JP2001296401A - Curable composition for high refractive index film, high refractive index film and antireflection laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for a high refractive index film which can be photo-cured, a high refractive index film and an antireflection laminated body using the film. SOLUTION: The curable composition contains (A) metal oxide particles having <=0.1 μm average particle diameter, (B) a hydroxyl-containing polymer, (C) a compound having both a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group and (D) a photopolymerization initiator. The high refractive index film obtained after the curing of the composition has a refractive index of >=1.50.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable composition for a high refractive index film, a high refractive index film, and an antireflection laminate. More specifically, the present invention relates to a photocurable curable composition for a high refractive index film, a high refractive index film using the same, and an antireflection laminate excellent in antireflection properties.

[0002]

2. Description of the Related Art As a material for forming an antireflection film, for example,
Thermosetting polysiloxane compositions are known, and are disclosed in JP-A-61-247743, JP-A-6-25599, JP-A-7-331115 and JP-A-10-115.
No. 2,232,301. However, the antireflection film obtained from such a thermosetting polysiloxane composition needs to be subjected to a heat treatment at a high temperature for a long time, resulting in a low productivity or a limited type of applied substrate. It was observed. In addition, since the thermosetting polysiloxane composition has poor storage stability, it is generally a two-pack type in which a main agent and a curing agent are separated, and there is a problem that handling is complicated.

Therefore, as disclosed in JP-A-8-94806, a high-refractive-index film in which fine particles are poled in a high-refractive-index binder resin on a substrate, and a fluorine-based copolymer An optical functional film has been proposed in which low refractive index films made of are sequentially laminated. More specifically, in order to form a high-refractive-index film, a fine particle layer of metal oxide particles of 200 nm or less is previously formed on a process paper, and is applied to a high-refractive-index binder resin on a base material. By pressing in contact with each other, the fine particle layer is buried in the high-refractive-index binder resin to polarize. As for the low refractive index film,
A monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene is copolymerized to have a fluorine content of 60 to 70% by weight.
100 parts by weight of a fluorine-containing copolymer, and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group,
When the total amount of these is 100 parts by weight, 0.5 to
A resin composition comprising 10 parts by weight of a polymerization initiator is cured to form a thin film having a thickness of 200 nm or less.

However, the optical functional film disclosed in Japanese Patent Application Laid-Open No. 8-94806 has a complicated manufacturing process of a high refractive index film, and as a result, it is difficult to produce a stable optical functional film. Was. In addition, in the curable composition for a high refractive index film, there was a problem that storage stability was poor because the type of the polymer used and the type of the curing agent were not appropriate. Further, such an optical functional film has a poor compatibility between the low-refractive-index film and the high-refractive-index film and an insufficient antireflection property, or an interface between the low-refractive-index film and the high-refractive-index film. Problem that the film was easily peeled off.

[0005]

The inventors of the present invention have conducted intensive studies, and as a result, have found that a curable composition for a high refractive index film has:
A metal oxide particle having a specific average particle diameter, a hydroxyl group-containing polymer, a compound having both a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group, and a photopolymerization initiator are mixed and formed. As a result, it has been found that the above-mentioned problem can be solved. That is, the present invention provides a curable composition for a high refractive index film having excellent photocurability, and a high refractive index film using the same, or an antireflection laminate having excellent antireflection properties. Aim.

[0006]

According to the present invention, the composition contains the following components (A) to (D) and has a refractive index of 1.5 after curing.
A curable composition for a high refractive index film characterized by being 0 or more is provided, and the above-mentioned problem can be solved. (A) Metal oxide particles having an average particle diameter of 0.1 μm or less (B) Hydroxyl group-containing polymer (C) Compound having both a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group (D) Photopolymerization initiation Agent With such a configuration, the photopolymerizable functional group of the component (C) can be rapidly photocured.
Therefore, a high-refractive-index film can be easily formed even on a non-heat-resistant material such as a plastic substrate. In addition, if the high refractive index film formed in this way, when a low refractive index film is provided on the surface to form an antireflection laminate, between the high refractive index film and the low refractive index film, Excellent adhesion can be obtained. That is, by using a functional group capable of reacting with a hydroxyl group contained in the component (C), a strong adhesive force can be obtained between the film and the low refractive index film.

In constituting the curable composition for a high refractive index film of the present invention, an acrylate compound (excluding the acrylate compound in the component (C)) is used as the component (E).
Is preferably further contained. By including the acrylate compound in this manner, the mechanical properties of the high refractive index film can be improved, and the photocuring properties can be adjusted.

In constituting the curable composition for a high refractive index film of the present invention, it is preferable to further contain a thermal acid generator as the component (F). By including the thermal acid generator in this way, heat treatment is performed, and the component (B) and
The reaction with the component (C) can proceed.

Further, in constituting the curable composition for a high refractive index film of the present invention, it is preferable that a mixed solvent composed of an alcohol solvent and a ketone solvent is further contained as the component (G). With this configuration, the storage stability of the curable composition for a high refractive index film can be improved, and a high refractive index film having a uniform thickness can be obtained.

In constituting the curable composition for a high refractive index film of the present invention, the photopolymerization initiator of the component (D) may be a combination of a photoradical initiator and a photoacid generator. preferable. With such a configuration, the photopolymerizable functional group contained in the component (C) can be reacted with the photoradical initiator, and the photoacid generator can react with the hydroxyl group contained in the component (C). The reaction between the reactive functional group and the component (B) can be promoted.

Another aspect of the present invention is a high-refractive-index film obtained by photo-curing any of the above-described curable compositions for a high-refractive-index film, or an antireflection laminate containing the high-refractive-index film. Body. By configuring the high refractive index film or the antireflection laminate including the high refractive index film as described above, excellent antireflection properties can be obtained when combined with a low refractive index film. In addition, since the photo-curing reaction is used for forming the high-refractive-index film, even if a low-refractive-index film is formed on the high-refractive-index film by thermosetting, the heat treatment conditions can be relaxed as a whole. Therefore, even when a high refractive index film and a low refractive index film are formed using a base material having relatively poor heat resistance as compared with the case where both of them are cured by heat as in the related art, these base materials can be used. Thermal degradation of the material can be reduced.

In constituting the antireflection laminate of the present invention, a low refractive index obtained by thermally curing a low refractive index film curable composition containing the following components and components on a high refractive index film: Preferably, a membrane is provided. Fluorine-containing copolymer having a hydroxyl group Curing agent having a functional group capable of reacting with a hydroxyl group By combining a low-refractive-index film having such a refractive index and a high-refractive-index film, more excellent antireflection property is obtained. be able to. In addition, a low refractive index film composed of such components is a component of the high refractive index film (C).
The functional group capable of reacting with the hydroxyl group of the component can react with the fluorine-containing copolymer having the hydroxyl group of the component. Similarly, the hydroxyl group of the component (B), which is a component of the high refractive index film, can be reacted with a functional group that can react with the hydroxyl group of the component. Therefore, they can react with each other, and a strong adhesion can be obtained between the high refractive index film and the low refractive index film.

Further, in forming the antireflection laminate of the present invention, when the curable composition for a low refractive index film is thermally cured, the curable composition for a low refractive index film and a high refractive index film Is preferably reacted with a part of With this configuration, a functional group capable of reacting with a hydroxyl group of the component (C), which is a component of the high refractive index film, is reacted with a fluorine-containing copolymer having a hydroxyl group as a component. Since the hydroxyl group of the component (B), which is a component of the high refractive index film, is reacted with a functional group capable of reacting with the hydroxyl group of the component, the hydroxyl group between the low refractive index film and the high refractive index film Thus, a stronger adhesive force can be reliably obtained.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments relating to the curable composition for a high refractive index film of the present invention (first embodiment) and embodiments relating to an antireflection laminate (second and third embodiments). Is specifically described. In the second embodiment,
As shown in FIG. 1, an antireflection laminate 16 includes a high refractive index film 10 and a low refractive index film 14 sequentially on a substrate 12. Further, the third embodiment has a configuration in which a hard coat layer 18 is interposed between the base material 12 and the high refractive index film 20, as shown in FIG. The antireflection laminate 24 includes a coat layer 18, a high refractive index film 20, and a low refractive index film 22 in that order.

