JPH10182745A - Fluorine-containing monomer composition and reflectivity-reduced film made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition which gives a low-refractivity material with both low refractive index and high surface hardness, reflectivity- reduced film and stocks that give the above, by incorporating a given quantity of a given, fluorine-containing, multi-functional (meth)acrylic ester. SOLUTION: This fluorine-containing monomer composition, giving a low- reflectivity material showing a low refractivity and high surface hardness, reduced-reflectivity film or the like, is obtained by compounding 5 to 100wt.% of a fluorine-containing, multi-functional (meth)acrylic ester shown by the formula [X is a 1-14C fluroroalkyl having 3 or more F atoms or 3-14C fluoroalkyl having 4 or more F atoms; Y<1> to Y<3> are each H or (meth)acryloyl, where at least 2 out of Y<1> to Y<3> ate each (meth)acryloyl; Z is H or a 1-3C alkyl; (n) and (m) are each 0 or 1; and (n)+(m)=1], e.g. tetraacrylate-4,4,5,5,6,6,7,7- octafluorodecane-1,2,9,10-tetraol), with another multi-functional monomer, e.g. tetramethylolmethane tetraacrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a monomer composition which has a high surface hardness and a low refractive index and can be used as a raw material of a low refractive index material which can be used for various substrate surfaces and the like. The present invention relates to a low refractive index material obtained by polymerizing and curing a body composition, and an antireflection film provided with the low refractive index material.

[0002]

2. Description of the Related Art Since a compound having a fluorine atom has a low refractive index, it can be used as an antireflection film or a cladding material for optical fibers. In any case, the performance improves as the refractive index decreases. For example, a polymer of a fluorine-containing (meth) acrylate, a copolymer with another monomer, a tetrafluoroethylene polymer, a copolymer of vinylidene fluoride and tetrafluoroethylene, or a copolymer of vinylidene fluoride and hexafluoropropylene Applications of polymers and the like to optical fibers have been proposed (JP-A-59-84203, JP-A-59-84204, JP-A-59-98116, JP-A-59-147001, JP-A-59-2
No. 04002). Recently, a fluorine-containing alkyl ester polymer of acrylic acid, a fluorine-containing alkyl ester polymer of methacrylic acid, or a non-product such as trade name "CYTOP" (manufactured by Asahi Glass Co., Ltd.) Attempts have been made to apply solvent-soluble low-refractive-index fluoropolymers such as crystalline perfluororesins to antireflection films (JP-A-64-16873, JP-A-1-149808, JP-A-6-149808). No. 115023). However, these fluorine-containing resins are all non-crosslinkable resins, and have the drawback that the surface hardness after curing is low, the abrasion resistance is poor, and the adhesion is insufficient.

In order to improve the surface hardness, a fluorine-containing monofunctional (meth) acrylate or a fluorine-containing bifunctional (meth) acrylate
A crosslinked polymer obtained by appropriately mixing an acrylate and a non-fluorine-containing polyfunctional (meth) acrylate has been proposed (JP-A-58-105943, JP-A-62-199643). JP-A-62-2500
No. 47). These crosslinked polymers are fluorinated (meth)
Fluorine content and non-fluorine-containing polyfunctionality in acrylic ester
By adjusting the mixing ratio with the (meth) acrylic acid ester, the low refractive index and the surface hardness can be adjusted within a certain range. However, the fluorinated monofunctional (meth) acrylate and the polyfunctional (meth) acrylate are incompatible with each other at an arbitrary ratio. Therefore, a sufficiently low refractive index cannot be achieved. On the other hand, the fluorinated bifunctional (meth) acrylate and the polyfunctional (meth) acrylate are compatible at an arbitrary ratio. However, if the content of fluorine atoms in the crosslinked polymer is increased to lower the refractive index, the crosslink density decreases. Therefore, low refractive index and surface hardness cannot be satisfactorily compatible, and it is difficult to impart surface hardness to the optical fiber and the antireflection film. In addition, there is a problem in adhesion.

[0004] Improvement of adhesion, and other fluorine-containing (meth)
For the purpose of using acrylic acid esters as raw materials, fluorine-containing hydroxy (meth) acrylic acid esters have been proposed (JP-A-4-321660, JP-A-4-356443, JP-A-4-356444). ). However, since these are monofunctional (meth) acrylates, they have the disadvantage that the surface hardness after curing is low and the abrasion resistance is poor.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a low-refractive-index material capable of satisfying a low refractive index and excellent surface hardness, a low-reflection film, and a fluorine-containing monomer composition which can be used as a raw material thereof. Is to provide.

[0006]

According to the present invention, there is provided a monomer composition represented by the following general formula (1) and containing 5 to 100% by weight of a fluorine-containing polyfunctional (meth) acrylate. Is done.

[0007]

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(Wherein X represents a C1-14 fluoroalkyl group having 3 or more fluorine atoms or a C3-14 fluorocycloalkyl group having 4 or more fluorine atoms; Y ¹ , Y ^{1 2} and Y ³ represent a hydrogen atom, an acryloyl group or a methacryloyl group, and at least two of Y ¹ , Y ² and Y ³ are the same or different groups and represent an acryloyl group or a methacryloyl group; Z
Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n and m each represent 0 or 1, and n + m = 1. According to the present invention, there is also provided a monomer composition containing the above-mentioned monomer composition and inorganic compound fine particles. Further, according to the present invention, there is provided a low refractive index material having a refractive index of 1.49 or less, which is obtained by polymerizing and curing the monomer composition. Further, according to the present invention, there is provided an anti-reflection film including a transparent substrate and a layer of the low refractive index material. Further, according to the present invention, there is provided an anti-reflection film including at least one material layer between a transparent substrate and the layer of the low refractive index material.

[0009]

DISCLOSURE OF THE INVENTION The monomer composition of the present invention is a composition containing 5 to 100% by weight of a fluorinated polyfunctional (meth) acrylate represented by the general formula (1),
When polymerized and cured, a cured film having a three-dimensional network structure and excellent in scratch resistance, adhesion, abrasion resistance, heat resistance, weather resistance and the like can be obtained.

The fluorine-containing polyfunctional (meth) acrylate of the present invention can be represented by the above formula (1). In the formula (1), when n = 1 and m = 0, it can be represented by the following formula (1a), and when n = 0 and m = 1, it can be represented by the following formula (1b).

