JP2008007680A - Curable resin composition and anti-reflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition which gives cured products having low refractive indexes and excellent scratch resistance, and to provide an antireflection film having a low refractive index layer comprising the same. <P>SOLUTION: This curable resin composition comprises the following components (A) to (C): (A) a hydroxyl group-containing fluoropolymer, (B) inorganic fluoride particles, (C) a cross-linkable compound. When the total amount of (A) and (B) is 100 pts.mass, (A) is 20 to 95 pts.mass, and (B) is 5 to 80 pts.mass. (B) is inorganic fluoride particles having a refractive index of <1.45 at a wavelength of 589 nm. (C) is a compound having an amino group capable of reacting with the hydroxyl group existing in the hydroxyl group-containing fluoropolymer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable resin composition and an antireflection film.

  Currently, with the development of multimedia, various developments have been seen in various display devices (display devices). Among various types of display devices, especially those used outdoors, mainly for portable use, the improvement in visibility has become increasingly important, and even in large display devices, it is easier to see. This is a technical issue as it is required by consumers.

  Conventionally, as one means for improving the visibility of a display device, an antireflection film made of a low refractive index material is coated on a substrate of the display device, and a method of forming the antireflection film For example, a method of forming a fluorine compound thin film by a vapor deposition method is known. However, in recent years, there has been a demand for a technique capable of forming an antireflection film for a large display device at a low cost centering on a liquid crystal display device. However, in the case of the vapor deposition method, it is difficult to form a high-efficiency and uniform antireflection film on a large-area substrate, and a vacuum apparatus is required, so that the cost can be reduced. Have difficulty.

  Under such circumstances, a method of forming an antireflection film by preparing a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent and applying it to the surface of a substrate has been studied. Yes. For example, it has been proposed to apply a fluorinated alkylsilane to the surface of a substrate (see, for example, Patent Document 1 and Patent Document 2). In addition, a method of applying a fluorine-based polymer having a specific structure has been proposed (see, for example, Patent Document 3).

  By the way, in order to improve the scratch resistance of the antireflection film, a technique of adding silica particles to a low refractive index film which is the outermost layer of the antireflection film is widely used (for example, Patent Documents 4 and 5). However, in many cases, since one type of silica particle having a relatively uniform particle size is used, the filling rate of the particles cannot be increased, and sufficient scratch resistance has not been obtained.

In addition, in order to provide an antireflection film having a lower reflectivity, a material for a low refractive index film having a lower refractive index than before is desired. Therefore, by utilizing the fact that the refractive index of air is lower than that of a resin component such as acrylic, a technique using particles having voids inside the particles such as porous particles and hollow particles (hereinafter collectively referred to as hollow particles). Is known (for example, Patent Documents 6 to 8).
However, when hollow particles are used, there is a drawback that the scratch resistance of the cured film is reduced as compared with particles having no voids (solid particles).

JP 61-40845 A Japanese Examined Patent Publication No. 6-98703 Japanese Patent Application Laid-Open No. 6-1115023 JP 2002-265866 A JP-A-10-316860 JP 2003-139906 A JP 2002-317152 A JP-A-10-142402

  Therefore, the present invention provides a curable resin composition that gives a cured film having a refractive index lower than that of conventional silica particles and excellent in scratch resistance, and an antireflection film having the cured film. Objective.

That is, this invention provides the following curable resin composition, the film | membrane and antireflection film which hardened it.
1. The following components (A), (B), and (C):
(A) a hydroxyl group-containing fluoropolymer,
(B) inorganic fluoride,
(C) Curable resin composition containing a crosslinkable compound.
2. When the total of the (A) hydroxyl group-containing fluoropolymer of the curable resin composition and the (B) inorganic fluoride is 100 parts by mass, the (A) hydroxyl group-containing fluoropolymer is 20 to 95 masses. The curable resin composition according to 1, which contains 5 to 80 parts by mass of the inorganic fluoride (B).
3. The curable resin composition according to 1 or 2, wherein the (B) inorganic fluoride is particles made of an inorganic fluoride having a refractive index of less than 1.45 at a wavelength of 589 nm.
4). The curable resin composition according to any one of 1 to 3, wherein the (B) inorganic fluoride is magnesium fluoride.
5. The curable resin composition according to any one of 1 to 4, wherein the crosslinkable compound (C) is a compound having an amino group capable of reacting with a hydroxyl group present in the hydroxyl group-containing fluoropolymer.
6). Furthermore, (D) Curable resin composition as described in any one of 1-5 containing an acid catalyst.
7). The curable resin composition according to any one of 1 to 6, which is for an antireflection film.
8). A film obtained by curing the curable resin composition according to any one of 1 to 7 above and having a refractive index of less than 1.45 at a wavelength of 589 nm.
9. 9. An antireflection film having the film described in 8 above.

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which gives the cured film which has a low refractive index and the outstanding scratch resistance, and the antireflection film which has this cured film are obtained.
Further, according to the present invention, by heating, a cured film having a low refractive index and excellent scratch resistance and an antireflection film having the cured film can be obtained simply and efficiently.

Embodiments of the curable resin composition and the antireflection film of the present invention will be described below.
1. Curable Resin Composition The curable resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) may include the following components (A) to (F). Among these components, (A) to (C) are essential components, and (D) to (F) are optional components that can be appropriately contained.
(A) Hydroxyl group-containing fluoropolymer (B) Inorganic fluoride (C) Crosslinkable compound (D) Acid catalyst (E) Organic solvent (F) Other additives

In the composition of the present invention, the component (A) can exhibit excellent functions as an antireflection film such as a low refractive index, water repellency, oil repellency, dust wiping property, and fingerprint wiping property.
By adding the inorganic fluoride (component (B)), a cured film having a low refractive index and a high hardness can be obtained.
In addition, since the component (A) has a hydroxyl group, it can be crosslinked with the thermally polymerizable component (C), and the scratch resistance is improved.
These components will be described below.

(A) Hydroxyl group-containing fluoropolymer The hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a) and / or (b), and (c) and / or (d) (provided that (Excluding hydroxyl-containing fluoropolymers comprising only (b) and (c)).
(A) A structural unit represented by the following formula (1).
(B) A structural unit represented by the following formula (2).
(C) A structural unit represented by the following formula (3).
(D) A structural unit represented by the following formula (4).