[First Embodiment] A first embodiment of the present invention relates to a curable composition for a high refractive index film comprising the following components (A) to (G), and has a refractive index of 1 after curing. .50 or more. Here, the refractive index means a value obtained by measuring the refractive index of a Na-D line at 25 ° C. (A) Metal oxide particles having an average particle diameter of 0.1 μm or less (B) Hydroxyl group-containing polymer (C) Compound having both a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group (D) Photopolymerization initiation (E) Acrylate compound (F) Thermal acid generator (G) Organic solvent

(1) Component (A) The average particle diameter of the metal oxide particles as the component (A) must be 0.1 μm or less. The reason is that when the average particle diameter of the metal oxide particles exceeds 0.1 μm, it becomes difficult to uniformly disperse the metal oxide particles in the curable composition for a high refractive index film, and the metal oxide particles Is liable to settle and lacks storage stability.
Furthermore, when the average particle diameter of the metal oxide particles exceeds 0.1 μm, the transparency of the obtained antireflection film is reduced,
This is because the turbidity (Haze value) may increase.
Therefore, the average particle diameter of the metal oxide particles is set to 0.08 μm.
The value is more preferably not more than m, and more preferably not more than 0.05 μm. The average particle diameter of the metal oxide particles is an average value of the particle diameter measured by an electron microscope.

Further, the metal oxide particles as component (A)
The type should be determined considering the ease of adjusting the refractive index
Is more preferable, and more specifically, zirconium oxide (Z
rO _Two, Refractive index 2.05), tin oxide (SnO)_Two, Refractive index
2.00), antimony tin oxide (ATO, refractive index 1.
95), titanium oxide (TiO)_Two, Refractive index 2.3-2.
7), zinc oxide (ZnO, refractive index 1.90), indium oxide
Didium tin (ITO, refractive index 1.95), selenium oxide
(SeO_Two, Refractive index 1.95), antimony oxide (Sb_Two
O_Five, Refractive index 1.71), aluminum oxide (Al
_TwoO_Three, Refractive index 1.63), yttrium oxide (Y_TwoO_Three,
Refractive index 1.87) etc. alone or in combination of two or more
For example. However, these metal oxide particles
Of these, the refractive index after curing was set to 1.5 with a relatively small amount of addition.
Because it can be easily adjusted to a value of 0 or more,
It is possible to use metal oxide particles having a folding ratio of 1.90 or more.
preferable. Specifically, zirconium oxide, tin oxide,
Antimony tin oxide, titanium oxide, zinc oxide, indium oxide
Indium tin, selenium oxide, etc. are applicable, but more transparent
Zirconium oxide
And antimony tin oxide are most preferred.

Preferably, the surface of the metal oxide particles is treated with a coupling agent. By performing the coupling agent treatment in this manner, the dispersibility of the metal oxide particles can be improved, and the storage stability of the curable composition for a high refractive index film can be further improved. Here, preferable coupling agents when performing the coupling agent treatment include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxysilane. Propyltrimethoxysilane, γ-aminopropyltriethoxytitanium, γ-
Aminopropyltriethoxyaluminum and the like.

(2) Component (B) As the hydroxyl group-containing polymer as the component (B), any polymer having a hydroxyl group in the molecule can be suitably used. More specifically, a single type of polyvinyl acetal resin (polyvinyl butyral resin, polyvinyl formal resin), a polyvinyl alcohol resin, a polyacrylic resin, a polyphenolic resin, a phenoxy resin, or the like, or a combination of two or more types is exemplified. However,
Among these hydroxyl group-containing polymers, polyvinyl butyral resins (including modified polyvinyl butyral resins) are excellent in adhesion and mechanical properties to a substrate, and are relatively easy to uniformly disperse metal oxide particles. .) Are most preferred. Among polyvinyl butyral resins, those having an average degree of polymerization of 1,000 or less, a polyvinyl alcohol unit in one molecule of 18% by weight or more, and a glass transition point of 70 ° C. or more have properties. More preferred.

It is preferable that the amount of the component (B) is in the range of 1 to 100 parts by weight based on 100 parts by weight of the metal oxide particles of the component (A). The reason for this is
If the amount of the component (B) is less than 1 part by weight, the adhesion of the obtained high refractive index film to the substrate may be reduced, while the amount of the component (B) is 100 parts by weight. If the ratio exceeds, the amount of metal oxide particles is relatively reduced, and it may be difficult to adjust the refractive index of the antireflection film after curing. Therefore, the amount of the component (B) is more preferably in the range of 3 to 70 parts by weight, and more preferably in the range of 5 to 50 parts by weight, per 100 parts by weight of the component (A). Is more preferred.

(3) Component (C) As the component (C), a compound having both a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group (hereinafter, may be referred to as a combined compound). A functional group capable of reacting with a hydroxyl group (hereinafter, may be referred to as a hydroxyl-reactive functional group) and a photopolymerizable functional group (hereinafter, may be referred to as a photopolymerizable functional group). Any compound can be suitably used.

Types of Functional Groups Examples of the hydroxyl group-reactive functional group contained in the component (C) include an amino group, an isocyanate group, a carboxyl group, an acid anhydride group, an aldehyde group, and a halogen. Similarly, examples of the photopolymerizable functional group included in the component (C) include an epoxy group, an oxetane group, and a vinyl group. It is preferable that both of these functional groups are contained in the compound alone or in combination of two or more.

Specific Examples Specific examples of the component (C) include t-butylaminoethyl
Acrylate, N, N-dimethylaminoethyl acryle
N, N-diethylaminoethyl acrylate, N
-Methacryloxy-N, N-dicarboxymethyl-p-
Phenylenediamine, melamine / formaldehyde / a
Lucyl monoalcohol (C₁~ C₁₂) Condensate and 2-H
Condensation product with droxyethyl acrylate, 2- [o-
(1'methylpropylideneamino) carboxyamino]
Ethyl acrylate, 2,3-dibromopropylacryl
Rate, 2,3-dibromopropyl methacrylate,
Tacryloxyethyl phthalate, N-methacryloxy-
N-carboxymethylpiperidine, 4-methacryloxy
Ethyl trimellitic acid, acryloxyethyl terephthala
EO-modified phthalic acrylate, EO-modified succinate
Acid acrylate, 4-methacryloxyethyl anhydride trim
One or a combination of two or more such as lit acid
I can do it. In addition, the compound having the component (C) may be used.
More excellent storage in the curable composition for high refractive index film
While stable, low-temperature curing is possible,
Lamin, formaldehyde, alkyl monoalcohol
(C₁~ C₁₂) Condensate and 2-hydroxyethylacry
Condensates with rates are more preferred. Note that such a
Lamin, formaldehyde, alkyl monoalcohol
(C ₁~ C₁₂) Condensate and 2-hydroxyethylacry
The condensate with a rate is commercially available under the trade name Nikarac MX-3
02 (manufactured by Sanwa Chemical Co., Ltd.)
it can.

The amount of the component (C) is preferably in the range of 10 to 300 parts by weight based on 100 parts by weight of the metal oxide particles of the component (A). The reason for this is (C)
If the amount of the component is less than 10 parts by weight, the curing of the hydroxyl group-containing polymer of the component (B) may be insufficient, while the amount of the component (C) exceeds 300 parts by weight. This is because the refractive index of the obtained high refractive index film may decrease. Therefore, it is more preferable that the added amount of the component (C) is in the range of 20 to 200 parts by weight with respect to 100 parts by weight of the component (A).
More preferably, the value is in the range of 0 parts by weight.

(4) Component (D) The photopolymerization initiator as the component (D) preferably contains the following photoradical initiator and photoacid generator. Also,
Each of these photopolymerization initiators can be used alone, but it is more preferable to use them in combination. The reason for this is that the combined use of the above-mentioned component (C), for example, melamine / formaldehyde / alkyl monoalcohol (C ₁ -C ₁₂ ) condensation by using a photo-radical initiator and a photo-acid generator in combination This is because, when a condensate of the compound and 2-hydroxyethyl acrylate is used, the functional group contained in the compound may be further reacted.

Photo-radical initiator A photo-radical initiator is a compound capable of producing a radical substance capable of photo-curing (cross-linking) the compound having component (C) by irradiating an energy ray such as light. Is defined as As such a photo-radical initiator,
1-hydroxycyclohexyl phenyl ketone, 2,
2'-dimethoxy-2-phenylacetophenone, xanthone, fluorene, fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4 '
-Diaminobenzophenone, Michler's ketone, benzoylpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) butan-1-one, 1-
[4- (2-hydroxyethoxy) -phenyl] -2-
One kind or a combination of two or more kinds such as hydroxy-2-methylpropan-1-one can be mentioned. Among these photoradical initiators, 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 1-hydroxycyclohexylphenyl ketone are more preferred. In addition, for example, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholinopropan-1-one can be obtained under the trade name Irgacure 907 or the like. Similarly, 1-hydroxycyclohexyl phenyl ketone is
It can be obtained under the trade name Irgacure 184 (all manufactured by Ciba Specialty Chemicals Co., Ltd.).