[0011]

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Specifically, in the above formula (1a), Y ¹ ,
^Two of Y ² and Y ^{3 represent} an acryloyl group or a methacryloyl group, and the other one represents a hydrogen atom, and has a (meth) acryloyl group and a hydroxyl group. The formula (1b)
Wherein ^{two of} Y ¹ , Y ² and Y ^{3 represent} an acryloyl group or a methacryloyl group, and the other one represents a hydrogen atom, wherein the fluorine-containing difunctional (meth) acrylic acid having a (meth) acryloyl group and a hydroxyl group Ester (hereinafter referred to as diester B); in the above formula (1a), Y ¹ , Y ² and Y ³ are the same or different groups, and represent an acryloyl group or a methacryloyl group, and a fluorine-containing trifunctional (meth) acrylate ester
(Hereinafter referred to as triester A); in the above formula (1b),
Y ¹ , Y ² and Y ³ are the same or different groups and represent an acryloyl group or a methacryloyl group, a fluorine-containing trifunctional
(Meth) acrylic acid ester (hereinafter referred to as triester B). In the formula (1), when X has more than 12 carbon atoms, production is difficult.

Examples of the diester A include 3-perfluorohexyl-2-hydroxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate and 3-perfluorohexyl-2-((meth) acryloyloxy)
Propyl = 2-((meth) acryloyloxymethyl) -2
-(Hydroxymethyl) propionate, 3-perfluorooctyl-2-hydroxypropyl = 2,2-bis
((Meth) acryloyloxymethyl) propionate, or 3-perfluorooctyl-2-((meth) acryloyloxy) propyl = 2-((meth) acryloyloxymethyl) -2- (hydroxymethyl) propionate .

As the diester B, 2-perfluorohexyl- (1-hydroxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate;
2-perfluorohexyl-1-((meth) acryloyloxymethyl) ethyl = 2-((meth) acryloyloxymethyl) -2- (hydroxymethyl) propionate, 2
-Perfluorooctyl- (1-hydroxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate or 2-perfluorooctyl-1-
((Meth) acryloyloxymethyl) ethyl = 2-((meth) acryloyloxymethyl) -2- (hydroxymethyl) propionate and the like are preferred.

As the triester A, 3-perfluorobutyl-2- (meth) acryloyloxypropyl =
2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorohexyl-2- (meth) acryloyloxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorooctyl-2 -(Meth) acryloyloxypropyl =
2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorocyclopentylmethyl-2
-(Meth) acryloyloxypropyl = 2,2-bis
((Meth) acryloyloxymethyl) propionate, 3
-Perfluorocyclohexylmethyl-2- (meth) acryloyloxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate or 3-perfluorocycloheptylmethyl-2- (meth) acryloyloxypropyl = 2,2- Bis ((meth) acryloyloxymethyl) propionate and the like are preferred.

As the triester B, 2-perfluorobutyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 2-perfluorohexyl- (1- ( (Meth) acryloyloxymethyl) ethyl = 2,2-bis
((Meth) acryloyloxymethyl) propionate, 2
-Perfluorooctyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 2-perfluorocyclopentylmethyl- (1- (meth) acryloyloxymethyl) ethyl = 2 , 2-Bis ((meth) acryloyloxymethyl) propionate, 2-perfluorocyclohexylmethyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl)
Propionate or 2-perfluorocycloheptylmethyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate is preferably exemplified.

These diester A, diester B, triester A and triester B can be used alone or as a mixture when used as a raw material such as a low refractive index resin (hereinafter, a mixture of diester A and diester B). Is referred to as a "diester mixture", a mixture of triester A and triester B is referred to as a "triester mixture", and a mixture of a diester and a triester, a diester mixture or a triester mixture is collectively referred to as an "ester mixture". There is).

The diesters A and B and the triesters A and B can be produced, for example, by a method for obtaining a diester mixture or a triester mixture. Further, diesters A and B and triesters A and B can be separated from the obtained ester mixture by an appropriate method. As a method for producing the ester mixture,
The following two types of manufacturing methods can be exemplified.

A first method for producing a diester mixture and a triester mixture is as follows: (a) First, a carboxylic acid having two hydroxymethyl groups and a corresponding fluorine-containing epoxide are subjected to a usual ring-opening reaction in the presence of a catalyst. Let it react
There is a two-step method in which a mixture of hydroxyfluoroalkyl 2,2-bis (hydroxymethyl) carboxylate is formed, and (b) the mixture is further esterified with (meth) acrylic acid chloride. At this time, by adjusting the equivalent of (meth) acrylic acid chloride, either the diester mixture or the triester mixture can be obtained as a main component. The second method for producing the diester mixture is as follows: (c) First, a carboxylic acid having two hydroxymethyl groups is prepared from a carboxylic acid having two hydroxymethyl groups by the method described in JP-A-63-99038. 2,2-bis ((meth) acryloyloxymethyl) carboxylic acid is produced by, for example, reacting (meth) acrylic acid chloride or (meth) acrylic acid ester in the presence of a suitable catalyst if necessary. (D) Then, a two-step method of reacting the carboxylic acid with the corresponding epoxide by a usual ring-opening reaction in the presence of a catalyst may be mentioned. The second method for producing the triester mixture includes a three-step method in which the diester mixture obtained in steps (c) and (d) is further esterified with (meth) acrylic acid chloride. A mixture of several structural isomers is obtained by any of the production methods,
In actual use, the mixture may be used as it is.

The composition of the present invention contains the fluorine-containing polyfunctional (meth) acrylate or the fluorine-containing polyfunctional (meth) acrylate and inorganic compound fine particles. The fluorinated polyfunctional (meth) acrylic acid ester is a compound represented by the formula (1), and specifically includes a group consisting of the diester A, diester B, triester A, triester B, and a mixture thereof. Fluorinated polyfunctional (meth) acrylic acid ester (hereinafter sometimes collectively referred to as polyfunctional ester A)
Is mentioned. When used as a mixture, various ester mixtures obtained in the course of the method for producing the polyfunctional ester A can be used as they are.

The content of the polyfunctional ester A is 5 to 100% by weight, preferably 10 to 100% by weight based on the total amount of the composition.
% By weight. On the other hand, the content ratio of the inorganic compound fine particles is
Less than 90% by weight based on the total weight of the composition is preferred. The lower limit in the case of blending the inorganic compound fine particles is not particularly limited, but is preferably 5% by weight. This composition, when polymerized and cured, exhibits a three-dimensional network structure by crosslinking, and can be a cured film or the like having excellent scratch resistance, adhesion, abrasion resistance, heat resistance, weather resistance, and the like. .

