) phenylsulfide-bis-hexafluorophosphate, 4,4'-bis (phenylsulfonio) Phenyl sulfide-bis-hexafluoroantimonate,
4- (4-benzoylphenylthio) phenyl-di-
(4- (β-hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- (4 -Benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (4-
Benzoylphenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-diphenylsulfonium hexafluoroantimonate, 4- (phenylthio)
Phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluorophosphate,
(Phenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- (phenylthio) phenyl-di-
(4-fluorophenyl) sulfonium hexafluorophosphate, 4- (phenylthio) phenyl-di-
(4-fluorophenyl) sulfonium hexafluoroantimonate 4- (phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (phenylthio)
Phenyl-diphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoro Antimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-hydroxyphenyl) sulfonium hexafluorophosphate,
(2-chloro-4-benzoylphenylthio) phenyl bis (4-hydroxyphenyl) sulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, (tolylcumyl) iodonium hexafluorophosphate, (tolylcumyl )
Iodonium hexafluoroantimonate, (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate, bis (tertiarybutylphenyl) iodonium hexafluorophosphate, bis (tertiarybutylphenyl) iodonium hexafluoroantimonate, bis (tertiarybutylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyldimethylsulfonium hexafluorophosphate, benzyldimethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-
Hydroxyphenylmethylsulfonium hexafluorophosphate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-
Methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate,
4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, α-naphthylmethyldimethylsulfonium hexafluorophosphate, α-naphthylmethyldimethylsulfonium hexafluoroantimonate, α-naphthylmethyltetramethylenesulfonium hexafluorophosphate, α-naphthylmethyltetra Methylenesulfonium hexafluoroantimonate, cinnamyldimethylsulfonium hexafluorophosphate, cinnamyldimethylsulfonium hexafluoroantimonate, cinnamyltetramethylenesulfonium hexafluorophosphate,
Cinnamyltetramethylenesulfonium hexafluoroantimonate, N- (α-phenylbenzyl) -2-
Cyanopyridinium hexafluorophosphate, N-
(Α-phenylbenzyl) -2-cyanopyridinium hexafluoroantimonate, N-cinnamyl-2-cyanopyridinium hexafluorophosphate, N-cinnamyl-2-cyanopyridinium hexafluoroantimonate, N- (α-naphthylmethyl)- 2-cyanopyridinium hexafluorophosphate, N- (α-
Naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, N-benzyl-2-cyanopyridinium hexafluorophosphate, N-benzyl-2
-Cyanopyridinium hexafluoroantimonate.

The preferred amount of the (2) energy ray-sensitive cationic polymerization initiator used is 0.1 to 50% by weight based on 100 parts by weight of the cationically polymerizable organic substance.
More preferably, the content is adjusted to 1.0 to 20% by weight. If (2) the amount of the energy ray-sensitive cationic polymerization initiator is less than 0.1% by weight based on 100 parts by weight of the cationically polymerizable organic substance, the curing may be insufficient and the surface hardness may be insufficient. Is undesirably caused. Further, if the content exceeds 50% by weight, various properties are not improved and the surface hardness may be lowered, which is not preferable.

The (3) radically polymerizable organic substance that can be used for the energy ray polymerizable material is preferably a compound having at least one or more unsaturated double bonds in one molecule.

Examples of such compounds include acrylate compounds, methacrylate compounds, allyl urethane compounds, unsaturated polyester compounds, styrene compounds and the like.

(3) Among radically polymerizable organic substances, compounds having a meta (acrylic) group are preferable because they are easy to synthesize and obtain and easy to handle. For example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and (meth) acrylate esters of alcohols may be mentioned.