The amount of the photo-radical initiator used is not particularly limited. For example, the photo-radical initiator is used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the component (C). Is preferred. The reason for this is that if the amount of the photoradical initiator is less than 0.1 part by weight, the curing of the component (C) may be insufficient. On the other hand, if the amount of the photo-radical initiator exceeds 20 parts by weight, the storage stability of the curable composition for a high refractive index film may decrease. Therefore, the amount of the photo-radical initiator used can be reduced by (C)
More preferably, the value is in the range of 0.5 to 10 parts by weight based on 100 parts by weight of the component.

Photoacid Generator The photoacid generator emits an acidic active substance capable of photocuring (crosslinking) the compound (C) by irradiating it with energy rays such as light. Are defined. The photo-acid generator and the above-described photo-radical initiator are decomposed to generate an acidic active substance or a radical. β-rays and γ-rays can be exemplified. However, it is preferable to use ultraviolet rays from the viewpoint of having a constant energy level, a high curing speed, a relatively low cost of the irradiation device, and a small size.

Examples of such a photoacid generator include onium salts (compounds of the first group) having the structure represented by the general formula (1) and sulfones having the structure represented by the general formula (2) Acid derivatives (the second group of compounds) can be mentioned.

[R¹ _aR^Two _bR^Three _cR^Four _dW]^{+ m}[MZ_{m + n}]^-m (1) [In the general formula (1), the cation is an onium ion;
W is S, Se, Te, P, As, Sb, Bi, O, I,
Br, Cl or -N≡N;¹, R^Two, R ^ThreeAnd
And R^FourAre the same or different organic groups, and a, b, c and
And d are each an integer of 0 to 3, and (a + b + c
+ D) is equal to the valence of W. M is a halide complex
Body [MX_{m + n}Metal or metallo constituting the central atom of
And B, P, As, Sb, Fe, Sn,
Bi, Al, Ca, In, Ti, Zn, Sc, V, C
r, Mn, and Co. Z is, for example, F, Cl, Br, etc.
M is a halogen atom or an aryl group
Is the net charge of the chloride complex ion, where n is the valence of M
is there. ]

Q _s- [S (= O) ₂ -R ⁵ ] _t (2) [In the general formula (2), Q represents a monovalent or divalent organic group;
⁵ is a monovalent organic group having 1 to 12 carbon atoms, the subscript s is 0 or 1, and the subscript t is 1 or 2. ]

In the general formula (1), the anion [M
Z _{m + n} ] include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ),
Hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) Borate and the like. It is also preferable to use an anion represented by the general formula [MZ _n OH ⁻ ] instead of the anion [MZ _{m + n} ] in the general formula (1). Furthermore, perchlorate ion (ClO ₄ ⁻ ), trifluoromethanesulfonic acid ion (CF ₃ SO ₃ ⁻ ), fluorosulfonic acid ion (FSO ₃ ⁻ ), toluenesulfonic acid ion, trinitrobenzenesulfonic acid anion, trinitrotoluenesulfonic acid Onium salts having other anions such as anions can also be used.

Of the above-mentioned compounds of the first group, more effective onium salts are aromatic onium salts, particularly preferably diaryliodonium salts or triaryliodonium salts represented by the following general formula (3). It is. [R ⁶ -Ar ¹ -I ⁺ -Ar ² -R ⁷ ] [Y ⁻ ] (3) [In the general formula (3), R ⁶ and R ⁷ are each a monovalent organic group, and are the same or different. At least one of R ⁶ and R ⁷ has an alkyl group having 4 or more carbon atoms, and Ar ¹ and Ar ² are each an aromatic group, and may be the same or different; Y ^- is a monovalent anion, periodic table group 3, group 5 fluoride anions or _{^{of, ClO 4 -, CF 3 -SO}} 3 - is an anion selected from. ]

Specific examples of such diaryliodonium salts include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4
-(2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy)
[Phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium tetrakis ( Pentafluorophenyl) borate, bis (4-t-
Butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium trifluorosulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate One or more of bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, etc. Combinations can be mentioned. In addition, for example, a screw (4-
t-Butylphenyl) iodonium trifluorosulfonate is commercially available under the trade name of IBCF (Sanwa Chemical Co., Ltd.)
Manufactured).

Further, among the compounds of the second group of the photoacid generators, examples of the sulfonic acid derivative represented by the general formula (2) include: disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylmethanes. Benzoylmethanes,
Imide sulfonates, benzoin sulfonates, 1
-Oxy-2-hydroxy-3-propyl alcohol sulfonates, pyrogallol trisulfonates, and benzyl sulfonates. Further, in the general formula (2), more preferred are imide sulfonates, and further preferred are imide sulfonates.
It is a trifluoromethylsulfonate derivative.

Specific examples of such sulfonates include diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, and phenylsulfonylbenzoyl. Diazomethane, bis (cyclohexylsulfonyl) methane, 1,8-naphthalenedicarboxylic acid imide methylsulfonate, 1,8-naphthalenedicarboxylic acid imidotosylsulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethylsulfonate, 1,8
-Naphthalenedicarboxylic acid imido camphorsulfonate, imido phenyl succinate, imido tosyl sulfonate, imido trifluoromethyl sulfonate, imido camphor sulfonate, imido trifluoro sulfonate, cis-5-norbornene-endo-2 , 3-dicarboxylic imide trifluoromethylsulfonate, benzoin tosylate, 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di (4-methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methyl Sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenyl methyl tosylate, ortho-nitrophenyl methyl tosylate, para-nitrophenyl tosylar It can be mentioned.

The amount of the photoacid generator to be added is not particularly limited.
When the amount is 00 parts by weight, the value is preferably in the range of 0.1 to 15 parts by weight. The reason for this is that if the amount of the photoacid generator is less than 0.1 part by weight, the components (B) and (C)
This is because the photocurability between the components may be reduced, and sufficient hardness may not be obtained. On the other hand, if the amount of the photoacid generator exceeds 15 parts by weight, the obtained cured product may have poor weather resistance and heat resistance. Therefore, since the balance between the photocurability and the weather resistance of the obtained cured product becomes better, the addition amount of the photoacid generator is set to 100 parts by weight as the total of the components (B) and (C). When you do
More preferably, the value is in the range of 10 parts by weight.

(5) Component (E) Type The acrylate compound as the component (E) is a (meth) acrylate compound other than the acrylate compound in the component (C), and has at least one (meth) acryloyl in the molecule. A compound containing a group. Therefore, the type thereof is not particularly limited, but is, for example, a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound, or any one of the (meth) acrylate compounds. In particular, the reactivity of the curable resin composition can be improved by adding a polyfunctional (meth) acrylate compound.

Among the components (E), monofunctional (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. ) Acrylate, isobutyl (meth)
Acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth)
Alkyl (meth) acrylates such as acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate; hydroxyethyl ( Hydroxyalkyl (meth) acrylates such as meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; phenoxyalkyl such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate (Meth) acrylates; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl Alkoxyalkyl (meth) acrylates such as meth) acrylate and methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate And polyethylene glycol (meth) acrylates such as nonylphenoxypolyethylene glycol (meth) acrylate; polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) Polypropylene glycol such as acrylate (meta Acrylates: cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate And cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and tricyclodecanyl (meth) acrylate; singly or in combination of two or more such as benzyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. Can be

Of the acrylate compounds of component (E), polyfunctional (meth) acrylate compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene. Alkylene glycol di (meth) such as glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate
Acrylates; trimethylolpropane tri (meth)
Acrylate, trimethylolpropane trihydroxyethyl tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hydroxypivalin Poly (meth) acrylates of polyhydric alcohols such as neopentyl glycol di (meth) acrylate; isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxy) Poly (meth) acrylates of isocyanurate such as ethyl) isocyanurate tri (meth) acrylate; tricyclodecanediyldimethyldi (meth) acrylate (Meth) acrylate of bisphenol A ethylene oxide adduct, di (meth) acrylate of bisphenol A propylene oxide adduct, di (meth) acrylate of bisphenol A alkylene oxide adduct (Meth) acrylate, di (meth) acrylate of ethylene oxide adduct of hydrogenated bisphenol A, di (meth) acrylate of propylene oxide adduct of hydrogenated bisphenol A, di (meth) acrylate of alkylene oxide adduct of hydrogenated bisphenol A ) Acrylate, bisphenol A diglycidyl ether and (meth)
(Meth) acrylate derivatives of bisphenol A such as (meth) acrylate obtained from acrylic acid;
3,4,4,5,5,6,6-octafluorooctanedi (meth) acrylate, 3- (2-perfluorohexyl) ethoxy-1,2-di (meth) acryloylpropane, Nn-propyl -N-2,3-di (meth) acryloylpropyl perfluorooctylsulfonamide and the like, and one or a combination of two or more kinds of fluorinated (meth) acrylates. Among these polyfunctional (meth) acrylate compounds, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate are particularly preferred. This is because these polyfunctional (meth) acrylate compounds are particularly excellent in photocurability and also particularly excellent in compatibility with the component (B) and the component (C).