［式（１）中、Ｒ¹はフッ素原子、フルオロアルキル基又は−ＯＲ²で表される基（Ｒ²はアルキル基又はフルオロアルキル基を示す）を示す］

[In formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

［式（２）中、Ｒ³は水素原子又はメチル基を、Ｒ⁴はアルキル基、−(ＣＨ₂)_x−ＯＲ⁵若しくは−ＯＣＯＲ⁵で表される基（Ｒ⁵はアルキル基、フルオロアルキル基又はグリシジル基を、ｘは０又は１の数を示す）、−Ｏ−(ＣＨ₂)_x’−Ｒ^5’で表される基（Ｒ^5’はパーフルオロアルキル基を、ｘ’は１〜１０の数を示す）、カルボキシル基又はアルコキシカルボニル基を示す］

[In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group, fluoroalkyl A group or a glycidyl group, x represents a number of 0 or 1, and a group represented by —O— (CH ₂ ) _{x ′} —R ^{5 ′} (R ^{5 ′} represents a perfluoroalkyl group, x ′ represents 1 -10 represents a carboxyl group or an alkoxycarbonyl group]

［式（３）中、Ｒ⁶は水素原子又はメチル基を、Ｒ⁷は水素原子又はヒドロキシアルキル基を、ｖは０又は１の数を示す］

[In formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

［式（４）中、Ｒｆはフッ素を含有する炭素数２〜１０の２価の有機基を示す。］

[In Formula (4), Rf shows a C2-C10 bivalent organic group containing a fluorine. ]

(I) Structural unit (a)
In the above formula (1), examples of the fluoroalkyl group represented by R ¹ and R ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorocyclohexyl group, and the like. A C1-C6 fluoroalkyl group is mentioned. The alkyl group R ^2, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an alkyl group having 1 to 6 carbon atoms such as a cyclohexyl group.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples thereof include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluoro Perfluoro (alkyl vinyl ethers) such as (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether) ) A single species or a combination of two or more species.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and it is more preferable to use these in combination.

In addition, the content rate of structural unit (a) is 20-70 mol% with respect to the total amount of structural unit (a)-(d) in a hydroxyl-containing fluoropolymer. The reason for this is that when the content is less than 20 mol%, it is sometimes difficult to develop a low refractive index, which is the characteristic of the optically fluorine-containing material intended by the present application. This is because when the ratio exceeds 70 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
For this reason, the content of the structural unit (a) is set to 25 to 65 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. More preferably, it is more preferably 30 to 60 mol%.

(Ii) Structural unit (b)
In the formula (2), examples of the alkyl group represented by R ⁴ or R ⁵ include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, and lauryl group. Examples of the group include a methoxycarbonyl group and an ethoxycarbonyl group. The fluoroalkyl group of R ^{5 ′} includes perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl. Group, perfluorononyl group, perfluorodecyl group and the like.

  The structural unit (b) can be introduced by using the above-mentioned vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n -Alkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; 3,3,3-propylfluoropropyl vinyl ether, 3,3,4,4,4-pentafluorobutyl vinyl ether, 3,3 , 4,4,5,5,5-heptafluoropentyl vinyl ether, 3,3,4,4,5,5,6,6,6-nonafluorohexyl vinyl ether 3 , 3,4,4,5,5,6,6,7,7,7-dodecafluoroheptyl vinyl ether, 3,3,4,4,5,5,6,6,7,7,8,8, 8-propadecafluorooctyl vinyl ether 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl vinyl ether, 3,3,4,4 , 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-fluoroalkyl vinyl ethers such as heptadecafluorodecyl vinyl ether; cycloalkyl vinyl ethers; ethyl allyl ether, butyl allyl ether Allyl ethers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl stearate, etc. Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ) (Meth) acrylic acid esters such as ethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids such as single or a combination of two or more Can be mentioned.

In addition, the content rate of a structural unit (b) is 10-70 mol% with respect to the total amount of the structural units (a)-(d) in a hydroxyl-containing fluoropolymer. This is because if the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For this reason, the content of the structural unit (b) is set to 20 to 60 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. More preferred.

(Iii) Structural unit (c)
In the formula (3), as the hydroxyalkyl group of R ⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group , 6-hydroxyhexyl group.

The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, Examples include hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, allyl alcohol, and the like.
Moreover, as a hydroxyl-containing vinyl monomer, in addition to the above, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, polypropylene Glycol (meth) acrylate or the like can be used.

In addition, it is preferable that the content rate of a structural unit (c) shall be 5-70 mol% with respect to the total amount of the structural units (a)-(d) in a hydroxyl-containing fluoropolymer. This is because if the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For this reason, the content of the structural unit (c) is set to 5 to 40 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. More preferably, it is more preferably 5 to 30 mol%.

(Iv) Structural unit (d)
It is also preferred that the hydroxyl group-containing fluoropolymer further comprises a structural unit (d). As a result, a cured film having a lower refractive index than that of conventional fluoropolymers can be obtained.
In the formula (4), examples of the divalent organic group having 2 to 10 carbon atoms containing fluorine of Rf include a tetrafluoroethylene group, a hexafluoropropylene group, and a structural unit represented by the following formula (5). .

  The structural unit (d) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. As such a fluorine-containing vinyl monomer, Unimatec brand name FVEP etc. are mentioned.

The content of the structural unit (d) is preferably 5 to 60 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. The reason for this is that when the content is less than 5 mol%, it is sometimes difficult to develop a low refractive index, which is the characteristic of the optically fluorine-containing material as intended by the present application. This is because if the rate exceeds 50 mol%, the solubility in an organic solvent such as methyl isobutyl ketone may decrease.
For these reasons, the content of the structural unit (d) is more preferably 10 to 60 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. More preferably, it is 25-60 mol%.

(V) Structural unit (e) and structural unit (f)
It is also preferable that the hydroxyl group-containing fluoropolymer further comprises the following structural unit (e).

［式（６）中、Ｒ⁸及びＲ⁹は、同一でも異なっていてもよく、水素原子、アルキル基、ハロゲン化アルキル基又はアリール基を示す］ (E) A structural unit represented by the following formula (6).

[In Formula (6), R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]

In the formula (6), the alkyl group of R ⁸ or R ^{9 is} an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, and the halogenated alkyl group is a trifluoromethyl group or perfluoro group. C1-C4 fluoroalkyl groups, such as an ethyl group, a perfluoropropyl group, a perfluorobutyl group, etc., A phenyl group, a benzyl group, a naphthyl group etc. are each mentioned as an aryl group.

  The structural unit (e) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (6). An example of such an azo group-containing polysiloxane compound is a compound represented by the following formula (7).

［式（７）中、Ｒ¹⁰〜Ｒ¹³は、同一でも異なっていてもよく、水素原子、アルキル基又はシアノ基を示し、Ｒ¹⁴〜Ｒ¹⁷は、同一でも異なっていてもよく、水素原子又はアルキル基を示し、ｐ、ｑは１〜６の数、ｓ、ｔは０〜６の数、ｙは１〜２００の数、ｚは１〜２０の数を示す。］

[In the formula (7), R ^{10 to} R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group, and R ^{14 to} R ¹⁷ may be the same or different and represent a hydrogen atom. Alternatively, it represents an alkyl group, p and q are numbers 1 to 6, s and t are numbers 0 to 6, y is a number 1 to 200, and z is a number 1 to 20. ]

  When the compound represented by the formula (7) is used, the structural unit (e) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (f).