Here, the epoxy (meth) acrylate is, for example, an acrylate obtained by reacting a conventionally known aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like with (meth) acrylic acid. It is. Among these epoxy acrylates, particularly preferred is an acrylate of an aromatic epoxy resin, in which a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof is reacted with (meth) acrylic acid. (Meta) obtained by reacting
Acrylate. For example, glycidyl ether obtained by reacting bisphenol A or an alkylene oxide adduct thereof with epichlorohydrin,
(Meth) acrylate obtained by reacting with (meth) acrylic acid, and (meth) acrylate obtained by reacting epoxy novolak resin with (meth) acrylic acid are exemplified. Preferred as urethane (meth) acrylates are (meth) acrylates obtained by reacting one or more hydroxyl-containing polyesters or hydroxyl-containing polyethers with hydroxyl-containing (meth) acrylates and isocyanates, (Meth) acrylates obtained by reacting the contained (meth) acrylic acid ester with isocyanates.

Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by reacting one or more polyhydric alcohols with one or more polybasic acids, Examples of the aliphatic polyhydric alcohol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol,
Neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol and the like can be mentioned. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, trimellitic acid and the like.

Preferred as the hydroxyl group-containing polyether are hydroxyl group-containing polyethers obtained by adding one or more alkylene oxides to a polyhydric alcohol. The same thing can be illustrated. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.

Preferred as the hydroxyl group-containing (meth) acrylic acid ester is a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction between a polyhydric alcohol and (meth) acrylic acid. The same compounds as those described above can be exemplified.

Among such hydroxyl group-containing (meth) acrylic acids, a hydroxyl group-containing (meth) acrylate obtained by an esterification reaction between a dihydric alcohol and (meth) acrylic acid is particularly preferred, for example, 2-hydroxyethyl (meth) acrylate. A) acrylate.

As the isocyanates, compounds having at least one isocyanate group in the molecule are preferable, and isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
Valent isocyanate compounds are particularly preferred.

The preferred polyester (meth) acrylate is a polyester (meth) obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid.
Acrylate. Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols with one or more monobasic acids or polybasic acids. As the polyhydric alcohol, those similar to the aforementioned compounds can be exemplified. Examples of the monobasic acid include formic acid, acetic acid, butyric acid, and benzoic acid.
Examples of polybasic acids include adipic acid, terephthalic acid,
Examples include phthalic anhydride and trimellitic acid.

Preferred as the polyether (meth) acrylate is a polyether (meth) acrylate obtained by reacting a hydroxyl group-containing polyether with meth (acrylic) acid. Preferred as the hydroxyl group-containing polyether to be used here is one of polyhydric alcohols.
A hydroxyl-containing polyether obtained by adding one or more alkylene oxides,
Examples of the polyhydric alcohol include the same compounds as those described above. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.

Preferred as (meth) acrylic acid esters of alcohols are aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule, and an alkylene oxide adduct thereof reacted with (meth) acrylic acid. (Meth) acrylate obtained by, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, benzyl (meth) acrylate, 1,3-butanediol di (meth)
Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified tri Methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate,
Examples thereof include fluorene derivative di (meth) acrylate and carbazole derivative di (meth) acrylate. One or more of these radically polymerizable organic substances can be used in combination according to desired performance.

(4) The energy ray-sensitive radical polymerization initiator which can be used for the energy ray-polymerizable material includes:
It is a compound capable of initiating radical polymerization by energy irradiation, and is preferably a ketone-based compound such as an acetophenone-based compound, a benzyl-based compound, a benzophenone-based compound, and a thioxanthone-based compound.

Examples of the acetophenone compounds include diethoxyacetophenone and 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenyl Ethane
1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin-n-butyl ether, benzoin isobutyl ether and the like.

Examples of the benzyl compound include benzyl, anisyl and the like.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like. No.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

One or more of these (4) energy ray-sensitive radical polymerization initiators can be used in combination according to the desired performance.

The above (4) energy ray-sensitive radical polymerization initiator is preferably used in an amount of 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on (3) the radically polymerizable organic substance. %. If it exceeds this range, sufficient strength may not be obtained, and if it is below this range, the resin may not be sufficiently cured.