Addition Amount The addition amount of the component (E) is not particularly limited. For example, a value within the range of 0.01 to 1,000 parts by weight per 100 parts by weight of the component (A). It is preferable that The reason for this is that if the added amount of the component (E) is less than 0.01 part by weight, the reactivity of the curable composition for a high refractive index film may decrease, and the content of the component (E) may be reduced. If the addition amount exceeds 1,000 parts by weight, the storage stability of the curable composition for a high refractive index film may decrease. Therefore, by limiting the amount of the component (E) to such a range, the reaction can be uniformly performed, and the resulting cured product has further improved scratch resistance, solvent resistance, transparency, and the like. . Therefore, since the balance between the reactivity and the storage stability of the curable composition for a high refractive index film becomes better, the amount of the component (E) to be added is 0.1 to 100 parts by weight per the component (A). The value is more preferably in the range of 300 parts by weight, and even more preferably in the range of 1 to 200 parts by weight.

(6) Component (F) Kinds The thermal acid generator as the component (F) includes aliphatic sulfonic acid, aliphatic sulfonic acid salt, aliphatic carboxylic acid, aliphatic carboxylic acid salt and aromatic sulfonic acid. , Aromatic sulfonate, aromatic carboxylic acid, aromatic carboxylate, metal salt,
One type of phosphoric acid ester and the like or a combination of two or more types may be mentioned. However, among these thermal acid generators,
Aromatic sulfonic acids are more preferable because the curing speed can be further improved. In addition, as such aromatic sulfonic acid, a commercially available trade name Catalyst 4050
(Manufactured by Mitsui Cytec Co., Ltd.) and the like.

Addition Amount The addition amount of the thermal acid generator of the component (F) is not particularly limited, either, but when the total of the components (B) and (C) is 100 parts by weight. It is preferred that the amount of the thermal acid generator be in the range of 0.1 to 30 parts by weight. The reason is that if the addition amount is less than 0.1 part by weight, the effect of adding the thermal acid generator may not be exhibited, while if it exceeds 30 parts by weight, the curable composition for a high refractive index film may This is because the storage stability of the product may decrease. Therefore, the addition amount of the thermal acid generator is 0.5 to
More preferably, the value is in the range of 20 parts by weight,
More preferably, the value is in the range of 10 parts by weight.

(7) Component (G) Kind It is preferable to add an organic solvent as the component (G) to the curable composition for a high refractive index film. By adding an organic solvent in this manner, the storage stability of the curable composition for a high refractive index film can be improved, and the high refractive index film as a thin film can be formed to have a uniform thickness. As such a component (G), methyl isobutyl ketone,
One type alone or a combination of two or more types such as methyl ethyl ketone, methanol, ethanol, t-butanol, isopropanol and the like can be mentioned. Further, by using a mixed solvent composed of an alcohol solvent and a ketone solvent as the component (G), the coatability of the curable composition for a high refractive index film is improved, and the reflection of the obtained high refractive index film is improved. The prevention and the transparency are excellent.

The amount of the component (G) is not particularly limited, either. The amount of the organic solvent is preferably 50 to 20 parts by weight per 100 parts by weight of the metal oxide particles of the component (A). 000
It is preferred that the value be within the range of parts by weight. The reason for this is
If the addition amount of the component (G) is less than 50 parts by weight, it may be difficult to adjust the viscosity of the curable composition for a high refractive index film, while the addition amount of the component (F) is 20, 000
If the amount is more than the weight part, the storage stability of the curable composition for a high refractive index film may be lowered, or the viscosity may be too low to make handling difficult. Therefore,
More preferably, the amount of the component (G) is in the range of 100 to 10,000 parts by weight, and more preferably in the range of 200 to 5,000 parts by weight, per 100 parts by weight of the component (A). More preferably,

(8) Additives The curable composition for a high refractive index film may contain a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wetting agent, as long as the object and effects of the present invention are not impaired. Property improver, surfactant,
It is also preferable to further include additives such as a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, a pigment, and a dye.

(9) Refractive index The refractive index after forming a cured film from the curable composition for a high refractive index film, that is, the refractive index of the high refractive index film is 1.50.
It is necessary to set the above value. This is because if the refractive index of the high refractive index film is less than 1.50, the antireflection effect may be significantly reduced when combined with the low refractive index film. Therefore, the refractive index of the high refractive index film is set to 1.5
More preferably, the value is in the range of 5 to 2.20.
That is, if the refractive index of the curable composition for a high refractive index film after curing exceeds 2.20, the types of usable materials may be excessively limited. When a plurality of high refractive index films are provided, at least one of them has only to have a refractive index value within the above-described range. It may have a value less than 50.

[Second Embodiment] In a second embodiment of the present invention, as shown in FIG. 1, a high refractive index film obtained from a curable composition for a high refractive index film is formed on a substrate 12. An anti-reflection laminate 16 sequentially including a low refractive index film 14 and a low refractive index film 14 obtained from the curable composition for a low refractive index film. Note that, in the example of the antireflection laminate 16, the hard coat layer is not provided, and the high refractive index film 10 itself has the function of the hard coat layer. Therefore, the configuration of the antireflection laminate 16 is simplified, and the antireflection laminate 16 can be formed with high accuracy. Hereinafter, the second embodiment will be specifically described.

(1) Curable composition for high-refractive-index film The curable composition for high-refractive-index film used in the second embodiment and the refractive index of the high-refractive-index film obtained therefrom are as follows:
This is the same as the content of the first embodiment. Therefore, a specific description here is omitted.

(2) Curable composition for low-refractive-index film The curable composition for low-refractive-index film for forming the low-refractive-index film can react with a fluorine-containing copolymer having a hydroxyl group with a hydroxyl group. It is composed of a thermosetting agent having a functional group, and preferably further contains a thermal acid generator organic solvent, and has a refractive index after curing of less than 1.50.

Fluorine-containing copolymer having a hydroxyl group As the fluorine-containing copolymer having a hydroxyl group, any fluorine-containing copolymer having a hydroxyl group in the molecule can be suitably used. More specifically, it can be obtained by copolymerizing a monomer containing a fluorine atom (component a) and a monomer containing a hydroxyl group or an epoxy group (component b). It is preferable to add an ethylenically unsaturated monomer (component c) other than the component a and the component b as needed. As the monomer containing a fluorine atom as the component a, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene,
One or two kinds of trifluoroethylene, tetrafluoroethylene, (fluoroalkyl) vinyl ether, (fluoroalkoxyalkyl) vinyl ether, perfluoro (alkyl vinyl ether), perfluoro (alkoxyvinyl ether), fluorine-containing (meth) acrylate, and the like The above combinations are given. The blending amount of the component a in the fluorine-containing copolymer having a hydroxyl group is not particularly limited.
The value is preferably in the range of ~ 99 mol%, more preferably in the range of 15-97 mol%.

The monomers containing a hydroxyl group or an epoxy group as the component b include hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyethyl allyl ether, and hydroxybutyl allyl. One type of ether, glycerol monoallyl ether, allyl alcohol, hydroxyethyl (meth) acrylate and the like, or a combination of two or more types may be mentioned. In addition, b in the fluorine-containing copolymer having a hydroxyl group
The amount of the component is not particularly limited, but is preferably, for example, a value within a range of 1 to 20 mol%, and more preferably a value within a range of 3 to 15 mol%.

Next, the degree of polymerization of the fluorine-containing copolymer having a hydroxyl group will be described. The degree of polymerization is preferably determined in consideration of the mechanical strength and coatability of the low refractive index film. 2.0 dl /
g, preferably in the range of 0.1 to 1.5 d
More preferably, the value is in the range of 1 / g. The reason is that by setting the intrinsic viscosity to a value within such a range, excellent mechanical strength and applicability can be obtained in the low refractive index film. The polymerization method for obtaining such an intrinsic viscosity is not particularly limited, and a solution polymerization method using a radical polymerization initiator, a suspension polymerization method, an emulsion polymerization method, a bulk polymerization method, or the like is employed. can do.