The inorganic compound fine particles are not particularly limited, but a compound having a refractive index of 1.5 or less is preferable. Specifically, magnesium fluoride (refractive index: 1.38), silicon oxide
(Refractive index: 1.46), aluminum fluoride (refractive index: 1.3)
3 to 1.39), calcium fluoride (refractive index: 1.44),
Lithium fluoride (refractive index 1.36 to 1.37), sodium fluoride (refractive index 1.32 to 1.34), thorium fluoride
Fine particles having a refractive index of 1.45 to 1.50 are desirable. The particle size of the fine particles is desirably sufficiently smaller than the wavelength of visible light in order to ensure transparency of the low refractive index material. Specifically, the thickness is preferably 100 nm or less, particularly preferably 50 nm or less.

When the inorganic compound fine particles are used, they are preferably in the form of an organic sol dispersed in an organic dispersion medium in advance so as not to lower the dispersion stability in the composition and the adhesion in the low refractive index material. It is desirable to use. Furthermore, in the composition, in order to improve the dispersion stability of the inorganic compound fine particles, the adhesion in the low refractive index material, and the like, it is possible to previously modify the surface of the inorganic fine particle compound using various coupling agents or the like. it can. Examples of various coupling agents include organically substituted silicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony and mixtures thereof; salts of organic acids; and coordination compounds bonded to coordination compounds. Can be

The composition of the present invention may contain, if necessary, a thermosetting monomer, an energy ray-curable monomer or the like usually used as another curable material in an amount of less than 95% by weight in the composition.
In particular, 90% by weight or less can be blended. As the thermosetting monomer and the energy ray-curable monomer, polyfunctional monomers having two or more polymerizable unsaturated groups, for example, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, ditrimethylolpropanetri
(Meth) acrylate, ditrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth)
Acrylate, trimethylolpropanedi (meth) acrylate, tetramethylolmethanetetraacrylate,
1,1,1-tris (acryloyloxyethoxyethoxy) propane, 2,2-bis (4-acryloyloxyethoxyethoxyphenyl) propane, 2,2-bis (4
-Acryloyloxyethoxyethoxycyclohexyl) propane, bis (4-acryloyloxyethoxyethoxyphenyl) methane, neopentyl glycol di (meth) acrylate, hydrogenated dicyclopentadienyl di (meth) acrylate, tris (hydroxyethyl) isocyanurate Triacrylate, tris (hydroxyethyl)
Isocyanurate diacrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isobornyl di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Preferable examples include polyalkylene glycol di (meth) acrylates such as polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate. When used, they are used alone or as a mixture.

The composition of the present invention may be monofunctional, if necessary.
(Meth) acrylic acid esters can be blended within a range that does not impair the desired effects of the present invention. As the monofunctional (meth) acrylate, a fluorine-containing monofunctional (meth) acrylate is particularly preferred for the purpose of lowering the refractive index of the monomer composition. For example, (meth) acrylic acid-2,2,2-trifluoroethyl, (meth) acrylic acid-2,2,3,3,3
Pentafluoropropyl, (meth) acrylic acid-2,
2,3,3,4,4,4-heptafluorobutyl, (meth) acrylic acid-2,2,3,3,4,4,5,5,5
Nonafluoropentyl, (meth) acrylic acid-2,2,
3,3,4,4,5,5,6,6,6-undecafluorohexyl, (meth) acrylic acid-2,2,3,3,4
4,5,5,6,6,7,7,7-tridecafluoroheptyl, (meth) acrylic acid-2,2,3,3,4,4
5,5,6,6,7,7,8,8,8-pentadecafluorooctyl, (meth) acrylic acid-3,3,4,4
5,5,6,6,7,7,8,8,8-tridecafluorooctyl, (meth) acrylic acid-2,2,3,3,4
4,5,5,6,6,7,7,8,8,9,9,10,
10,10-nonadecafluorodecyl, (meth) acrylic acid-3,3,4,4,5,5,6,6,7,7,8,
8,9,9,10,10,10-heptadecafluorodecyl, 2-trifluoromethyl (meth) acrylate-
3,3,3-trifluoropropyl, 3-trifluoromethyl-4,4,4-trifluorobutyl (meth) acrylate, 1-methyl-2,2,3, (meth) acrylate
Preferable examples include 3,3-pentafluoropropyl or 1-methyl-2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, which is used alone or as a mixture when used. .

The composition of the present invention may further comprise, if necessary, a fluorine-containing difunctional compound other than a diester mixture as a curable material.
(Meth) acrylic acid esters can be blended within a range that does not impair the desired effects of the present invention. As the fluorine-containing bifunctional (meth) acrylate other than the diester mixture, di (meth)
Acrylic acid-2,2,2-trifluoroethylethylene glycol, di (meth) acrylic acid-2,2,3,3,3
-Pentafluoropropylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,4-heptafluorobutylethylene glycol, di (meth) acrylic acid-2,2,3,3,4 , 4,5,5,5-Nonafluoropentyl ethylene glycol, di (meth) acrylic acid
2,2,3,3,4,4,5,5,6,6,6-undecafluorohexylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5 5,6,6,6
7,7,7-tridecafluoroheptyl ethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4
5,5,6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6 6,7,7,
8,8,9,9,10,10,10-nonadecafluorodecylethylene glycol, di (meth) acrylic acid-2,
2,3,3-tetrafluorobutanediol, di (meth)
Acrylic acid-2,2,3,3,4,4-hexafluoropentadiol, di (meth) acrylic acid-2,2,3,
3,4,4,5,5-octafluorohexanediol, di (meth) acrylic acid-2,2,3,3,4,4
5,5,6,6-decafluoroheptanediol, di
(Meth) acrylic acid-2,2,3,3,4,4,5,5
6,6,7,7-dodecafluorooctanediol, di
(Meth) acrylic acid-2,2,3,3,4,4,5,5
6,6,7,7,8,8-tetradecafluorononanediol, di (meth) acrylic acid-2,2,3,3,4
4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecanediol, di (meth) acrylic acid-
2,2,3,3,4,4,5,5,6,6,7,7,
8,8,9,9,10,10-octadecafluoroundecanediol or di (meth) acrylic acid-2,2,3
3,4,4,5,5,6,6,7,7,8,8,9,
Preferred are 9,10,10,11,11-eicosafluorododecanediol and the like, and when used, they are used alone or as a mixture.