In the energy ray polymerizable material, (1)
The weight ratio (1) :( 3) of the cationically polymerizable organic substance and (3) the radically polymerizable organic substance is preferably from 10 to 100: 0 to 90. (1) When the content of the cationically polymerizable organic substance is less than 10% by weight, that is, when the content of the radically polymerizable organic substance (4) is more than 90% by weight, the high refractive index layer is formed of a thin film. Because of this, the crosslinking at the time of curing does not proceed sufficiently due to oxygen inhibition, and a weak cured film becomes unsuitable. Therefore, at least (1) the cation polymerizable organic substance is preferably contained in the energy ray polymerizable material in an amount of 10% by weight or more, and more preferably (1) the cation polymerizable organic substance is contained in the energy ray polymerizable material. It is preferred that the content be 20% by weight or more because the influence of oxygen inhibition is reduced.

The energy ray polymerizable material used in the present invention can be used together with an organic compound having two or more hydroxyl groups in one molecule, if necessary. For example, two molecules per molecule of a polyhydric alcohol, a hydroxyl group-containing polyether, a hydroxyl group-containing polyester, a polyhydric phenol, etc.
By blending an organic compound having at least two hydroxyl groups, the mechanical strength of the cured coating film can be increased.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and the like.

The hydroxyl group-containing polyether is a compound obtained by adding one or more alkylene oxides to one or more polyhydric alcohols or polyphenols. Examples of the polyhydric alcohol used for this include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, 1,3-butanediol, 1,4-butanediol. , 1,6-hexanediol and the like. Examples of the polyhydric phenol include bisphenol A, bisphenol F, phenol novolak resin, and cresol novolak resin. Examples of the alkylene oxide include butylene oxide, propylene oxide, and ethylene oxide.

The hydroxyl group-containing polyester is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols or polyphenols with one or more monobasic acids or polybasic acids. And a hydroxyl-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols or phenols with one or more lactones. Examples of the polyhydric alcohol and the polyhydric phenol include the same as those described above. Examples of the monobasic acid include formic acid, acetic acid, butyric acid, and benzoic acid. Examples of the polybasic acid include adipic acid, terephthalic acid, trimellitic acid and the like. Lactones include β-propiolactone, γ-butyrolactone, ε-caprolactone, and the like.

The polyhydric phenol is a compound containing two or more hydroxyl groups directly bonded to an aromatic ring in one molecule.
The same as those described above can be used.

The fluorine-containing silane coupling agent used in the low-refractive index layer-forming antireflection film agent of the present invention has the following formula: (Wherein, R ¹ is a straight-chain or branched carbon atom having 1 to 3 carbon atoms.
R ² is a fluorine-containing hydrocarbon group having 1 to 16 carbon atoms which may be straight-chain or branched; R ³ is an alkyl group having 1 to ³ carbon atoms; R ¹ , R ² , R 3 ³
May be the same or different, and the number of fluorine atoms in all R ² is 3
M is a number of 1 to 3, n is a number of 1 to 3,
And m + n ≦ 4).

At least one of R ^{1 to} R ³ in the above formula must be an alkoxy group, and at least one must be a hydrocarbon group containing a fluorine atom.

If the above conditions are satisfied, R ^{1 to} R ³ may have the same structure or different structures. Hydrocarbon group containing a fluorine atom may be linear or branched, at least 3 as the total R ² hydrocarbon chain is from 1 to 16 carbon atoms
Contains more than one fluorine atom.

Further, the content of fluorine atoms contained in the fluorine-containing silane coupling agent is more preferably 3% by weight or more from the viewpoint of lowering the refractive index, and furthermore an amount giving a refractive index of 1.40 or less. It is good to do.

The agent for forming an antireflection film having a low refractive index layer according to the present invention is obtained by dissolving the fluorine-containing silane coupling agent as a low refractive index component in an organic solvent and then subjecting the agent to hydrolysis treatment.

The organic solvent that can be used here is not particularly limited, but preferred examples thereof include organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, and isopropanol.