Thermosetting agent having a functional group capable of reacting with a hydroxyl group As the thermosetting agent having a functional group capable of reacting with a hydroxyl group (hereinafter sometimes simply referred to as a thermosetting agent), a methylol group and a It is preferable to use a melamine compound having two or more alkoxylated methyl groups or either one. More specifically, one or a combination of two or more of a melamine compound, a urea compound, a guanamine compound, a phenol compound, an epoxy compound, an isocyanate compound, and a polybasic acid are exemplified. However,
Among these thermosetting agents, a melamine compound having a methylol group and / or an alkoxylated methyl group in a molecule or two or more thereof in a molecule, since the thermosetting agent has relatively excellent storage stability and can be cured at a relatively low temperature. Is most preferred.
Further, among these melamine compounds, methylated melamine such as hexamethyletherified methylolmelamine compound, hexabutyletherified methylolmelamine compound, methylbutyl mixed etherified methylolmelamine compound, methyletherified methylolmelamine compound, butyletherified methylolmelamine compound, etc. Compounds are more preferred. In addition, it is also preferable to use a compound having both a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group in the curable composition for a high refractive index film as such a thermosetting agent. As described above, in the curable composition for a low-refractive-index film, by using the same kind of compound as the curable composition for a high-refractive-index film, the compatibility between the high-refractive-index film after formation and the low-refractive-index film is improved. Is better, and further excellent antireflection properties and adhesion can be obtained. Further, the addition amount of the thermosetting agent is preferably set to a value within the range of 1 to 70 parts by weight based on 100 parts by weight of the fluorine-containing copolymer having a hydroxyl group. The reason for this is that if the amount of the thermosetting agent is less than 1 part by weight, the curing of the fluorine-containing copolymer having a hydroxyl group may be insufficient, whereas if it exceeds 70 parts by weight. This is because the storage stability of the curable composition for a low refractive index film may decrease.

Thermal Acid Generator As the thermal acid generator, any one which promotes the reaction between the hydroxyl group-containing polymer and the thermosetting agent can be suitably used. It is preferable to use the same thermal acid generator as the thermal acid generator in the acidic composition.

The amount of the thermal acid generator to be added is not particularly limited, either, but the total amount of the above-mentioned fluorine-containing copolymer having a hydroxyl group and the thermosetting agent having a functional group capable of reacting with the hydroxyl group is included. When the amount is 100 parts by weight,
It is preferable to set the amount of the thermal acid generator to a value within the range of 0.1 to 30 parts by weight. The reason is that the addition amount is 0.1
When the amount is less than 10 parts by weight, the effect of adding the thermal acid generator may not be exhibited. On the other hand, when the amount exceeds 30 parts by weight, the storage stability of the curable composition for a low refractive index film may decrease. Because there is. Therefore, the amount of the thermal acid generator to be added is more preferably set to a value within the range of 0.5 to 20 parts by weight, and even more preferably set to a value within the range of 1 to 10 parts by weight.

Organic Solvent As the organic solvent used in the curable composition for a low refractive index film, it is preferable to use the same type as the organic solvent in the curable composition for a high refractive index film. Further, the amount of the organic solvent to be added is preferably set to a value within the range of 100 to 10,000 parts by weight based on 100 parts by weight of the fluorine-containing copolymer having a hydroxyl group. This is because if the amount of the organic solvent is less than 100 parts by weight, it may be difficult to form a low-refractive-index film having a uniform thickness. If the ratio exceeds the above range, the storage stability of the curable composition for a low refractive index film may decrease.

(3) Refractive index of low refractive index film The value of the refractive index (the refractive index of the Na-D line,
The lower the measurement temperature (25 ° C.), the more excellent the antireflection effect can be obtained when combined with a high refractive index film, but 1.50.
More preferably, the value is less than. The reason is that if the refractive index exceeds 1.50, the antireflection effect may be significantly reduced when combined with a high refractive index film. Therefore, the refractive index of the low refractive index film is more preferably set to a value within the range of 1.25 to 1.45,
More preferably, the value is in the range of 1.30 to 1.42. If the refractive index of the low refractive index film is less than 1.25, the types of usable materials may be excessively limited. When a plurality of low-refractive-index films are provided, at least one of the low-refractive-index films may have a refractive index value in the above-described range. There may be.

When a low-refractive-index film is provided, it is preferable to set the difference in refractive index between the high-refractive-index film and the high-refractive-index film to a value of 0.05 or more, since a better antireflection effect can be obtained. The reason for this is that when the refractive index difference between the low refractive index film and the high refractive index film is less than 0.05, a synergistic effect of these antireflection film layers cannot be obtained, but rather an antireflection effect. This is because there is a case where is decreased. Therefore, the refractive index difference between the low refractive index film and the high refractive index film is more preferably set to a value in the range of 0.10 to 0.50, and more preferably in the range of 0.15 to 0.50. More preferably, it is set to a value.

(4) Thickness First, the thickness of the high refractive index film is not particularly limited, but is preferably, for example, a value in the range of 50 to 30,000 nm. This is because the high refractive index film has a thickness of 5
When the thickness is less than 0 nm, when combined with a low refractive index film, the antireflection effect and the adhesion to the substrate may be reduced. On the other hand, when the thickness exceeds 30,000 nm, optical interference occurs. This is because the anti-reflection effect may be reduced. Therefore, the thickness of the high refractive index film is more preferably set to a value within a range of 50 to 1,000 nm, and further preferably set to a value within a range of 60 to 500 nm. In the case where a plurality of high-refractive-index films are provided to form a multilayer structure in order to obtain higher antireflection properties, the total thickness may be set to a value in the range of 50 to 30,000 nm. When a hard coat layer is provided between the high refractive index film and the base material, the thickness of the high refractive index film is set to 50 to 3
The value can be in the range of 00 nm.

The thickness of the low refractive index film is not particularly limited, but is preferably, for example, in the range of 50 to 300 nm. The reason for this is that if the thickness of the low refractive index film is less than 50 nm, the adhesion to the high refractive index film as a base may decrease, while if the thickness exceeds 300 nm, light interference may occur. This is because the antireflection effect may be reduced. Therefore, the thickness of the low refractive index film is more preferably set to a value within a range of 50 to 250 nm, and further preferably set to a value within a range of 60 to 200 nm. When a plurality of low-refractive-index films are provided to form a multilayer structure in order to obtain higher antireflection properties, the total thickness is 50 to 300 n.
It may be a value within the range of m.

(5) Substrate Next, a substrate for providing a high refractive index film or a hard coat layer or the like as necessary will be described. The type of substrate on which such a high refractive index film or the like is provided is not particularly limited, but examples thereof include glass, polycarbonate resin, polyester resin, acrylic resin, triacetyl acetate resin (TAC), norbornene resin, and the like. The base material which consists of can be mentioned. By forming an anti-reflection laminate including these substrates, it is excellent in the field of use of a wide range of anti-reflection films such as a lens part of a camera, a screen display part of a television (CRT), or a color filter in a liquid crystal display device. The anti-reflection effect can be obtained. In the present invention, a substrate having relatively low heat resistance can be used because a photo-curing reaction is used instead of thermosetting when providing a high refractive index film or the like. Therefore, as a substrate,
For example, when an acrylic resin or a triacetyl acetate resin (TAC) is used, the effect can be remarkably exhibited.

(6) Forming Method 1 Coating When forming a high refractive index film or a low refractive index film from the curable composition for a high refractive index film or the curable composition for a low refractive index film, respectively,
These are preferably applied (coated) to a substrate (applied member). Such a coating method is not particularly limited, but includes, for example, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, or an inkjet method. A method such as a method can be used.

High Refractive Index Film In forming the antireflection laminate of the second embodiment, the high refractive index film is formed by photocuring a curable composition for a high refractive index film. Become. In this case, an ultraviolet irradiation device (such as a metal halide lamp)
It is preferable that the light irradiation condition be in the range of 01 to 10 J / cm ² . The reason is that under such irradiation conditions, a sufficiently cured high refractive index film can be obtained, but the production time does not become excessively long. Accordingly, the light irradiation conditions, more preferably, to 0.01~5J / cm ^2, and even more preferably from 0.1~3J / cm ^2.

In order to form the antireflection laminate of the second embodiment, the low-refractive-index film is obtained by coating the curable composition for a low-refractive-index film on a high-refractive-index film. It will be formed by thermosetting. In this case, it is preferable to heat at 30 to 120 ° C. for 1 to 180 minutes. The reason for this is that under such heating conditions, it is possible to more efficiently obtain an antireflection laminate having excellent antireflection properties without damaging the base material or the formed antireflection film. is there. Therefore, as the heating condition, heating at 50 to 100 ° C. for 2 to 120 minutes is more preferable, and heating at 60 to 90 ° C. for 5 to 60 minutes is further preferable.