A polymer can be added to the composition of the present invention, if necessary, to improve the ability to form a coating film. The polymer for addition is not particularly limited, and examples thereof include a polymer of a fluorinated (meth) acrylate or a copolymer of a fluorinated (meth) acrylate and another monomer. The blending ratio of the polymer for addition is desirably 25 parts by weight or less, particularly preferably 10 parts by weight or less, based on 100 parts by weight of the curable material in the composition.

The low refractive index material of the present invention is obtained by polymerizing and curing the above composition, and has a refractive index of 1.49 or less, preferably 1.35.
It is a material that shows 1.49. The polymerization and curing may be performed, for example, by adding and mixing a curing initiator, if necessary, to a solvent such as isopropyl alcohol or toluene, to the composition, and then performing a usual coating method such as a roll coating method, a gravure coating method, or a dip coating method. It can be applied to a substrate such as a transparent substrate by a spin coating method or the like, dried, and then heat-cured or irradiated with active energy rays such as ultraviolet rays, electron beams or radiation. The polymerization curing conditions are
It can be appropriately selected according to the curable material in the composition. When the low refractive index material is formed in a film shape, the film thickness can be appropriately selected depending on the purpose.

Examples of the curing initiator include azo radical polymerization initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile and azobisvaleronitrile; benzoyl peroxide, tert-butyl hydroperoxide, cumene Organic peroxide radical polymerization initiators such as peroxide or diacyl peroxide; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether or benzoin isopropyl ether; carbonyl compounds such as benzyl, benzophenone, acetophenone or Michler's ketone; An azo compound such as azobisisobutyronitrile or azodibenzoyl, or a photopolymerization initiator such as a mixture of α-diketone and tertiary amine can be used. The amount of the curing initiator used is preferably 0.01 to 10% by weight based on the total amount of the curable material and the curing initiator in the monomer composition.

The antireflection film of the present invention includes a transparent substrate and a layer of the low refractive index material. This low refractive index material layer preferably has an appropriate thickness. An appropriate film thickness is such that the wavelength showing the minimum value of the reflectance of the anti-reflection film is usually 42%.
It is desirable to set the film thickness to be 0 to 720 nm, more preferably 520 to 620 nm. The transparent substrate is not particularly limited as long as it is transparent, but a PET (polyethylene terephthalate) film, a TAC (triacetyl cellulose) film, an acrylic film, a polycarbonate film, or the like is used.

In the antireflection film of the present invention, even if the transparent substrate and the low refractive index material layer are provided, at least one layer is provided between the transparent substrate and the low refractive index material layer. A material provided with the above material layers may be used. As this material layer, a layer of a high refractive index material can be provided in order to enhance the anti-reflection effect. The layer of the high refractive index material preferably has a refractive index of 1.55 or more and a thickness of 50 to 500.
It is preferably nm. The low-refractive-index material layer and the high-refractive-index material layer may be provided one by one on the transparent substrate surface, or may be provided in two or more layers. When two or more layers are provided, layers of a low-refractive-index material and layers of a high-refractive-index material can be alternately laminated, and the low-refractive-index material layer can be provided as the outermost layer. When providing two or more layers, each layer of the low refractive index material or the high refractive index material,
They may be made of the same material or different materials. As the material layer, in addition to the high refractive index material layer, a medium refractive index material (refractive index 1.4) is used.
9 to 1.55).
The antireflection film of the present invention may be provided with a layer of a medium refractive index material and / or a layer of a high refractive index material together with a layer of a low refractive index material.

In order to provide the layer of the low refractive index material, a curing initiator; a solvent such as isopropyl alcohol or toluene is added to the fluorine-containing monomer composition, if necessary, and then mixed. A method such as a roll coating method, a gravure coating method, a dip coating method, a spin coating method, etc., is applied to a substrate such as a transparent substrate, dried, and then heat-cured or irradiated with an active energy ray such as ultraviolet rays, an electron beam or radiation. And the like. The polymerization curing conditions can be appropriately selected according to the curable material in the composition. The high-refractive-index material layer can be provided by a method according to the method of providing the low-refractive-index material layer, or a sputtering method, an evaporation method, or the like of an inorganic compound.

In the antireflection film of the present invention, a hard coat film can be provided in order to further improve the scratch resistance. The hard coat film can be provided between each of the laminates of the low refractive index material and the high refractive index material and the transparent substrate. The hard coat film is not particularly limited, and a usual hard coat resin obtained by a polyfunctional monomer having two or more polymerizable unsaturated groups can be used. If the refractive index differs greatly from the film, reflection occurs at the interface. Therefore, it is preferable that the difference between the two refractive indexes is as small as possible. The thickness of the hard coat film is preferably 1 to 10 μm, particularly preferably 3 to 7 μm. The method for forming the hard coat film is not particularly limited, and is usually applied to a substrate such as a transparent substrate by a coating method such as a roll coating method, a gravure coating method, a dip coating method, a spin coating method, and the like. A method of forming by a usual curing method using wire or heat or the like is used.

In the antireflection film of the present invention, an antiglare film can be provided in order to further improve the antiglare property. The anti-glare film may be provided between each of the laminates of the low refractive index material and the high refractive index material and the transparent substrate. The anti-glare film is not particularly limited. However, if the refractive index of the transparent substrate and the anti-glare film are significantly different, reflection occurs at the interface. Therefore, it is preferable that the difference in refractive index between the two is as small as possible. The thickness of the antiglare film is preferably 1 to 10 μm, particularly preferably 3 to 7 μm. The method of forming the anti-glare film is not particularly limited, and a method usually performed, for example, a method of applying a resin containing fine particles, or a method of forming an uneven surface using an embossing roll or the like after coating can be used. .

[0035]

Since the composition of the present invention has the specific fluorine-containing polyfunctional (meth) acrylate, the polymerized and cured product has both low refractive index and (meth) acrylate hardness. Can be formed into a film by coating on a substrate or the like and polymerizing and curing, and can be a low refractive index material of the present invention. This low refractive index material has a low refractive index
It has both characteristics of (meth) acrylate-based hardness, shows low refractive index and high surface hardness, and can further improve adhesion to other substances by using a diester mixture having a hydroxyl group. it can. Further, the composition of the present invention may contain inorganic compound fine particles in addition to the specific fluorine-containing polyfunctional (meth) acrylate. By blending the inorganic compound, the scratch resistance of the obtained low refractive index material can be improved. The anti-reflection film of the present invention,
Since it has the layer of the low refractive index material, it has a low refractive index, a high surface hardness and a high adhesion, and can be applied to various uses. That is, by using the composition of the present invention, an anti-reflection film provided with a layer of a low-refractive index material having a large area at a low cost can be continuously and efficiently obtained as compared with the conventional magnesium fluoride vapor deposition method. Can be.