［式（８）中、Ｒ¹⁰〜Ｒ¹³、Ｒ¹⁴〜Ｒ¹⁷、ｐ、ｑ、ｓ、ｔ及びｙは、上記式（７）と同じである。］ (F) A structural unit represented by the following formula (8).

[In Formula (8), R < ¹⁰ > -R < ¹³ >, R < ¹⁴ > -R < ¹⁷ >, p, q, s, t, and y are the same as the said Formula (7). ]

In the formulas (7) and (8), examples of the alkyl group represented by R ^{10 to} R ¹³ include C 1-12 alkyl groups such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. Examples of the alkyl group of ^{14 to} R ¹⁷ include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

  In the present invention, the azo group-containing polysiloxane compound represented by the above formula (7) is particularly preferably a compound represented by the following formula (9).

［式（９）中、ｙ及びｚは、上記式（７）と同じである。］

[In Formula (9), y and z are the same as those in Formula (7) above. ]

The content of the structural unit (e) is 0.1 to 10 mole parts when the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer is 100 mole parts. Is preferred. The reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing is lowered, and the scratch resistance of the coated film may be lowered. If the amount exceeds 10 parts by mole, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling and the like are likely to occur during coating.
For these reasons, the content of the structural unit (e) is more preferably 0.1 to 5 mole parts relative to the total amount of the hydroxyl group-containing fluoropolymer, More preferably, the molar part. For the same reason, the content of the structural unit (f) is desirably determined so that the content of the structural unit (e) contained therein falls within the above range.

(Vi) Structural unit (g)
It is also preferred that the hydroxyl group-containing fluoropolymer further comprises the following structural unit (g).

［式（１０）中、Ｒ¹⁸は乳化作用を有する基を示す］ (G) A structural unit represented by the following formula (10).

[In the formula (10), R ¹⁸ represents a group having an emulsifying action]

In the formula (10), the group having an emulsifying action of R ¹⁸ includes a group having both a hydrophobic group and a hydrophilic group, and the hydrophilic group having a polyether structure such as polyethylene oxide and polypropylene oxide. preferable.

［式（１１）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］ Examples of the group having such an emulsifying action include a group represented by the following formula (11).

[In Formula (11), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]

  The structural unit (g) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (12).

［式（１２）中、ｎ、ｍ及びｕは、上記式（１１）と同様である］

[In the formula (12), n, m and u are the same as in the above formula (11)]

The content of the structural unit (g) is 0.1 to 5 mole parts when the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer is 100 mole parts. Is preferred. The reason for this is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 5 mol parts, the curable resin composition This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
For these reasons, the content of the structural unit (g) is more preferably 0.1 to 3 mole parts relative to the total amount of the hydroxyl group-containing fluoropolymer, and 0.2 to 3 More preferably, the molar part.

(Vii) Molecular Weight The hydroxyl group-containing fluoropolymer preferably has a polystyrene equivalent number average molecular weight of 5,000 to 500,000 measured by gel permeation chromatography using tetrahydrofuran as a solvent. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be lowered. On the other hand, when the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult.
For these reasons, the number average molecular weight in terms of polystyrene of the hydroxyl group-containing fluoropolymer is more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000.

Although it does not restrict | limit especially about the addition amount of (A) component, When the sum total of (A) component and (B) component is 100 mass parts, it is 20-95 mass parts normally. The reason for this is that when the addition amount is less than 20 parts by mass, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. This is because if the amount exceeds 95 parts by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.
For this reason, the amount of component (A) added is more preferably 25 to 85 parts by mass, and still more preferably 30 to 80 parts by mass.

In the present invention, the hydroxyl group-containing fluoropolymer can be produced by polymerizing the monomers forming the respective structural units using a radical polymerization initiator. As the polymerization method, any of an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method can be used, and the polymerization operation can be appropriately selected from a batch operation, a semi-continuous operation, a continuous operation, or the like. Can be selected.
Known radical polymerization initiators can be used.

  The polymerization reaction for obtaining the hydroxyl group-containing fluoropolymer is preferably carried out in a solvent system using a solvent. Examples of preferable organic solvents include (1) esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and cellosolve; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; (3) Cyclic ethers such as tetrahydrofuran and dioxane; (4) Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; (5) Aromatic hydrocarbons such as toluene and xylene; be able to. Further, if necessary, alcohols, aliphatic hydrocarbons and the like can be mixed and used.

(B) Inorganic fluoride The inorganic fluoride used in the present invention preferably has a refractive index of less than 1.45 at a wavelength of 589 nm. The component (B) has the effect of improving the strength of the cured film, and the refractive index of the cured film is less than when silica particles are used by using an inorganic fluoride having a refractive index of less than 1.45 at a wavelength of 589 nm. The antireflection film having excellent antireflection properties can be obtained. Such inorganic fluorides include aluminum fluoride (refractive index: 1.38), calcium fluoride (refractive index: 1.23-1.45), lithium fluoride (refractive index: 1.30), fluorine Magnesium fluoride (refractive index: 1.38 to 1.40) and the like. Among these, lithium fluoride, calcium fluoride, and magnesium fluoride are preferable, and magnesium fluoride is particularly preferable.

  In view of particle hardness, hygroscopicity, and refractive index, magnesium fluoride is most preferable. Examples of commercially available magnesium fluoride include Stella Chemifa's magnesium fluoride, magnesium fluoride OP, magnesium fluoride G1, magnesium fluoride H, and Sanwa polished magnesium fluoride.

The curable resin composition of the present invention has an inorganic fluoride having a number average particle size of 200 nm or less, preferably a particle size of 100 nm or less, particularly preferably a number average particle size of 10 to 50 nm, and more preferably a number average particle size of 10 to 30 nm. Is used. The particle size is measured with a transmission electron microscope. If the number average particle size is larger than 200 nm, the transparency of the formed coating film may be lowered. In addition, when a cured film obtained by curing the curable resin composition of the present invention is used as a low refractive index layer of an antireflection film, since the film thickness of the low refractive index layer is about 100 nm, inorganic fluoride particles If the particle size is larger than the film thickness, the optical properties and mechanical properties of the antireflection film may be deteriorated.
The inorganic fluoride preferably has a particle size distribution in which particles within 10 nm above and below the average particle size are 95% by weight or more of the particles, and particles within 5 nm above and below the average particle size are centered. It is particularly preferred to have a particle size distribution that is 95% by weight or more of the total.
In addition, since the said commercial item is a coarse particle with a particle size of several micrometers, in order to use as (B) component in this invention, it is necessary to grind | pulverize and disperse | distribute using a grinder.

  Further, these inorganic fluorides may be used by dispersing in water or an organic solvent. Examples of organic solvents that can be used as the dispersion medium include alcohols such as methanol, ethanol, isopropyl alcohol, ethylene glycol, butanol, and ethylene glycol monopropyl ether; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and aromatics such as toluene and xylene. Group hydrocarbons; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane Among these, alcohols and ketones are preferable. These organic solvents can be used alone or in admixture of two or more as a dispersion medium. Examples of commercially available magnesium fluoride sol dispersed in such an organic solvent include MFS-10P manufactured by Nissan Chemical Industries.