[0066]

Hereinafter, embodiments of the present invention will be described in detail.
The scope of the present invention is not limited to the description of these examples. In the examples, the amounts of the respective components mean parts by weight unless otherwise specified.

Example 1 (1) Preparation of Curable Composition for High Refractive Index Film The following components (A) were placed in a container equipped with a stirrer.
After containing (B), (G1) and (G2), they are uniformly mixed and dispersed to obtain solvent-dispersed ATO fine particles (solid content of 3%).
(3% by weight) 150 parts by weight were prepared. (A): Antimony-doped tin oxide fine particles (average particle diameter: 20 nm; hereinafter, ATO fine particles) 35 parts by weight (B): Denkabutyral # 2000-L (manufactured by Denki Kagaku Kogyo KK, polyvinyl butyral resin, average polymerization) Degree of about 300, polyvinyl alcohol unit in one molecule is 21% by weight or more, glass transition temperature is 71 ° C.) 15 parts by weight (G1): methyl isobutyl ketone (hereinafter abbreviated as MIBK) 60 parts by weight (G2): t -Butanol 40 parts by weight

Then, the following components (C) and (D) were added while stirring the inside of the container, and the mixture was further stirred for 60 minutes to obtain a viscosity of 10 mPa · s (measuring temperature of 25 ° C.) and a solid concentration of 50 wt. % Of the curable composition for a high refractive index film (high concentration product: A type). (C): Nicalac MX302 (manufactured by Sanwa Chemical Co., Ltd., 45 parts by weight of melamine / formaldehyde / alkyl monoalcohol (C ₁ -C ₁₂ ) condensate and 2-hydroxyethyl acrylate) (D) : 5 parts by weight of Irgacure 907 (optical radical initiator manufactured by Ciba Specialty Chemicals Co., Ltd.)

Then, 200 parts by weight of the obtained curable composition for a high refractive index film (A type) was charged into a container equipped with a stirrer, and 420 parts by weight of t-butanol was added to the mixture while stirring.
After further charging BK630 parts by weight, the mixture was stirred for 10 minutes to obtain a curable composition for a high refractive index film having a viscosity of 2 mPa · s (measuring temperature 25 ° C.) and a solid concentration of 8.0% by weight (low concentration product: B type).

(2) Evaluation of Storage Stability of Curable Composition for High Refractive Index Film The storage stability of the obtained curable compositions for high refractive index film (A and B types) was evaluated according to the following criteria. did.
Table 1 shows the obtained results. 〇: No sedimentation of metal oxide particles was observed even after the curable composition for a high refractive index film was allowed to stand at room temperature for 30 days, and a metal halide lamp (Eye Graphics Co., Ltd.)
And light curing under light irradiation conditions of 0.5 J / cm ² . Δ: After the curable composition for a high refractive index film was allowed to stand at room temperature for 30 days, slight sedimentation of the metal oxide particles was observed, but the composition could be photocured under the above irradiation conditions. ×: After the curable composition for a high refractive index film was allowed to stand at room temperature for 30 days, remarkable sedimentation of metal oxide particles was observed.
Alternatively, photocuring cannot be performed under the above irradiation conditions.

(3) Evaluation of coatability of curable composition for high-refractive-index film The coatability of the curable composition for high-refractive-index film (A and B types) was visually observed according to the following criteria. evaluated. Table 1 shows the obtained results. 〇: The curable composition for a high refractive index film can be applied to a uniform thickness using a wire bar coater (# 3). Δ: The curable composition for a high refractive index film can be applied to a substantially uniform thickness using a wire bar coater (# 3). ×: The curable composition for a high refractive index film cannot be coated to a uniform thickness using a wire bar coater (# 3).

(4) Measurement of Refractive Index of Curable Composition for High Refractive Index Film The curable composition for high refractive index film (B type) was obtained using a spin coater (rotation speed: 1,000 rpm × 20 seconds). Then, it was coated on a silicon wafer and air-dried at room temperature for 5 minutes to form a coating film. Next, the coating film was photocured under the light irradiation condition of 0.5 J / cm ² by using the above-mentioned metal halide lamp to form a high refractive index film having a thickness of 0.3 μm. The refractive index of the Na-D line in the obtained high refractive index film was measured using a spectroscopic ellipsometer at a measurement temperature of 25 ° C. Table 1 shows the obtained results. Note that A
The refractive index of the type composition was the same as the refractive index of the B type of the same composition.

(5) Preparation of Curable Composition for Low Refractive Index Film A stainless steel autoclave with an inner volume of 1.5 L equipped with an electromagnetic stirrer.
After thoroughly replacing the inside of the reactor with nitrogen gas, ethyl acetate 5
00 g and 57.2 g of ethyl vinyl ether (EVE)
And hydroxybutyl vinyl ether (HBVE) 1
0.2 g and 3 g of lauroyl peroxide
After cooling down to -50 ° C with ice-methanol,
Oxygen in the system was removed with elemental gas. Next, hexafluo
Charge 146g of polypropylene (HFP) and start heating
did. When the temperature in the autoclave reaches 60 ° C
Is 5.2 × 10 ^FivePa was indicated. Then 60
The reaction was continued under stirring at 20 ° C. for 20 hours, and the pressure was 1.5 × 1.
0^FiveWhen the autoclave was cooled down to Pa,
Response was stopped. After reaching room temperature, unreacted gas monomer
And the autoclave is opened to bring the solids concentration to 2
A polymer solution of 8.1% by weight was obtained. This polymer
After pouring the solution into methanol to precipitate the polymer,
The polymer is further washed with methanol, and
193 g of fluorine-containing copolymer having hydroxyl group after air drying
I got a body.

The obtained fluorine-containing copolymer having a hydroxyl group has an intrinsic viscosity (using an N, N-dimethylacetamide solvent, measuring temperature of 25 ° C.) of 0.26 dl / g,
The glass transition temperature (DSC measurement, heating rate 5 ° C./min, in a nitrogen stream) is 20 ° C., the fluorine content (Alizarin complexon method) is 53.4% by weight, and the hydroxyl value (using acetic anhydride) Acetyl value method) is 27.1 mg KOH /
g.

Next, 100 parts by weight of a fluorinated copolymer having a hydroxyl group and Cymer 303 are placed in a container equipped with a stirrer.
10 parts by weight of an alkoxylated methyl melamine compound (manufactured by Mitsui Cytec Co., Ltd.) and 900 parts by weight of MIBK were added, and the mixture was stirred at 100 ° C. for 5 hours at a temperature of 100 ° C. for 5 hours. Cymel 303
Was reacted. Then, as a thermal acid generator, Catalyst 4050 (manufactured by Mitsui Cytec Co., Ltd., solid content concentration 3)
2%) was further added and stirred for 10 minutes to obtain a curable composition for a low refractive index film having a viscosity of 2 mPa · s (measuring temperature 25 ° C).

The refractive index of the obtained curable composition for a low refractive index film was measured in the same manner as the curable composition for a high refractive index film. That is, the curable composition for a low-refractive-index film was prepared using a spin coater (rotation speed: 1,000 rpm × 20 seconds).
Coat on a silicon wafer and air dry at room temperature for 5 minutes,
A coating was formed. Next, the coating film was photocured using the above-mentioned metal halide lamp under a light irradiation condition of 0.5 J / cm ² to form a low refractive index film having a thickness of 0.3 μm. The refractive index of the Na-D line in the obtained low refractive index film was measured using a spectroscopic ellipsometer at a measurement temperature of 25 ° C. Table 1 shows the obtained results.

(6) Formation of Antireflection Laminate The obtained curable composition for high refractive index film (A type) was applied to a polymethacrylstyrene plate (2 mm thick) using a wire bar coater (# 12). , Manufactured by Mitsubishi Gas Chemical Co., Ltd.) and air-dried at room temperature for 5 minutes to form a coating film. Then, using the above-mentioned metal halide lamp, 0.5 J / c
The coating film was photocured under light irradiation conditions of m ² to form a high refractive index film (A type) having a thickness of 5 μm. Further, the obtained curable composition for a high refractive index film (B type) is coated on a polymethacrylstyrene plate using a wire bar coater (# 3), and air-dried at room temperature for 5 minutes to form a coating. A film was formed. Then, 0.5 J /
The coating film was photocured under the light irradiation condition of cm ² to form a high refractive index film (B type) having a thickness of 0.3 μm.