[0036]

The present invention will be described in more detail with reference to the following examples.
The present invention is not limited to these. Synthesis Example 1 476 g of 3-perfluorooctyl-1,2-epoxypropane was placed in a reactor equipped with a stirrer, a cooling pipe, and a gas introduction pipe.
(1.0 mol), 161 g (1.2 mol) of 2-bis (hydroxymethyl) propionic acid, 6.4 g of tetraethylammonium bromide, and 600 ml of isopropyl alcohol, and gradually heated in an oil bath to 95-1.
The temperature was adjusted to 00 ° C., and the mixture was stirred at the same temperature for 4 hours, and then cooled to room temperature. 5 L of water was added to the obtained reaction solution to precipitate a paste-like substance. 1000ml after filtering the precipitate
Of ethyl acetate, washed three times with 1000 ml of water, and the solvent was distilled off under reduced pressure to obtain white crystals. This is considered to be a mixture of compounds having the structures shown in formulas (2) and (3).

[0037]

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In a reactor equipped with a stirrer, a thermometer, a gas inlet tube and a dropping funnel, 303.6 g of the white crystals obtained from the above reaction, 303.6 g of triethylamine, and 1000 m of chloroform.
11.5 g of acrylic acid chloride under ice-cooling.
(3.0 mol) was dissolved in 300 ml of chloroform and added dropwise from a dropping funnel so that the temperature of the reaction solution did not exceed 5 ° C. After the completion of the dropwise addition, the mixture was stirred for 2 hours while cooling with ice. Chloroform was distilled off under reduced pressure, and the obtained yellow crystals were further purified by column chromatography using a mixed solvent of ethyl acetate / n-hexane (volume ratio 1: 4) as a developing solvent, and the solvent was distilled off under reduced pressure to obtain white crystals. Was obtained (30% yield). The product B has the following formula (4), (5),
It was a mixture of compounds having the structures shown in (6) and (7).

[0039]

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Synthesis Example 2 The same as Synthesis Example 1 except that 376.1 g (1.0 mol) of 3-perfluorohexyl-1,2-epoxypropane was used instead of 3-perfluorooctyl-1,2-epoxypropane. Then, 198 g (yield: 32%) of the target product C as white crystals was obtained via the compounds having the structures represented by the formulas (8) and (9). The product C has the formula (10), (11),
It was a mixture of compounds having the structures shown in (12) and (13).

[0041]

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Synthesis Example 3 In a reactor equipped with a stirrer, a thermometer, a gas inlet tube, and a dropping funnel, the total amount of the product B synthesized in the same manner as in Synthesis Example 1, 455.4 g of triethylamine, and 1000 parts of chloroform
of acrylic acid chloride 479.3 under ice-cooling.
g (4.5 mol) was dissolved in 450 ml of chloroform and added dropwise from a dropping funnel so that the temperature of the reaction solution did not exceed 5 ° C. After the completion of the dropwise addition, the mixture was stirred for 2 hours while cooling with ice. Chloroform was distilled off under reduced pressure, and the obtained yellow crystals were further purified by column chromatography using a mixed solvent of ethyl acetate / n-hexane (volume ratio 1: 4) as a developing solvent, and the solvent was distilled off under reduced pressure to obtain white crystals. Desired product D232
g (30% yield). Product D was a mixture of compounds having the structures shown in the following formulas (14) and (15).

[0043]

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Synthesis Example 4 In the same manner as in Synthesis Example 3 except that the entire amount of Product D synthesized in Synthesis Example 3 was used instead of Product C, 215 g (yield: 32%) of a product E of white crystals was obtained. Was. The product E has the formula (1)
It was a mixture of compounds having the structures shown in (6) and (17).

[0045]

Embedded image

Synthesis Example 5 30% was added to a reactor equipped with a stirrer, a cooling pipe and a gas introduction pipe.
Silica sol (trade name "XBA-ST", manufactured by Nissan Chemical Industries, Ltd.) 5
00 parts by weight, 3-acryloxypropyltrimethoxysilane (trade name “KBM-510”) as a silane coupling agent
3 ", manufactured by Toshiba Silicone Co.) 100 parts by weight and 20 parts by weight of water, and gradually heated in an oil bath to obtain an oil bath temperature of 100 ° C.
After stirring for 2 hours, the cooling tube was removed and the oil bath temperature was adjusted to 12
The solution was stirred at room temperature for 2 hours, cooled to room temperature, and
I got It is considered that in the reaction solution F, the silane coupling agent modified a part of the surface of the colloidal silica. A part of the reaction solution F was placed in a petri dish, and the weight before and after drying at 120 ° C. for 2 hours was precisely weighed, and the solid content concentration was measured to be 44.6%.

Production Example 1 45 parts by weight of dipentaerythritol hexaacrylate (manufactured by Hitachi Chemical Co., Ltd.), 30 parts by weight of polyethylene glycol diacrylate (trade name “A-400”, manufactured by Shin-Nakamura Chemical Co., Ltd.)
A microgravure coater was prepared by mixing 4 parts by weight of "Irgacure 184" (trade name, manufactured by Ciba Geigy) as a curing initiator and 20 parts by weight of isopropyl alcohol as a solvent.
5μm thick on PET film using (manufactured by Yasui Seiki)
It was applied so that A hard coat film was formed by irradiating 800 mJ / cm ² of ultraviolet light with an ultraviolet irradiator (manufactured by Iwasaki Electric Co., Ltd.) to form a hard coat film, thereby producing a hard coat film-formed PET film (hereinafter abbreviated as HC-PET).