  Moreover, what carried out surface treatments, such as chemical modification, on the surface of inorganic fluoride can be used, for example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule or a hydrolyzate thereof Etc. can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane, hexamethyl-1,3-disilazane, and the like.

  The blending amount of the component (B) in the resin composition is usually 5 to 80 parts by mass, preferably 15 to 75 parts by mass when the total of the component (A) and the component (B) is 100 parts by mass. 20-70 mass parts is still more preferable. The amount of particles means solid content, and when the particles are used in the form of a solvent-dispersed sol, the amount of the solvent does not include the amount of solvent.

(C) Crosslinkable compound In practice, the composition of the present invention needs to have curability, and when the hydroxyl group-containing fluoropolymer itself does not have sufficient curability, a crosslinkable compound is used. By blending, necessary curability can be imparted and curing characteristics can be improved. Examples of the crosslinkable compound include various amino compounds, various hydroxyl group-containing compounds such as pentaerythritol, polyphenol, and glycol, and others.

  The amino compound used as the crosslinkable compound is a total of two amino groups capable of reacting with the hydroxyl group present in the hydroxyl group-containing fluoropolymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group. Specific examples of the compound that can be used include melamine compounds, urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total. Specifically, methylolated melamine, alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine and formaldehyde under basic conditions is preferable, and good storage stability is obtained particularly for the curable resin composition. Alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained. There are no particular restrictions on the methylolated melamine and alkoxylated methylmelamine used as the crosslinkable compound. For example, the methylolated melamine and alkoxylated methylmelamine can be obtained by the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun). Various resinous materials can be used.

  In addition to urea, examples of the urea compound include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, methylolated uron having a uron ring, and alkoxylated methyluron. And also about compounds, such as a urea derivative, the use of the various resinous materials described in said literature is possible.

式（１３）及び（１４）中、Ｒ^２５、Ｒ^２７、Ｒ^２９はメチレン基又は炭素数２〜４のアルキレン基を示し、好ましくはメチレン基である。Ｒ^２６、Ｒ^２８、Ｒ^３０は水素又は炭素数１〜４のアルキル基を示し、好ましくはメチル基である。
上記式（１３）又は（１４）で示される構造を有する化合物の例としては、サイメル３００、３０１、３０３、３５０、３７０、７７１、３２５、３２７、７０３、７１２、２７２、２０２、２０７、２１２、２５３、２５４、５０６、５０８、１１２３、１１２３−１０、１１２８、１１７０、１１７２、１１４１、１１２５−８０、マイコート１０２、１０５、１０６、１３０（いずれも三井サイテック製）等が挙げられる。 As the crosslinkable compound, a compound having a structure represented by the following formula (13) or (14) is preferable.

In formulas (13) and (14), R ²⁵ , R ²⁷ and R ²⁹ represent a methylene group or an alkylene group having 2 to 4 carbon atoms, preferably a methylene group. R ²⁶ , R ²⁸ and R ³⁰ represent hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
Examples of the compound having the structure represented by the above formula (13) or (14) include Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, 272, 202, 207, 212, 253, 254, 506, 508, 1123, 1123-10, 1128, 1170, 1172, 1141, 1125-80, My Coat 102, 105, 106, 130 (all manufactured by Mitsui Cytec) and the like.

  The content of the component (C) in the composition of the present invention is preferably 1 to 50 parts by mass, more preferably 1 to 50 parts by mass when the total of the component (A) and the component (B) is 100 parts by mass. 45 parts by mass, particularly preferably 1 to 40 parts by mass. If the amount of the crosslinkable compound used is too small, the durability of the thin film formed by the resulting curable resin composition may be insufficient. If it exceeds 50 parts by mass, the hydroxyl group-containing fluoropolymer and In this reaction, it is difficult to avoid gelation, and the cured film does not have a low refractive index, and the cured product may become brittle.

  In the present invention, the hydroxyl group-containing fluorine-containing polymer (A) and the crosslinkable compound (C) can be reacted in advance. For example, a crosslinkable compound may be added to a solution of an organic solvent in which a fluoropolymer is dissolved, and the reaction system may be made uniform by heating, stirring, or the like for an appropriate time. The heating temperature for this reaction is preferably in the range of 30 to 150 ° C, more preferably in the range of 50 to 120 ° C. When the heating temperature is less than 30 ° C, the reaction proceeds very slowly. When the heating temperature exceeds 150 ° C, in addition to the intended reaction, a crosslinking reaction due to the reaction between methylol groups and alkoxylated methyl groups in the crosslinkable compound occurs. This is not preferable because a gel is formed. The progress of the reaction is quantitative by measuring the amount of methylol group or alkoxylated methyl group by infrared spectroscopic analysis or by collecting the dissolved polymer by reprecipitation method and measuring the increase. Can be confirmed.

  In addition, it is preferable to use the same organic solvent as that used in the production of the hydroxyl group-containing fluoropolymer for the reaction between the hydroxyl group-containing fluoropolymer and the crosslinkable compound. In the present invention, the reaction solution obtained by the hydroxyl group-containing fluoropolymer and the crosslinkable compound thus obtained can be used as it is as the solution of the composition of the present invention, and various additives can be used as necessary. It can also be used after blending.

(D) Acid catalyst An acid catalyst is added for the purpose of improving the hardness and durability of the cured film formed from the composition of the present invention.
The acid catalyst that can be blended in the composition of the present invention is a substance that can improve the heating conditions to be milder when the coating film of the composition of the present invention is heated and cured. is there.
Examples of the acid catalyst that can be used in the present invention include a thermal acid generator that generates an acid by heating and a photosensitive acid generator that generates an acid by irradiation with radiation.

(i) Thermal acid generator Specific examples of the thermal acid generator include, for example, various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids such as citric acid, acetic acid, and maleic acid and salts thereof, benzoic acid, phthalic acid, and the like. Examples thereof include various aromatic carboxylic acids such as acids and salts thereof, alkylbenzene sulfonic acids and ammonium salts thereof, various metal salts, phosphoric acid esters of organic acids and the like.

(ii) Photosensitive acid generator The photosensitive acid generator imparts photosensitivity to the coating film of the composition of the present invention and, for example, photocures the coating film by irradiating light such as light. It is a substance that makes it possible. Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts; (2) β-ketoesters, β-sulfonylsulfones and these. sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; and (4) sulfonimide compounds represented by the following formula (15): (5) Diazomethane compounds represented by the following formula (16); and the like.

式（１５）中、Ｘは、アルキレン基、アリレーン基、アルコキシレン基等の２価の基を示し、Ｒ^１９は、アルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。

In formula (15), X represents a divalent group such as an alkylene group, an arylene group or an alkoxylene group, and R ¹⁹ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group. The group of is shown.