The amount of the fluorine-containing silane coupling agent dissolved in the organic solvent is arbitrary. That is, since the organic solvent is removed (evaporated) when the low refractive index layer is formed, the organic solvent may be adjusted so that the amount of the fluorine-containing silane coupling agent has a desired low refractive index layer thickness.

However, if the amount of the fluorine-containing silane coupling agent is extremely small, an amount sufficient to give a desired low refractive index layer thickness is required in a simple coating step because of the viscosity. It is difficult to arrange in a simple coating process if the amount of the fluorine-containing silane coupling agent is extremely large, so that it is not particularly limited, but generally about 3 to 10% by weight. It is preferred that

The hydrolysis treatment here is not particularly limited, and any conventionally known method for obtaining a hydrolyzate of a silane coupling agent may be used as long as the object of the present invention is not impaired. By adding a small amount of an acid component such as acetic acid, hydrochloric acid, sulfuric acid and the like and stirring the mixture at room temperature for 20 to 30 minutes, the desired hydrolyzed liquid can be easily obtained.

Next, the method for producing an antireflection film according to the present invention comprises:
A) a step of applying the above-mentioned agent for forming an antireflection film having a high refractive index layer to the surface of an antireflection body; Irradiating the surface of the body with energy rays to cure the coating to form a high-refractive-index layer; and c) coating the low-refractive-index layer-forming antireflection film agent on the high-refractive-index layer. And d) applying the low-refractive-index-layer-forming antireflection-coating agent and curing the coating to form a low-refractive-index layer.

Here, as the antireflection target, any material can be used as long as it has sufficient resistance to the organic solvent in the antireflection film forming agent having a high refractive index layer. Those having a heat resistance of 150 ° C. or more can be subjected to a heat treatment in removing (drying) an organic solvent when forming a high refractive index layer or a low refractive index layer, and thus it is preferable.

The method of applying the antireflection film forming agent having a high refractive index layer is not particularly limited, but is preferably a method capable of controlling the coating film thickness, such as spin coating or gravure coating. It is mentioned as a preferred method.

At this time, the antireflection film forming agent having a high refractive index layer can be diluted with an organic solvent if necessary. For example, the organic solvent used for dispersing the titanium oxide particles as described above is preferable. Can be used.

In the method of the present invention, the agent for forming an antireflection film having a high refractive index layer is polymerized and cured by irradiation with active energy rays. Examples of the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are the most economical and preferable. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, particularly a (ultra) high-pressure mercury lamp, a xenon lamp, an alkali metal lamp, and a commercially available electrodeless lamp (for example, Fus)
ion valve (trade name), D valve (trade name)) and the like. When position selectivity is required for polymerization and curing of the photopolymerizable composition of the present invention, a laser beam having a good light-collecting property (especially an oscillation wavelength of 300 nm to 450 nm) is used.
m) is preferred. If the position selectivity is not so high, a mercury lamp or the like is economical and preferable.

After applying the antireflection film forming agent having a high refractive index layer, the organic solvent in the antireflection film forming agent having a high refractive index layer may be removed (dried) prior to curing. preferable.

The removal (drying) of the organic solvent can be carried out by leaving it at room temperature. However, when the antireflection member has heat resistance, heating (for example, 40 to 1) is performed.
(For several minutes at 00 ° C.).

The method of applying the antireflection film forming agent having a low refractive index layer is also not particularly limited, but a method capable of controlling the applied film thickness is preferable.
Gravure coating method and the like are mentioned as preferred methods,
It can also be easily achieved by a dipping method in which the object to be coated on which the high refractive index layer is formed is dipped in a hydrolyzed solution of a fluorine-containing silane coupling agent.

The curing of the coated low refractive index layer is achieved by removing (drying) the organic solvent, and the method is not particularly limited. The method can be carried out by leaving it at room temperature. Heat treatment at 1 ° C. for 1 to 30 minutes is excellent in terms of quickness and simplicity.

In the method for manufacturing an antireflection film of the present invention, the thickness of each of the high refractive index layer and the low refractive index layer is the same as the relationship between the high refractive index layer and the low refractive index layer in the conventional antireflection film. do it.

Specifically, for example, when the high refractive index layer is
5,000 nm, preferably 50 to 3,000 nm, and the low refractive index layer has a thickness of 5 to 5,000 nm, preferably 25 to 1,
The thickness may be adjusted to 500 nm, and the thickness of each layer may be adjusted to an optimum thickness that causes interference of incident light.

Here, the adjustment of the film thickness can be easily achieved by adjusting the solid content at the time of coating each layer, that is, by changing the solvent dilution ratio.

Further, when the wavelength of the incident light is λ, the optimum film thickness at which the incident light causes interference is λ / 2 in the optical film thickness of the high refractive index layer and λ / 2 in the optical film thickness of the low refractive index layer.
/ 4, and the closer to this relationship, the better.

The optical film thickness is represented by the product of the refractive index of the film and the film thickness. The required actual coating film thickness is calculated by calculation, and the film may be coated by the above-described method.

[0093]

Next, the present invention will be described with reference to examples. Agents for forming a high refractive index layer and an antireflection film having a low refractive index layer having the composition shown in Tables 1 and 2 below were prepared and evaluated as follows. The obtained results are also shown in Tables 1 and 2. In addition, a method for producing an evaluation sample and an evaluation method according to the present invention are described below. Hereinafter, the agent for an antireflection film having a high refractive index layer is abbreviated as a high refractive index solution, and the cured film thereof is abbreviated as a high refractive index film. The refractive index solution and its cured film are abbreviated as a low refractive index film.

Preparation of Evaluation Sample: Surface Easy Treatment PE
A high refractive index solution diluted with methyl ethyl ketone was applied to a T film (Lumirror U-98 manufactured by Toray Industries, Inc.) using a bar coater, dried at 80 ° C. for 3 minutes, and then 1000 mJ / cm ^{2 with} a high-pressure mercury lamp. And irradiated with an energy ray for curing. The polyethylene terephthalate (PET) film on which the high refractive index film was formed was immersed in a low refractive index solution which had been previously diluted with methanol and hydrolyzed with acetic acid, and pulled up at a speed of 30 mm / min. 10
A curing treatment was performed at 0 ° C. for 30 minutes to obtain a test sample. The fluorine-containing silane coupling agent was diluted with methanol to make a 5% by weight liquid.

Refractive index measurement: Measured at 23 ° C. with an Atsube refractometer. Tables 1 and 2 show the measured values of the high refractive index solution and the low refractive index solution.

Reflectance measurement: Light having a wavelength of 500 to 700 nm was vertically incident from the antireflection film side of the test sample, and the reflectance and transmittance were measured with a spectrophotometer, and the average reflectance in the visible light region was measured therefrom. And the average transmittance.

Adhesion: Evaluated by a cross-cut peeling test using a cellophane tape. If no peeling occurred, "○",
"X" when peeled between the low refractive index film and the high refractive index film,
When the substrate and the antireflection film were peeled off, it was described as “XX”.

The materials used in Tables 1 and 2 are as follows. Epoxy resin 1: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate Epoxy resin 2: Bisphenol A type epoxy resin Epoxy resin 3: Bisphenoxyfluorene epoxide Acrylic resin 1: Dipentaerythritol hexaacrylate Acrylic resin 2 : Bisphenoxyfluorene acrylate Solvent-dispersed colloidal titanium oxide: Dispersed in methyl isobutyl ketone (TiO ₂ content 20% by weight, average particle diameter 25)
nm, (Catalyst Kasei Co., Ltd. Optics) Photocationic polymerization initiator: 4,4′-bis (di (β-hydroxyethoxy) phenylsulfonio) phenylsulfide-bis-hexafluoroantimonate Photoradical polymerization Initiator: 1-hydroxycyclohexyl phenyl ketone Fluorine-containing silane coupling agent I: Heptadecafluorodecylmethyldimethoxysilane Fluorine-containing silane coupling agent II: Heptadecafluorodecyltrimethoxysilane Fluorine-containing silane coupling agent III: Trifluoropropyl Trimethoxysilane

[0099]

[Table 1]

[0100]

[Table 2] * Not cured at 160

[0101]

According to the present invention, the adhesion to the treated substrate is good and the transparency is high by a simple method which is excellent in that the treatment cost, the treatment time and the complexity of the treatment are eliminated. An antireflection film can be obtained.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 8, 1999 (1999.6.8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

The average particle size of TiO ₂ dispersed in the organic solvent is 5 to 100 nm, more preferably, 7 to 70 nm. If the average particle size is less than 5 nm , stable colloidal state cannot be maintained, and the stability of the compounded energy ray polymerizable composition will be deteriorated. Conversely, 100 nm
If it exceeds, the transparency of the cured film is deteriorated, and the transparency which is a feature of the present invention becomes inappropriate.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroyuki Tachikawa 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. F-term (reference) 2K009 AA02 AA05 BB24 CC03 CC23 CC24 CC33 CC34 DD05 4F071 AA33 AA42 AA44 AA80 AB18 AC13 AC16 AD02 AE02 AE06 AF29 AF30 AF31 AH19 BA02 BB02 BB13 BC01 BC02 BC17

Claims (6)

[Claims] An essential component is 100 parts by weight of an energy ray-polymerizable material, and an average particle size of 5 to 300 parts by weight based on TiO _{2 with} respect to the energy ray-polymerizable material.
A high refractive index layer-forming antireflection coating agent comprising an organic solvent-dispersed colloidal titanium oxide having a thickness of from 100 to 100 nm. 2. The method according to claim 1, wherein the energy ray polymerizable material is (1)
2. The agent for an antireflection film having a high refractive index layer according to claim 1, comprising a cationically polymerizable organic substance and (2) an energy ray-sensitive cationic polymerization initiator. 3. The method according to claim 1, wherein the energy ray polymerizable material is (1)
2. The high refractive index according to claim 1, comprising a cationically polymerizable organic substance, (2) an energy ray-sensitive cationic polymerization initiator, (3) a radically polymerizable organic substance, and (4) an energy ray-sensitive radical polymerization initiator. Layer-forming antireflective coating agent. 4. In the energy ray polymerizable material,
The weight ratio (1) :( 3) of (1) the cationically polymerizable organic substance to (3) the radically polymerizable organic substance is 10 to 100: 0.
The antireflection coating agent according to claim 3, which has a refractive index of from 90 to 90. 5. An essential component for an organic solvent is represented by the following formula: (Wherein, R ¹ is a straight-chain or branched carbon atom having 1 to 3 carbon atoms.
R ² is a fluorine-containing hydrocarbon group having 1 to 16 carbon atoms which may be straight-chain or branched; R ³ is an alkyl group having 1 to ³ carbon atoms; R ¹ , R ² , R 3 ³
May be the same or different, and the number of fluorine atoms in all R ² is 3
M is a number of 1 to 3, n is a number of 1 to 3,
And a solution in which a fluorine-containing silane coupling agent represented by the formula (m + n ≦ 4) is dissolved, and subjected to hydrolysis treatment. 6. A) a step of applying the agent for forming an antireflection film capable of forming a high refractive index layer according to any one of claims 1 to 4 on the surface of an antireflection object; and b) a high refractive index. A step of irradiating the surface of the anti-reflective body coated with the layer-forming anti-reflection film agent with energy rays to cure the coating to form a high refractive index layer; c) forming a high refractive index layer on the high refractive index layer 6. A step of applying the low-refractive-index layer-forming antireflection film agent according to claim 5; and d) curing the coating material coated with the low-refractive-index layer-forming antireflection film agent. Forming a refractive index layer.