Production Example 2 In the same manner as in Production Example 1, a hard coat film was formed on a TAC film to produce a hard coat film-formed TAC film (hereinafter abbreviated as HC-TAC). Next, a 30% zinc oxide fine particle toluene dispersion (trade name “ZS-300”, manufactured by Sumitomo Osaka Cement Co., Ltd.) 24
0 parts by weight, trimethylolpropane triacrylate
(Hereinafter abbreviated as TMPTA) 28 parts by weight, `` DAR
1 part by weight of OCUR1116 (trade name, manufactured by Merck, acetophenone-based compound) (hereinafter simply referred to as "DAROCUR1116") and 900 parts by weight of toluene as a solvent were mixed to prepare a coating solution.
Next, this coating solution is subjected to HC using a microgravure coater.
-Applied to TAC. 1000mJ /
the high refractive index material layer a layer of cm ² of ultraviolet rays are irradiated high refractive index material by performing the curing is formed form a TAC film (hereinafter HR-
TAC-A). At this time, an instantaneous multi-photometry system equipped with a 0 ° regular reflection measurement device (Otsuka Electronics IMUC-70)
00), the wavelength at which the reflectance has the maximum value is 550 to 60
The thickness of the high refractive index material layer was adjusted to be 0 nm.

Production Example 3 The same procedure as in Production Example 2 was carried out except that the thickness of the high refractive index material layer was adjusted so that the wavelength at which the reflectance exhibited the maximum value became 750 to 800 nm using the instantaneous multi-photometry system. A high refractive index material layer forming TAC film (hereinafter abbreviated as HR-TAC-B) was produced.

Production Example 4 Production Example 2 except that an antiglare film-forming PET film (hereinafter abbreviated as AG-PET) was used instead of HC-TAC.
High refractive index material layer and anti-glare film forming PET
A film (hereinafter abbreviated as HR-AG-PET film) was prepared.

Production Example 5 Production Example 2 except that an anti-glare film-forming TAC film (hereinafter abbreviated as AG-TAC) was used instead of HC-TAC.
High refractive index material layer and antiglare film forming TAC
A film (hereinafter abbreviated as HR-AG-TAC film) was produced.

Examples 1-1 and 1-2 The product B synthesized in Synthesis Example 1 and tetramethylolmethanetetraacrylate (hereinafter abbreviated as TMMTA) were mixed at the mixing ratio shown in Table 1 to obtain a monomer composition. Obtained. To each of the compositions, 900 parts by weight of toluene was mixed as a solvent to prepare two types of coating liquids. Next, each coating liquid was applied on the HC-PET produced in Production Example 1 using a microgravure coater. Accelerator voltage 1 by electron beam irradiator (Iwasaki Electric)
An electron beam having an absorption dose of 15 Mrad was irradiated at a beam current of 35 mA at 25 kV to cure the coated monomer composition, thereby producing a low-reflection PET film having a low refractive index material layer formed thereon. At this time, the thickness of the low refractive index material layer was adjusted using an instantaneous multi-photometry system so that the wavelength at which the reflectance exhibited the minimum value was 550 to 600 nm. As an evaluation test, the following films (a) spectral reflectance, (b) scratch resistance and (c) adhesion for the obtained film, and the obtained coating solution for the following (d) low refractive index material The measurement of the refractive index was performed.

(A) Spectral reflectance Measured by a UV spectrum (trade name “U-best35” manufactured by JASCO Corporation) equipped with a 5 ° regular reflection measuring device. However, the coated surface was used as a measurement surface, and the back surface was roughened with sandpaper to block reflection and measured. The results are shown in FIGS. Table 1 shows the minimum reflectance. (A) Scratch resistance The steel wool hardness (SW hardness) of 0000 was measured and evaluated according to the following evaluation criteria. Table 1 shows the results. A: Scratch is not caused even when strongly rubbed, B: Slightly scratched when strongly rubbed, C: Slightly scratched when rubbed lightly, D: Markedly scratched even when rubbed lightly. (C) Adhesion A cross-cut peel test was performed in accordance with JIS K 5400. Table 1 shows the results. (D) A refractive index coating liquid of a low refractive index material is applied on glass so that the thickness after drying becomes 100 μm, and an electron beam having an acceleration voltage of 175 kV, a beam current of 5 mA and an absorption dose of 5 Mrad is applied by an electron beam irradiator. After irradiation and curing, the obtained film was peeled off from the glass, and the refractive index was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.). Table 1 shows the results.

Examples 1-3 and 1-4 The product C synthesized in Synthesis Example 2 and TMMTA were mixed in the mixing ratio shown in Table 1 to obtain a monomer composition. To each of the compositions, 900 parts by weight of toluene was mixed as a solvent to prepare two types of coating liquids. Next, each coating liquid was applied on the HC-PET produced in Production Example 1 using a microgravure coater. Accelerator voltage 125k by electron beam irradiator (Iwasaki Electric)
V, an electron beam with an absorbed dose of 15 Mrad was irradiated at a beam current of 35 mA, and the coated monomer composition was cured to produce a low-reflection PET film on which a layer of a low refractive index material was formed. At this time, the thickness of the low refractive index material layer was adjusted using an instantaneous multi-photometry system so that the wavelength at which the reflectance exhibited the minimum value was 550 to 600 nm. About the obtained coating liquid and the anti-reflection film, Examples 1-1 and 1-2
The measurement of the evaluation test was performed in the same manner as described above. The results are shown in FIGS.

Examples 1-5 and 1-6 Product B synthesized in Synthesis Example 1, TMMTA, 10% magnesium fluoride sol (trade name "MFS-10P", manufactured by Nissan Chemical Co., Ltd.)
(Hereinafter abbreviated as “MFS-10P”) and DAROCUR1116 were mixed in the mixing ratio shown in Table 1 to obtain a monomer composition. To each of the compositions, 900 parts by weight of toluene was mixed as a solvent to prepare two types of coating liquids. Next, each coating solution was applied onto HR-TAC-A prepared in Production Example 2 using a microgravure coater. The coated monomer composition was cured by irradiating ultraviolet rays of 1000 mJ / cm ² three times with an ultraviolet irradiator, thereby producing a low reflection index TAC film in which layers of a low refractive index material and a high refractive material were laminated. . At this time, the wavelength at which the reflectance has the minimum value is 5 using the instantaneous multi-photometry system.
The thickness of the low refractive index material layer was adjusted to 50 to 600 nm. About the obtained coating liquid and the anti-reflection film, the measurement of the evaluation test was performed like Example 1-1 and 1-2. The results are shown in FIGS.

Examples 1-7 and 1-8 Product B synthesized in Synthesis Example 1, tetraacrylic acid-4,
4,5,5,6,6,7,7-octafluorodecane-
1,2,9,10-Tetraol (hereinafter abbreviated as F ₈ DTA), the reaction solution F synthesized in Synthesis Example 5, and DAROCUR1116 were mixed at the mixing ratio shown in Table 1 to obtain a monomer composition. To each of the compositions, 900 parts by weight of toluene was mixed as a solvent to prepare two types of coating liquids. Next, each coating liquid was applied onto HR-TAC-B produced in Production Example 3 using a microgravure coater. 1000mJ / cm by UV irradiator
^The coated monomer composition was cured by irradiating it with the ultraviolet ray of No. ² three times to prepare a low-reflection TAC film in which layers of a low-refractive-index material and a high-refractive-index material were laminated. At this time, the thickness of the low refractive index material layer was adjusted using an instantaneous multi-photometry system so that the wavelength at which the reflectance exhibited the minimum value was 550 to 600 nm. About the obtained coating liquid and the anti-reflection film, the measurement of the evaluation test was performed like Example 1-1 and 1-2. The results are shown in FIGS. 7 and 8 and Table 1.

Comparative Examples 1 and 2 The spectral reflectance, minimum reflectance and abrasion resistance of HC-PET and HC-TAC produced in Production Examples 1 and 2 were measured in Examples 1-1 and 1
-2. The results are shown in FIGS. 9 and 10 and Table 1.

Comparative Example 3 Diacrylic acid-2,2,3,3,4,4,5,5,6
6,7,7,8,8,9,9,9-Heptadecafluorononylethylene glycol (hereinafter abbreviated as F ₁₇ EDA) or F ₈ DTA and TMMTA are mixed at the mixing ratio shown in Table 1, and the solvent is mixed. Was mixed with 900 parts by weight of toluene to prepare a coating solution. Production example 1 using a microgravure coater
Each coating solution was applied on the HC-PET prepared in the above. An electron beam irradiator (manufactured by Iwasaki Electric Co., Ltd.) irradiates an electron beam with an absorbed dose of 15 Mrad at an accelerator voltage of 125 kV and a beam current of 35 mA, and cures the coating liquid to form a low-refractive-index layer.
A PET film was produced. At this time, the wavelength at which the reflectance has the minimum value is 550 to 60 using the instantaneous multi-photometry system.
The thickness of the low refractive index material layer was adjusted to be 0 nm. About the obtained coating liquid and the anti-reflection film, the measurement of the evaluation test was performed like Example 1-1 and 1-2. The results are shown in FIGS.

D.1116 in Tables 1 to 3 is “DAROCUR1116” (trade name, manufactured by Merck, (1- (4-isopropylphenyl)-
2-hydroxy-2-methylpropan-1-one).

[0060]

[Table 1]

Examples 2-1 and 2-2 Product D synthesized in Synthesis Example 3 and TMMTA were mixed at the compounding ratio shown in Table 2 to obtain a monomer composition. Each composition was mixed with 900 parts by weight of toluene to prepare two kinds of coating liquids. Next, a low-reflection PET film on which a layer of a low refractive index material was formed in the same manner as in Examples 1-1 and 1-2,
The (a) spectral reflectance and (a) abrasion resistance test and (d) the refractive index of the obtained coating liquid were measured. Each evaluation test was measured. The results are shown in FIGS.
Shown in

Examples 2-3 and 2-4 The products E and TMMTA synthesized in Synthesis Example 4 were mixed in the mixing ratio shown in Table 2 to obtain a monomer composition. To each of the compositions, 900 parts by weight of toluene was mixed as a solvent to prepare two types of coating liquids. Next, a low-reflection PET film on which a layer of a low refractive index material was formed was prepared in the same manner as in Examples 1-3 and 1-4, and the same evaluation test as in Examples 2-1 and 2-2 was performed. Was. The results are shown in FIGS.

Examples 2-5 and 2-6 Product D synthesized in Synthesis Example 3, TMMTA, MFS-10P and DAR
OCUR1116 was mixed in the mixing ratio shown in Table 2 to obtain a monomer composition. To each of the compositions, 900 parts by weight of toluene was mixed as a solvent to prepare two types of coating liquids. Then, Example 1
As in -5 and 1-6, a low-reflection TAC film in which layers of a low-refractive index material and a high-refractive index material were laminated was prepared.
The same evaluation test as that of -1 and 2-2 was performed. The results are shown in FIGS.

Examples 2-7 and 2-8 Product D synthesized in Synthesis Example 3, TMMTA, reaction solution F synthesized in Synthesis Example 5, and DAROCUR1116 were mixed at the compounding ratio shown in Table 2 to obtain a monomer composition. I got something. To each of the compositions, 900 parts by weight of toluene was mixed as a solvent to prepare two types of coating liquids. Next, similarly to Examples 1-7 and 1-8, the anti-reflection TAC in which the layers of the low refractive index material and the high refractive material were laminated.
A film was prepared, and the same evaluation test as in Examples 2-1 and 2-2 was performed. The results are shown in FIGS.

Comparative Example 5 A coating liquid was prepared by mixing 100 parts by weight of heptadecafluorodecyl acrylate (hereinafter abbreviated as F ₁₇ A) and 900 parts by weight of toluene as a solvent. Next, each solution was applied onto the HC-PET produced in Production Example 1 using a microgravure coater. Absorbed dose of 15 with an accelerator voltage of 125 kV and a beam current of 35 mA using an electron beam irradiator (Iwasaki Electric)
Irradiation of Mrad electron beam to cure the coated monomer composition to form a low refractive index material layer
A PET film was produced. At this time, the wavelength at which the reflectance has the minimum value is 550 to 60 using the instantaneous multi-photometry system.
The thickness of the low refractive index material layer was adjusted to be 0 nm. The same evaluation test as in Examples 2-1 and 2-2 was performed on the obtained coating liquid and antireflection film. The results are shown in FIG.

[0066] and Comparative Examples 6 and 7 F ₁₇ EDA or TMMTA, and was prepared by mixing toluene 900 parts by weight 2 kinds of the coating liquid as a solvent, respectively and mixed at the mixing ratio shown in Table 2 DAROCUR1116. Then, Example 1-5
In the same manner as in Examples 1-6, a low-reflection TAC film on which a layer of a low refractive index material was formed was produced. The same evaluation test as in Examples 2-1 and 2-2 was performed on the obtained coating liquid and antireflection film. The results are shown in FIG.

Comparative Examples 8 to 10 F ₁₇ A and TMMTA were mixed in the proportions shown in Table 2, but none of them were compatible.

[0068]

[Table 2]

Examples 3-1 and 3-2 The product B synthesized in Synthesis Example 1, TMMTA, and DAROCUR1116
Were mixed in the proportions shown in Table 3 to obtain a monomer composition.
900 parts by weight of toluene were mixed to prepare a coating solution. Next, using a microgravure coater, the HR-AG-PET film prepared in Production Example 4 or H prepared in Production Example 5 was used.
Each was applied on an R-AG-TAC film. Irradiation of ultraviolet rays of 1000 mJ / cm ² three times with an ultraviolet ray irradiator, curing and curing, low-refractive index material coated anti-reflection
An AG-PET film was prepared. At this time, the wavelength at which the reflectance has the minimum value is 550 to 550 using the instantaneous multi-photometry system.
The film thickness of the low refractive index material was adjusted to be 600 nm. With respect to the obtained film, the following (e) total light transmittance and haze were measured in addition to the (a) spectral reflectance, (a) abrasion resistance and (c) adhesion tests.
The results are shown in FIGS. (E) Total light transmittance and haze Turbidity / color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name "ND-1001D
P ".

Examples 3-3 and 3-4 The product B and F ₈ DTA synthesized in Synthesis Example 1, the reaction solution F synthesized in Synthesis Example 5, and DAROCUR1116 were mixed in the mixing ratio shown in Table 3 to obtain a single amount. A body composition was obtained. 900 parts by weight of toluene were mixed to prepare a coating solution. Next, using a microgravure coater, it was applied on the HR-AG-PET film produced in Production Example 4 or on the HR-AG-TAC film produced in Production Example 5, respectively. 1000mJ /
Irradiation was carried out three times with ultraviolet rays of ² cm ² , and curing was performed to produce a low-reflection AG-PET film coated with a low refractive index material. At this time, the film thickness of the low refractive index material was adjusted using an instantaneous multi-photometry system so that the wavelength at which the reflectance had the minimum value was 550 to 600 nm. An evaluation test was performed on the obtained film in the same manner as in Examples 3-1 and 3-2. The results are shown in FIGS.

Comparative Examples 11 and 12 For the AG-PET film used in Production Example 4 or the AG-TAC film used in Production Example 5, the (a) spectral reflectance,
(A) Scratch resistance, (E) Total light transmittance and haze were measured. The results are shown in FIGS.

[0072]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a graph showing a measurement result of a spectral reflectance of Example 1-1.

FIG. 2 is a graph showing a measurement result of a spectral reflectance of Example 1-2.

FIG. 3 is a graph showing a measurement result of a spectral reflectance of Example 1-3.

FIG. 4 is a graph showing a measurement result of a spectral reflectance of Example 1-4.

FIG. 5 is a graph showing a measurement result of a spectral reflectance of Example 1-5.

FIG. 6 is a graph showing the measurement results of the spectral reflectance of Example 1-6.

FIG. 7 is a graph showing the measurement results of the spectral reflectance of Example 1-7.

FIG. 8 is a graph showing the measurement results of the spectral reflectance of Example 1-8.

FIG. 9 is a graph showing the measurement results of the spectral reflectance of Comparative Example 1.

FIG. 10 is a graph showing a measurement result of a spectral reflectance of Comparative Example 2.

FIG. 11 is a graph showing a measurement result of a spectral reflectance of Comparative Example 3.

FIG. 12 is a graph showing the measurement results of the spectral reflectance of Comparative Example 4.

FIG. 13 is a graph showing the measurement results of the spectral reflectance of Example 2-1.

FIG. 14 is a graph showing the measurement results of the spectral reflectance of Example 2-2.

FIG. 15 is a graph showing the measurement results of the spectral reflectance of Example 2-3.

FIG. 16 is a graph showing the measurement results of the spectral reflectance of Example 2-4.

FIG. 17 is a graph showing the measurement results of the spectral reflectance of Example 2-5.

FIG. 18 is a graph showing the measurement results of the spectral reflectance of Example 2-6.

FIG. 19 is a graph showing the measurement results of the spectral reflectance of Example 2-7.

FIG. 20 is a graph showing the measurement results of the spectral reflectance of Example 2-8.

FIG. 21 is a graph showing the measurement results of the spectral reflectance of Comparative Example 5.

FIG. 22 is a graph showing measurement results of spectral reflectances of Comparative Examples 6 and 7.

FIG. 23 is a graph showing the measurement results of the spectral reflectance of Example 3-1.

FIG. 24 is a graph showing the measurement results of the spectral reflectance of Example 3-2.

FIG. 25 is a graph showing the measurement results of the spectral reflectance of Example 3-3.

FIG. 26 is a graph showing the measurement results of the spectral reflectance of Example 3-4.

FIG. 27 is a graph showing the measurement results of the spectral reflectance of Comparative Example 11.

FIG. 28 is a graph showing the measurement results of the spectral reflectance of Comparative Example 12.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G02B 1/11 G02B 1/10 A (72) Inventor Tetsuya Ito 2-20-3 Kasuga, Tsukuba, Ibaraki Prefecture (72) Inventor Goto Yoshitaka 6-5-7 Kinunodai, Yawahara Village, Tsukuba, Ibaraki Prefecture

Claims (5)

[Claims] 1. A monomer composition containing 5 to 100% by weight of a fluorine-containing polyfunctional (meth) acrylate represented by the following general formula (1). Embedded image (Wherein X is a carbon number of 1 to 1 having 3 or more fluorine atoms)
4 represents a fluoroalkyl group or a fluorocycloalkyl group having 3 to 14 carbon atoms having 4 or more fluorine atoms,
Y ¹ , Y ² and Y ³ represent a hydrogen atom, an acryloyl group or a methacryloyl group, and at least two of Y ¹ , Y ² and Y ³ are the same or different groups, and are an acryloyl group or a methacryloyl group. Z represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n and m each represent 0 or 1, and n + m = 1. ) 2. The monomer composition according to claim 1, further comprising inorganic compound fine particles. 3. A low refractive index material having a refractive index of 1.49 or less, obtained by polymerizing and curing the monomer composition according to claim 1. 4. An anti-reflection film comprising a transparent substrate and a layer of the low refractive index material according to claim 3. 5. The anti-reflection film according to claim 4, further comprising at least one material layer between the transparent substrate and the layer of the low refractive index material according to claim 3.