式（１６）中、Ｒ^２０及びＲ^２１は、互いに同一でも異なってもよく、アルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。

In formula (16), R ²⁰ and R ²¹ may be the same as or different from each other, and represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

  The thermal acid generator and the photosensitive acid generator can be used in combination, and each can be used alone or in combination of two or more. The thermal acid generator or the photosensitive acid generator is used for the purpose of improving the hardness and durability of the cured film to be formed, and in particular, does not decrease the transparency after curing of the composition of the present invention, and is a solution thereof. It is preferable to select and use one that dissolves uniformly.

Content of component (D) in the composition of this invention is 0.01-20 mass parts normally, when the sum total of (A) component and (B) component is 100 mass parts. When the content of the component (D) is less than 0.01 parts by mass, the added effect may not be obtained, and when it exceeds 20 parts by mass, the strength of the obtained cured film may be reduced.
For the above reason, the content of the component (D) is preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass.

(E) Organic solvent The organic solvent is usually used for the reaction of (A) the solvent used for the production of the hydroxyl group-containing fluoropolymer, or (A) the hydroxyl group-containing fluoropolymer with (C) the crosslinkable compound. Therefore, usually, the solvent is contained as it is, but the solvent of the composition of the present invention is improved to improve the coating property, etc. can do.

  Further, preferred solvents contained in the composition of the present invention include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetone, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, methanol, ethanol, Examples include alcohols such as isopropyl alcohol, sec-butanol, t-butanol, and propylene glycol monomethyl ether; aromatics such as benzene, toluene, xylene, nitrobenzene, chlorobenzene, and phenol; and ethers such as dimethyl ether and diethyl ether. . Of these solvents, ketones, alcohols and esters are particularly preferred.

  Content of the component (E) in the composition of this invention is 100-10000 mass parts normally, when the sum total of (A) component and (B) component is 100 mass parts, and 500-5000 mass parts is. Preferably, 1000 to 5000 parts by weight are more preferable.

(F) Additive The composition of the present invention includes, for example, various polymers having a hydroxyl group for the purpose of improving the coating properties of the composition and the physical properties of the thin film after curing, and imparting photosensitivity to the coating film. And colorants such as monomers, pigments or dyes, stabilizers such as anti-aging agents and ultraviolet absorbers, surfactants, polymerization inhibitors, solvents, hollow particles based on silica, and silica based Various additives such as real particles can be contained.

(i) Polymer having hydroxyl group The polymer having a hydroxyl group that can be blended in the composition of the present invention is obtained, for example, by copolymerizing a hydroxyl group-containing copolymerizable monomer such as hydroxyethyl (meth) acrylate. Examples of the polymer, novolak resin or resol resin include resins having a known phenol skeleton.

(ii) Colorant such as pigment or dye Examples of the colorant that can be incorporated into the composition of the present invention include (1) extender pigments such as alumina white, clay, barium carbonate, and barium sulfate; (2) zinc Inorganic pigments such as white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black; (3) Brilliant Carmine 6B, Permanent Red 6B, Permanent Red R, Benzidine Yellow, Phthalocyanine Organic pigments such as blue and phthalocyanine green; (4) basic dyes such as magenta and rhodamine; (5) direct dyes such as direct scarlet and direct orange; (6) acidic dyes such as roserine and methanyl yellow; be able to.

(iii) Stabilizers such as anti-aging agents and UV absorbers As anti-aging agents and UV absorbers that can be blended in the composition of the present invention, known ones can be used.
Specific examples of the antioxidant include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone Monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl) -4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimidazole, and the like.

  Specific examples of the UV absorber include, for example, salicylic acid UV absorbers represented by phenyl salicylate, benzophenone UV absorbers such as dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, and benzotriazole UV absorbers. Ultraviolet absorbers used as additives for various plastics such as cyanoacrylate-based ultraviolet absorbers can be used.

(iv) Surfactant A surfactant can be added to the composition of the present invention for the purpose of improving the coating property of the composition. As this surfactant, known ones can be used. Specifically, for example, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used. In particular, a cationic surfactant is preferably used so that the cured film has excellent strength and good optical properties. Furthermore, a quaternary ammonium salt is preferable, and among them, the use of a quaternary polyether ammonium salt is particularly preferable because dust wiping property is further improved. Examples of cationic surfactants that are quaternary polyether ammonium salts include Adekacol CC-15, CC-36, and CC-42 manufactured by Asahi Denka Kogyo Co., Ltd. The use ratio of the surfactant is preferably 5 parts by weight or less with respect to 100 parts by weight of the composition of the present invention.

Next, the preparation method and curing conditions of the curable resin composition of the present invention will be described.
The curable resin composition of the present invention includes the components (A), (B), and (C), or the component (D), the organic solvent (E), and the additive (F) as necessary. Thus, it can be prepared by mixing at room temperature or under heating conditions.

When component (C) is added, component (A) and component (C) may be reacted in advance.
The reaction between the hydroxyl group-containing fluoropolymer as component (A) and the crosslinkable compound as component (C) is, for example, adding component (C) to a solution of an organic solvent in which component (A) is dissolved, What is necessary is just to carry out, making a reaction system uniform by heating, stirring, etc. for an appropriate time.

  The heating temperature for this reaction is preferably in the range of 30 to 150 ° C, more preferably in the range of 50 to 120 ° C. When the heating temperature is less than 30 ° C, the reaction proceeds very slowly. When the heating temperature exceeds 150 ° C, in addition to the intended reaction, a crosslinking reaction due to the reaction between methylol groups and alkoxylated methyl groups in the crosslinkable compound occurs. This is not preferable because a gel is formed. The progress of the reaction is quantitative by measuring the amount of methylol group or alkoxylated methyl group by infrared spectroscopic analysis or by collecting the dissolved polymer by reprecipitation method and measuring the increase. Can be confirmed.

In addition, it is preferable to use the same thing as the organic solvent used in manufacture of an organic solvent, for example, a hydroxyl-containing fluoropolymer, for reaction of (A) component and (C) component. In the present invention, the reaction solution obtained by the hydroxyl group-containing fluoropolymer and the crosslinkable compound thus obtained can be used as it is as a solution of the curable resin composition, and various additives can be used as necessary. It can also be used after blending.
After the reaction between the component (A) and the component (C), the component (B), or the component (D), the organic solvent (E), and the additive (F) may be added as necessary.

The curable resin composition of the present invention can be applied to various substrates in the form of a solution, and an excellent low refractive index film is formed by curing the obtained coating film.
As the coating method, a known coating method can be used, and in particular, various methods such as a dip method, a coater method, and a printing method can be applied.

  The coating film of the curable resin composition formed by coating is particularly preferably given a heat history by heating in order to form a cured film having excellent optical properties and durability. Of course, even when left at room temperature, the curing reaction proceeds with the passage of time, and the desired cured film is formed. However, in practice, curing by heating is effective in reducing the required time. Is. Moreover, the curing reaction can be further promoted by adding a thermal acid generator (D) as a curing catalyst. The heating conditions for the curing reaction can be selected as appropriate, but the heating temperature needs to be equal to or lower than the heat resistant limit temperature of the substrate to be coated.