Next, the curable composition for a low refractive index film is applied onto each of the high refractive index films (A and B types) using a wire bar coater (# 3), and air-dried at room temperature for 5 minutes. Thus, a coating film was formed. Then use an oven for 8
Heating was performed at 5 ° C. for 60 minutes to obtain a high refractive index film (A
When a low-refractive-index film having a thickness of 110 nm is formed on the substrate by curing, an antireflection laminate (type I) is formed on the high-refractive-index film (type B) on the substrate. When the refractive index film is cured, the antireflection laminate (II
Type). That is, the antireflection laminate using the curable composition for a high refractive index film as a hard coat is an I type, and the antireflection laminate using the curable composition for a high refractive index film as an optical thin film is II. Type.

(7) Evaluation of Antireflection Laminate The antireflection properties, transparency, turbidity (Haze value) and hardness of the obtained antireflection laminates (types I and II) were determined by the following methods. Was measured. In addition, the adhesion between the antireflection film and the substrate was evaluated according to the following criteria.

Anti-reflection property The anti-reflection properties of the obtained anti-reflection laminates (I and II types) were measured by using a spectral reflectance measuring device (a magnetic spectrophotometer U- 3410, manufactured by Hitachi, Ltd.)
The reflectance was measured and evaluated in the range of 40 to 700 nm.
That is, the reflectance of the aluminum vapor-deposited film is set as a reference (10
0%), the reflectance of the antireflection laminate (antireflection film) at each wavelength was measured, and the antireflection property was evaluated from the reflectance of light at a wavelength of 550 nm according to the following criteria. Table 1 shows the results. A: The reflectance is 1% or less. ：: The reflectance is 2% or less. Δ: The reflectance is 3% or less. X: The reflectance is a value exceeding 3%.

Transparency The light transmittance (T%) at a wavelength of 550 nm in the obtained anti-reflection laminates (I and II types) was measured using a spectrophotometer. The transparency was evaluated based on criteria. Table 1 shows the obtained results. ：: The light transmittance is 95% or more. Δ: Light transmittance is a value of 80 to less than 95%. X: The light transmittance is a value of less than 80%.

Turbidity Turbidity (Haze value) of the obtained anti-reflection laminates (I and II types) was measured using a Haze meter. Table 1 shows the obtained results.

Hardness To avoid the influence of the softness of the base material, a quartz plate having a high hardness value was used instead of the polymethacrylic styrene plate.
A high-refractive-index film and a low-refractive-index film were sequentially laminated from the lower side to prepare an antireflection laminate for hardness measurement. The pencil hardness of the obtained antireflection laminate was measured according to JIS K54.
It was measured according to 00. The determination of the pencil hardness was made by visually observing the presence or absence of scratches. Table 1 shows the obtained results.

Adhesion The surface of the obtained antireflection laminate (I and II type) was coated with paper (Kimwipe, manufactured by Crecia Corporation).
Rubbing was performed under a load of 1 kg / cm ² , and the scratch resistance of the antireflection film was evaluated according to the following criteria. Table 1 shows the obtained results. A: No scratches on the antireflection film and no peeling of the antireflection film are observed even after rubbing under the condition of reciprocating 1,000 times. ：: When rubbing was performed 1,000 times back and forth, fine scratches were observed on the antireflection film, but no peeling of the antireflection film was observed. Alternatively, even when the substrate is rubbed under the condition of reciprocating 200 times, generation of scratches on the antireflection film and peeling of the antireflection film are not observed. Δ: When rubbing was performed 200 times in a reciprocating manner, fine scratches were observed on the antireflection film, but peeling of the antireflection film was not observed. X: When rubbing was performed 200 times back and forth, peeling of the antireflection film was observed.

[0085]

[Table 1]

Example 2 In Example 2, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., polyfunctional acrylate, hereinafter referred to as D
Abbreviated as PHA. ) Was investigated. That is, 150 parts by weight of the solvent-dispersed ATO fine particles prepared in the same manner as in Example 1 were accommodated in a container equipped with a stirrer, and while stirring the inside of the container, Nicalac MX30230 parts by weight and D
15 parts by weight of PHA and 5 parts by weight of Irgacure 907 were sequentially added, and the mixture was stirred for 60 minutes to give a viscosity of 10 mPa ·
As a result, a curable composition for a high refractive index film (high concentration product: A type) having a s (measuring temperature of 25 ° C.) and a solid concentration of 50% by weight was obtained.

Then, 200 parts by weight of the obtained curable composition for a high refractive index film (A type) was charged into a container equipped with a stirrer, and 420 parts by weight of t-butanol was added with stirring.
After further charging BK630 parts by weight, the mixture was stirred for 10 minutes to obtain a curable composition for a high refractive index film having a viscosity of 2 mPa · s (measuring temperature 25 ° C.) and a solid concentration of 8.0% by weight (low concentration product: B type).

Next, for each of the curable compositions for a high refractive index film (A and B types), as in Example 1,
The storage stability and the like were evaluated. In addition, the antireflection laminates (I and II) were obtained from the respective curable compositions for high refractive index films.
Type) was formed, and the antireflection property and the like were evaluated. Table 1 shows the obtained results.

Example 3 In Example 3, the effect of adding Catalyst 4050 as a thermal acid generator was examined. That is, the following components were uniformly mixed and dispersed in a vessel equipped with a stirrer to prepare 147.8 parts by weight of solvent-dispersed ATO fine particles (solids concentration: 33.8% by weight). ATO fine particles 35 parts by weight Denka butyral # 2000-L 15 parts by weight MIBK 58.7 parts by weight t-butanol 39.1 parts by weight Next, while stirring the inside of the container, Nicalac MX302
30 parts by weight, 15 parts by weight of DPHA, and Irgacure 9
07 parts by weight and 6.25 parts by weight of Catalyst 4050 (3 parts by weight of solid content) are added in sequence, and the mixture is stirred for 60 minutes to have a viscosity of 10 mPa · s (measuring temperature 25 ° C.) and a solid content concentration of 50% by weight. Of the high refractive index film (high concentration product: A type) was obtained.

Next, 204 parts by weight of the obtained curable composition for a high refractive index film (A type) was charged into a vessel equipped with a stirrer, and 428.9 parts by weight of t-butanol (468 parts by weight in total) was stirred. And MIBK 642.3 parts by weight (total amount: 701 parts by weight), and then stirred for 10 minutes to obtain a high refractive index having a viscosity of 2 mPa · s (measuring temperature 25 ° C.) and a solid concentration of 8.0% by weight. A curable composition for film (low concentration product: B type) was obtained. Next, for each of the curable compositions (A and B types) for a high refractive index film, Example 1 was used.
Evaluation of storage stability and the like was performed in the same manner as described above. Further, an antireflection laminate (I and II type) was formed from each of the curable compositions for a high refractive index film, and the antireflection properties and the like were evaluated. Table 1 shows the obtained results.

Example 4 In Example 4, the effect of adding IBCF (manufactured by Sanwa Chemical Co., Ltd.) as a photoacid generator was examined. That is, MIBK is placed in a container with a stirrer.
In the same manner as in Example 3 except that the amount of t-butanol was 40.3 parts by weight, and
It contained 150.8 parts by weight of O fine particles. Next, 30 parts by weight of Nikarac MX302 while stirring the inside of the container,
15 parts by weight of DPHA, 5 parts by weight of Irgacure 907, 6.25 parts by weight of Catalyst 4050, IBC
F 3 parts by weight, and stirred for 60 minutes to obtain a curable composition for a high refractive index film having a viscosity of 10 mPa · s (measuring temperature 25 ° C.) and a solid concentration of 50% by weight (high concentration product: A type) ) Got.

Next, 210 parts by weight of the obtained curable composition for a high refractive index film (A type) was charged into a container equipped with a stirrer, and 440.7 parts by weight of t-butanol (total amount: 481 parts by weight) was stirred. And 661.5 parts by weight of MIBK (total amount of 722.0 parts by weight) were further charged, and then stirred for 10 minutes to obtain a liquid having a viscosity of 2 mPa · s (measuring temperature of 25 ° C.) and a solid content of 8.0% by weight. A curable composition for a refractive index film (low concentration product: B type) was obtained. Next, storage stability and the like were evaluated for each of the curable compositions for high refractive index films (A and B types) in the same manner as in Example 1. Further, an antireflection laminate (I and II type) was formed from each of the curable compositions for a high refractive index film, and the antireflection properties and the like were evaluated. Table 1 shows the obtained results.

Example 5 In Example 5, the influence of the type of the organic solvent was examined. That is, as an organic solvent, Table 1
As shown in Example 1, except that only t-butanol was used, curable compositions for high refractive index films (A and B types) were prepared in the same manner as in Example 1. Next, for each of the curable compositions (A and B types) for a high refractive index film, Example 1 was used.
Evaluation of storage stability and the like was performed in the same manner as described above. Further, an antireflection laminate (I and II type) was formed from each of the curable compositions for a high refractive index film, and the antireflection properties and the like were evaluated. Table 1 shows the obtained results.