2. Antireflective film The antireflective film of this invention contains the low-refractive-index layer which consists of a film | membrane which hardened the said curable resin composition. Furthermore, the antireflection film of the present invention can contain a high refractive index layer, a hard coat layer, and / or a substrate under the low refractive index layer.
FIG. 1 shows such an antireflection film 10. As shown in FIG. 1, a hard coat layer 14 and a low refractive index layer 18 are laminated on a substrate 12.
At this time, a high refractive index layer (not shown) may be directly formed on the substrate 12 without providing the hard coat layer 14, or the hard coat layer 14 and the low refractive index layer 18 may be formed. A high refractive index layer may be provided therebetween.
Further, an intermediate refractive index layer (not shown) may be further provided between the high refractive index layer and the low refractive index layer 18 or between the high refractive index layer and the hard coat layer 14.

(1) Low refractive index layer A low refractive index layer is comprised from the film | membrane obtained by hardening | curing the curable resin composition of this invention. Since the configuration and the like of the curable resin composition are as described above, a specific description thereof will be omitted, and the refractive index and thickness of the low refractive index layer will be described below.

The refractive index at 589 nm of the cured product obtained by curing the curable resin composition (refractive index of Na-D line, measurement temperature 25 ° C.), that is, the refractive index of the low refractive index film should be less than 1.45. Is preferred. This is because when the refractive index of the low refractive index film is 1.45 or more, the antireflection effect may be significantly lowered when combined with the high refractive index film.
Therefore, the refractive index of the low refractive index film is more preferably 1.44 or less, and further preferably 1.43 or less.
In the case where a plurality of low refractive index films are provided, at least one of the low refractive index films only needs to have a refractive index value within the above-described range. Therefore, the other low refractive index films exceed 1.45. It may be a value.

Moreover, when providing a low-refractive-index layer, since the more outstanding antireflection effect is acquired, it is preferable to make the refractive index difference between a low-refractive-index layer and a lower layer into 0.05 or more value. The reason for this is that when the refractive index difference between the low refractive index layer and the lower layer is a value less than 0.05, the synergistic effect in these antireflection film layers cannot be obtained, and the antireflection effect decreases instead. Because there is.
Therefore, the refractive index difference between the low refractive index layer and the lower layer is more preferably set to a value within the range of 0.1 to 0.5, and the value within the range of 0.15 to 0.5. Is more preferable.

The thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 300 nm, for example. The reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index film as the base may be reduced. On the other hand, when the thickness exceeds 300 nm, optical interference occurs. This is because the antireflection effect may be reduced.
Therefore, the thickness of the low refractive index layer is more preferably 50 to 250 nm, and further preferably 60 to 200 nm.
In order to obtain higher antireflection properties, when a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness may be set to 50 to 300 nm.

(2) High refractive index layer Although it does not restrict | limit especially as a curable composition for forming a high refractive index layer, As a film formation component, epoxy-type resin, phenol-type resin, melamine-type resin, It is preferable to include one kind or a combination of two or more kinds of alkyd resins, cyanate resins, acrylic resins, polyester resins, urethane resins, siloxane resins and the like. If these resins are used, a strong thin film can be formed as the high refractive index layer, and as a result, the scratch resistance of the antireflection film can be remarkably improved.
However, the refractive index of these resins alone is usually 1.45 to 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to blend high refractive index inorganic particles, for example, metal oxide particles. Moreover, as a hardening form, although the curable composition which can be thermosetting, ultraviolet curing, and electron beam curing can be used, the ultraviolet curable composition with favorable productivity is used more suitably.

The thickness of the high refractive index layer is not particularly limited, but is preferably 50 to 30,000 nm, for example. The reason for this is that when the thickness of the high refractive index layer is less than 50 nm, the antireflection effect and adhesion to the substrate may be reduced when combined with the low refractive index layer, while the thickness is If the thickness exceeds 30,000 nm, optical interference may occur, and the antireflection effect may be reduced.
Therefore, the thickness of the high refractive index layer is more preferably 50 to 1,000 nm, and further preferably 60 to 500 nm.
Further, in order to obtain higher antireflection properties, when a plurality of high refractive index layers are provided to form a multilayer structure, the total thickness may be set to 50 to 30,000 nm.
In addition, when providing a hard-coat layer between a high refractive index layer and a base material, the thickness of a high refractive index layer can be 50-300 nm.

(3) Hard coat layer The constituent material of the hard coat layer used in the antireflection film of the present invention is not particularly limited. Examples of such a material include one kind of siloxane resin, acrylic resin, melamine resin, epoxy resin, or a combination of two or more kinds.

  Moreover, although it does not restrict | limit especially also about the thickness of a hard-coat layer, it is preferable to set it as 1-50 micrometers, and it is more preferable to set it as 5-10 micrometers. The reason for this is that when the thickness of the hard coat layer is less than 1 μm, the adhesion of the antireflection film to the substrate may not be improved. On the other hand, when the thickness exceeds 50 μm, it is uniform. This is because it may be difficult to form.

(4) Substrate The type of the substrate used for the antireflection film of the present invention is not particularly limited. For example, glass, polycarbonate resin, polyester resin, acrylic resin, triacetyl cellulose resin (TAC) And a substrate made of norbornene-based resin or the like. By using an antireflection film containing these base materials, excellent reflection can be achieved in a wide range of application areas of antireflection films such as camera lens parts, television (CRT) screen display parts, and color filters in liquid crystal display devices. The prevention effect can be obtained.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to the description of these examples.

(Production Example 1)
Synthesis of Hydroxyl-Containing Fluoropolymer 1 A stainless steel autoclave with an internal volume of 2.0 liters equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 400 g of ethyl acetate, 53.2 g of perfluoro (propyl vinyl ether), 36.1 g of ethyl vinyl ether. , Hydroxyethyl vinyl ether 44.0 g, lauroyl peroxide 1.00 g, azo group-containing polydimethylsiloxane represented by the above formula (8) (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) 6.0 g and After charging 20.0 g of nonionic reactive emulsifier (NE-30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.) and cooling to −50 ° C. with dry ice-methanol, the oxygen in the system was again nitrogen gas. Removed.

Next, 120.0 g of hexafluoropropylene was charged, and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer. This is referred to as a hydroxyl group-containing fluoropolymer. Table 1 shows the amounts (g) of monomers and solvents used.

Attached to the obtained hydroxyl group-containing fluoropolymer, the number average molecular weight in terms of polystyrene by gel permeation chromatography and the fluorine content by the alizarin complexone method were measured. ^{Further, 1 H-NMR, 13 C} -NMR both results of NMR analysis, elemental analysis and fluorine content to determine the percentage of each monomer component constituting the hydroxyl group-containing fluoropolymer. The results are shown in Table 2.

VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (8) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000. NE-30 is a nonionic reactive emulsifier wherein n is 9, m is 1 and u is 30 in the above formula (11).
Furthermore, in Table 2, the correspondence between the monomer and the structural unit is as follows.
Monomer Structural unit Hexafluoropropylene (a)
Perfluoro (propyl vinyl ether) (a)
Ethyl vinyl ether (b)
Hydroxyethyl vinyl ether (c)
NE-30 (g)
Polydimethylsiloxane skeleton (e)

(Production Example 2)
Synthesis of Hydroxyl-Containing Fluoropolymer 2 A stainless steel autoclave with an internal volume of 2.0 liters equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 200 g of ethyl acetate, 1-vinyloxy-3,3,4, , 6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecane (FAVE-8) 41.2 g, 1H, 1H-perfluoro-2- (2-vinyloxy) Ethoxy) propanol (FVEP) 58.8 g, lauroyl peroxide 0.5 g, azo group-containing polydimethylsiloxane (VPS1001) represented by the above formula (8) 3.0 g and nonionic reactive emulsifier (NE-30) 5 0.0 g was charged and cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.
Next, the temperature was raised and the reaction was continued with stirring at 70 ° C. for 20 hours. At 20 hours, the reaction was stopped by cooling the autoclave with water. After reaching room temperature, the autoclave was opened to obtain a polymer solution having a solid content concentration of 24.0%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 100 g of a hydroxyl group-containing fluoropolymer. This is referred to as a hydroxyl group-containing fluoropolymer. Table 3 shows the monomers and solvents used.

Attached to the obtained hydroxyl group-containing fluoropolymer, the number average molecular weight in terms of polystyrene by gel permeation chromatography and the fluorine content by the alizarin complexone method were measured. ^{Further, 1 H-NMR, 13 C} -NMR both results of NMR analysis, elemental analysis and fluorine content to determine the percentage of each monomer component constituting the hydroxyl group-containing fluoropolymer. The results are shown in Table 4.

In Table 4, the correspondence between the monomer and the structural unit is as follows.
Monomer structural unit FAVE-8 (b)
FVEP (d)
NE-30 (g)
Polydimethylsiloxane skeleton (e)

(Production Example 3)
Preparation of Magnesium Fluoride Particle-Dispersed Sol (B-1) (Component (B)) 1400 parts of methyl isobutyl ketone, 10 parts of a polymeric surfactant (Marialim AAB0851 manufactured by NOF Corporation), magnesium fluoride sol (made by Stella Chemifa) A liquid obtained by mixing 190 parts of magnesium fluoride OP (number average particle size 5 μm) with a homomixer was dispersed using a disperser (Ultra Aspec Mill manufactured by Kotobuki Industries). As pre-dispersion, 600 parts of zirconia beads (particle size 0.5 mm) were added to the previous mixed solution, and dispersion was performed at a peripheral speed of 5 m / s for 1 hour. Thereafter, the pre-dispersion liquid was collected, and zirconia beads were filtered off. As the main dispersion using the filtrate, 600 parts of zirconia beads (particle size: 0.2 μm) were added to the filtrate, and dispersed at a peripheral speed of 10 m / s for 2 hours to obtain a white transparent particle dispersion B-1. . After weighing 2 g of B-1 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 12% by mass.
The average particle diameter of the magnesium fluoride-based particles was 20 to 50 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 4)
Preparation of Magnesium Fluoride Dispersion Sol (B-2) (Component (B)) Magnesium fluoride IPA sol / San colloid MSF-10P (particle size: about 0.2 μm) manufactured by Nissan Chemical. After weighing 2 g of B-2 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, and it was 10% by mass.
After mixing 1900 parts of sun colloid MSF-10P, 10 parts of a polymeric surfactant (Marialim AAB0851 manufactured by NOF Corporation) and 1900 parts of MIBK, the mixture was concentrated by an evaporator and concentrated until the solution was 1910 parts.
1900 parts of MIBK is added to this concentrated liquid and concentrated again. This operation is repeated and the solvent of the dispersion is replaced with MIBK.

(Production Example 5)
Preparation of silica particles (C-1) Solid content 20% by weight, pH 2.7, specific surface area by BET method 226 m ² / g, silanol concentration on silica particles determined by methyl red adsorption method is 4. 1 × 10 ⁻⁵ mol / g, water-dispersed colloidal silica having a metal content of 4.6 ppm as Na, 0.013 ppm as Ca, and 0.011 ppm as K as determined by atomic absorption spectrometry (Nissan Chemical Co., Ltd.) ), Product name: Snowtex-O) 30 kg is placed in a tank, heated to 50 ° C., circulation flow rate 50 liters / minute, pressure 1 kg / cm ² , ultrafiltration membrane module (manufactured by Tritech Co., Ltd.) and alumina ultrafiltration membrane (NGK insulators, Ltd., trade name: ceramic UF element, specifications: 4 mm diameter, 19 holes, length 1 m, molecular cutoff = 150,000, membrane area = 0.24 m ²⁾ and There were concentrated. After 0.5 hour, 10 kg of the filtrate was discharged, and the solid content became 30% by weight. The average permeation flow rate (unit area of ultrafiltration membrane, membrane permeation weight per unit time) before the start of concentration was 90 kg / m ² / hour, and 55 kg / m ² / hour at the end of concentration. The number average particle size determined by the dynamic light scattering method was 11 nm, which did not change before and after concentration.

After completion of the above-mentioned steps, 14 kg of methanol is added, concentration is performed using the ultrafiltration membrane module and the ultrafiltration membrane at a temperature of 50 ° C., a circulation flow rate of 50 liters / minute, and a pressure of 1 kg / cm ² , and 14 kg of filtrate is obtained. By repeating the discharging operation 6 times, methanol-dispersed colloidal silica having a solid content of 30% by weight, a water content determined by the Karl Fischer method of 1.5% by weight, and a number average particle size determined by the dynamic light scattering method of 11 nm. 20 kg was prepared. The average permeation flow rate of 6 times was 60 kg / m ² / hour, and the required time was 6 hours. The specific surface area of the obtained methanol-dispersed colloidal silica by the BET method was 237 m ² / g, and the silanol concentration on the silica particles determined by the methyl red adsorption method was 3.5 × 10 ⁻⁵ mol / g. The methanol-dispersed colloidal silica obtained as described above is referred to as “C-1”.

(Production Example 6)
Synthesis of specific organic compound (Bb-1) To a mixed solution of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in a vessel equipped with a stirrer, 222 parts of isophorone diisocyanate was added in dry air at 50 ° C for 1 hour. Then, the mixture was further stirred at 70 ° C. for 3 hours.
Subsequently, NK ester A-TMM-3LM-N (made of 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., is involved in the reaction. (Only pentaerythritol triacrylate having a hydroxyl group.) 549 parts were added dropwise at 30 ° C. over 1 hour, and then stirred at 60 ° C. for 10 hours to obtain a reaction solution.
The product in this reaction solution, that is, the amount of residual isocyanate in the organic compound having a polymerizable unsaturated group was measured by FT-IR and found to be 0.1% by mass or less, and each reaction was performed almost quantitatively. I confirmed that. In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of the mercapto group in the raw material and the absorption peak of 2260 Kaiser characteristic of the raw material isocyanate compound disappear, and new urethane bonds and S (C = C = O) The 1660 Kaiser peak characteristic of the NH-group and the 1720 Kaiser peak characteristic of the acryloxy group are observed, and the acryloxy group and -S (C = O) NH-, urethane bond as the polymerizable unsaturated group are observed. It was shown that an acryloxy group-modified alkoxysilane having the same structure was produced. Thus, 773 parts of a compound having a thiourethane bond, a urethane bond, an alkoxysilyl group, and a polymerizable unsaturated group and a composition (Bb-1) of 220 parts of pentaerythritol tetraacrylate not involved in the reaction were obtained. Obtained.

(Production Example 7)
Preparation of acrylic modified silica particles (C′-1) 8.7 parts of specific organic compound (Bb-1) synthesized in Production Example 6, methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST (number) (Average particle size 0.022 μm, silica concentration 30%)) 91.3 parts (solid content 27.4 parts), isopropanol 0.2 parts and ion-exchanged water 0.1 parts were stirred at 80 ° C. for 3 hours. Thereafter, 1.4 parts of methyl orthoformate was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a colorless transparent particle dispersion C′-1. 2 g of C′-1 was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 35% by mass.
The average particle diameter of the silica-based particles was 20 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 8)
Preparation of silica particle-containing composition for hard coat layer In a container shielded from ultraviolet rays, 86 parts of C′-1 synthesized in Production Example 7 (30 parts as a solid content), 65 parts of dipentaerythritol hexaacrylate, 2- A composition for a hard coat layer having a uniform solution was obtained by stirring 5 parts of methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 44 parts of MIBK at 50 ° C. for 2 hours. . 2 g of this composition was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 50% by mass.

(Production Example 9)
Preparation of base material for coating curable resin composition Single-sided easy-adhesive polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) on the easy-adhesion treated surface of silica particle-containing hard coat layer prepared in Production Example 8 The coating composition was coated with a wire bar coater to a film thickness of 3 μm, dried in an oven at 80 ° C. for 1 minute to form a coating film, and a curable resin composition coating substrate was prepared.

(Example 1)
As shown in Table 5, 1.70 g of the hydroxyl group-containing fluoropolymer obtained in Production Example 1 and 15 g of magnesium fluoride sol B-1 obtained in Production Example 3 in a solid content, urea compound Cymel 303 (Nippon Cytec) 10 g, thermal acid generator catalyst 4050 (manufactured by Nippon Cytec Co., Ltd.) 22.2 g (solid content concentration 22.5%) and MIBK 1982.8 g, glass separable flask equipped with a stirrer And stirred at room temperature for 1 hour to obtain a uniform curable resin composition. Moreover, it was 5 mass% when solid content concentration was calculated | required by the method of manufacture example 3. FIG.

(Examples 2-6, Comparative Examples 1-4)
Each curable composition was obtained in the same manner as in Example 1 except that the composition in Table 5 was followed. The composition unit of the component in a table | surface is the mass%, and the compounding quantity of each component shows solid content.
The

(Evaluation example 1)
Appearance Evaluation Each curable resin composition was coated on the hard coat obtained in Production Example 9 using a wire bar coater so as to have a film thickness of 0.1 μm. An antireflection film layer was formed by heating for 1 hour. The appearance of the obtained antireflection film was visually evaluated. The evaluation criteria are as follows. The results are shown in Table 5.
○: Transparent and free of coating unevenness Δ: Slightly uneven coating or slightly turbid ×: There is coating unevenness or turbidity on the entire surface

(Evaluation example 2)
Measurement of Refractive Index of Cured Film Each curable resin composition was applied on a silicon wafer by a spin coater so that the thickness after drying was about 0.1 μm, and then cured by heating at 120 ° C. for 1 hour. The obtained cured product was measured refractive index at a wavelength of 589nm at 25 ° C. using an ellipsometer to ^{_(n D 25).} The results are shown in Table 5.

(Evaluation example 3)
Reflectivity measurement of antireflection film The back surface of the antireflection film obtained in Evaluation Example 1 was painted with black spray, and a spectral reflectance measurement device (a self-recording spectrophotometer U incorporating a large sample chamber integrating sphere attachment device 150-09090 was incorporated. -3410, manufactured by Hitachi, Ltd.), the reflectance was measured from the microlens side in the wavelength range of 340 to 700 nm and evaluated. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength is measured using the reflectance of the aluminum deposited film as a reference (100%), and the reflectance is reflected from the reflectance of light at a wavelength of 589 nm. The prevention was evaluated.

(Evaluation example 4)
Scratch resistance test (steel wool resistance test)
The cured film obtained in Evaluation Example 1 was attached with steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.). The surface of the cured film was repeatedly rubbed 10 times under the condition of a load of 500 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The results are shown in Table 5.
A: Hardened film peeling or scratches are hardly observed.
○: Slight thin scratches are observed on the cured film.
Δ: Streaky scratches are observed on the entire surface of the cured film.
X: Peeling of the cured film occurs.

  The curable resin composition of the present invention is excellent in scratch resistance, coating property and durability, and is particularly useful as an antireflection film.

It is sectional drawing of the antireflection film by one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Antireflection film 12 Base material 14 Hard-coat layer 18 Low refractive index layer

Claims (9)

The following components (A), (B), and (C):

(A) a hydroxyl group-containing fluoropolymer,
(B) inorganic fluoride,
(C) Curable resin composition containing a crosslinkable compound.   When the total of the (A) hydroxyl group-containing fluoropolymer of the curable resin composition and the (B) inorganic fluoride is 100 parts by mass, the (A) hydroxyl group-containing fluoropolymer is 20 to 95 masses. Part, said curable resin composition of Claim 1 containing 5-80 mass parts of said (B) inorganic fluorides.   The curable resin composition according to claim 1 or 2, wherein the (B) inorganic fluoride is a particle made of an inorganic fluoride having a refractive index of less than 1.45 at a wavelength of 589 nm.   The curable resin composition according to claim 1, wherein the (B) inorganic fluoride is magnesium fluoride.   The curable resin composition according to any one of claims 1 to 4, wherein the crosslinkable compound (C) is a compound having an amino group capable of reacting with a hydroxyl group present in the hydroxyl group-containing fluoropolymer.   Furthermore, (D) The curable resin composition as described in any one of Claims 1-5 containing an acid catalyst.   The curable resin composition according to any one of claims 1 to 6, which is used for an antireflection film.   A film obtained by curing the curable resin composition according to any one of claims 1 to 7, and having a refractive index of less than 1.45 at a wavelength of 589 nm. An antireflection film comprising the film according to claim 8.

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