Comparative Example 1 In Comparative Example 1, the influence of the average particle size of the ATO particles was examined. That is, a curable composition for a high refractive index film (C and D types) was prepared in the same manner as in Example 1 except that tin oxide particles doped with antimony having an average particle diameter of 200 nm were used as metal oxide particles. Prepared. That is, the C type is a high concentration product and the D type is a low concentration product. Next, storage stability and the like were evaluated for each of the curable compositions for a high refractive index film (C and D types) in the same manner as in Example 1. Further, from each of the curable compositions for a high refractive index film, an antireflection laminate (I
And II type), and the antireflection property and the like were evaluated.
That is, heating is performed at 85 ° C. for 60 minutes using an oven, and a thickness of 11 mm is formed on the high refractive index film (C type) on the substrate.
The case where a low-refractive-index film of 0 nm is formed is referred to as an antireflection laminate (I-type), and a high-refractive-index film (D-type) on a substrate.
A case where a low refractive index film having a thickness of 110 nm is formed on
This was an antireflection laminate (II type). Table 2 shows the obtained results.

[0095]

[Table 2]

Comparative Example 2 In Comparative Example 2, the effect of the hydroxyl group-containing polymer was examined. That is, without using a hydroxyl group-containing polymer, a solvent-dispersed ATO comprising 35 parts by weight of ATO fine particles (20 nm), 60 parts by weight of methyl isobutyl ketone, and 40 parts by weight of t-butanol was placed in a container equipped with a stirrer. Fine particles (solid concentration 26% by weight) 135
Nikalac MX while stirring the container by weight
302 60 parts by weight and Irgacure 907 5 parts by weight are sequentially added and stirred for 60 minutes to give a viscosity of 10 mPa ·
As a result, a curable composition for a high refractive index film (high concentration product: C type) having a s (measuring temperature of 25 ° C.) and a solid concentration of 50% by weight was obtained.

Then, 200 parts by weight of the obtained curable composition for a high refractive index film (C type) was charged into a vessel equipped with a stirrer, and 420 parts by weight of t-butanol (total amount of 460 parts by weight) was stirred. MIBK 630 parts by weight (total amount 69
0 parts by weight) and further stirred for 10 minutes.
7. Viscosity 2 mPa · s (measuring temperature 25 ° C.), solid content concentration 8.
0% by weight of a curable composition for a high refractive index film (low concentration product: D type) was obtained. Next, storage stability and the like were evaluated for each of the curable compositions for a high refractive index film (C and D types) in the same manner as in Example 1. Further, an antireflection laminate (I and II type) was formed from each of the curable compositions for a high refractive index film, and the antireflection properties and the like were evaluated. Table 2 shows the obtained results.

[Comparative Example 3] In Comparative Example 3, the effect of the compound was examined. That is, the ATO fine particles (20 n
m) 35 parts by weight of Denka Butyral # 2000-L
150 parts by weight of solvent-dispersed ATO fine particles (solid content concentration: 33% by weight) composed of 15 parts by weight, 60 parts by weight of MIBK, and 40 parts by weight of t-butyl alcohol were contained. Next, while stirring the inside of the container, 45 parts by weight of DPHA,
9075 parts by weight of Irgacure are sequentially added, and the mixture is stirred for 60 minutes. The curable composition for a high refractive index film having a viscosity of 10 mPa · s (measuring temperature 25 ° C.) and a solid concentration of 50% by weight (high concentration product: C type) ) Got.

Next, 200 parts by weight of the obtained curable composition for a high refractive index film (C type) was charged into a vessel equipped with a stirrer, and 428.9 parts by weight of t-butanol (468 parts by weight in total) was stirred. And 630 parts by weight of MIBK (690 parts by weight in total), and then stirred for 10 minutes to obtain a high refractive index film having a viscosity of 2 mPa · s (measuring temperature 25 ° C.) and a solid concentration of 8.0% by weight. Curable composition (low concentration product:
D type). Next, storage stability and the like were evaluated for each of the curable compositions for a high refractive index film (C and D types) in the same manner as in Example 1. Further, an antireflection laminate (I and II type) was formed from each of the curable compositions for a high refractive index film, and the antireflection properties and the like were evaluated. Table 2 shows the obtained results.

[0100]

According to the curable composition for a high refractive index film of the present invention, a photocuring reaction can be utilized, and a high refractive index film can be formed quickly and without heating. Therefore, conventionally, a high-refractive-index film can be easily formed even on a substrate that is easily thermally degraded. Further, according to the curable composition for a high refractive index film of the present invention, since it has a predetermined refractive index after curing, when combined with a low refractive index film, excellent antireflection properties can be obtained. Became. Further, according to the high refractive index film of the present invention, it has a specific refractive index while being composed of specific constituent components, and when combined with a low refractive index film, excellent antireflection properties are obtained. As a result, a strong adhesive force can be obtained. Furthermore, according to the antireflection laminate of the present invention, a high-refractive-index film composed of a specific component and a low-refractive-index film composed of a specific component are combined, and excellent antireflection properties are obtained. At the same time, between the high refractive index film and the low refractive index film,
Strong adhesion has been obtained.

According to the antireflection laminate of the present invention, since a photocuring reaction is used for forming the high refractive index film,
Even if the low-refractive-index film is cured by heat, the heat treatment conditions are relaxed as a whole. Therefore, compared to the case where both the high-refractive-index film and the low-refractive-index film are conventionally formed by thermosetting, a substrate having relatively poor heat resistance, such as an acrylic resin or a triacetyl acetate resin (TAC), is used. In the case where the base materials are used, the effect of reducing the thermal deterioration of these base materials can be obtained.

[Brief description of the drawings]

FIG. 1 is a view showing a cross section of an antireflection laminate of the present invention (part 1).

FIG. 2 is a view showing a cross section of the antireflection laminate of the present invention (part 2).

[Explanation of symbols]

 10, 20 high refractive index film 12 base material 14, 22 low refractive index film 16, 24 antireflection laminate 18 hard coat layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 2/50 C08F 2/50 291/08 291/08 C08J 7/18 CEY C08J 7/18 CEY G02B 1 / 11 C08L 33:06 // C08L 33:06 G02B 1/10 A (72) Inventor Akira Nishikawa 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR term in JSR Corporation (reference) 2K009 AA05 AA15 BB13 CC03 CC21 CC24 CC26 DD02 DD05 DD06 4F073 AA32. PA27 PA63 PA67 PA69 PA85 PB40 PC02 SA04 SA06 SA25 SA26 SA27 SA34 SA54 SA61 SA62 SA63 SA64 SA82 SA83 SA84 SA87 UA01 UA04 UA06 VA01 WA02 4J026 AA28 AA44 AA45 AB01 AB22 AC09 AC36 BA26 BA50 DB06 DB36 GA06 GA07 GA08

Claims (9)

[Claims] 1. A curable composition for a high refractive index film, comprising the following components (A) to (D) and having a refractive index after curing of 1.50 or more. (A) Metal oxide particles having an average particle diameter of 0.1 μm or less (B) Hydroxyl group-containing polymer (C) Compound having both a functional group capable of reacting with a hydroxyl group and a photopolymerizable functional group (D) Photopolymerization initiation Agent 2. The curable composition for a high refractive index film according to claim 1, further comprising an acrylate compound (excluding the acrylate compound in the component (C)) as the component (E). . 3. The curable composition for a high refractive index film according to claim 1, further comprising a thermal acid generator as the component (F). 4. The high refractive index film according to claim 1, further comprising a mixed solvent comprising an alcohol-based solvent and a ketone-based solvent as the component (G). Curable composition. 5. The method according to claim 1, wherein the photopolymerization initiator as the component (D) comprises a combination of a photoradical initiator and a photoacid generator. Curable composition for high refractive index film. 6. A high-refractive-index film obtained by curing the curable composition for a high-refractive-index film according to claim 1. 7. An antireflection laminate comprising a high refractive index film obtained by curing the curable composition for a high refractive index film according to any one of claims 1 to 5. 8. A low-refractive-index film formed by thermally curing a curable composition for a low-refractive-index film containing the following components and components, and a refractive index of the low-refractive-index film on the high-refractive-index film. The antireflection laminate according to claim 7, wherein the ratio is set to a value less than 1.50. Fluorine-containing copolymer having hydroxyl group Thermosetting agent having functional group capable of reacting with hydroxyl group 9. When thermally curing the curable composition for a low-refractive-index film, the curable composition for a low-refractive-index film may react with a part of the high-refractive-index film. The anti-reflection laminate according to claim 7 or 8, wherein: