JP4816986B1 - Curable composition and antireflection laminate - Google Patents

Abstract

（式（１）中、Ｒ^１は炭素数２〜４のアルキレンを表し、Ｒｆは２〜１０個のＣＦ_３基を有する炭素数３〜２０のフッ化炭素基を表し、Ｌは芳香環を含んでいてもよい炭素数６〜１２の連結基を表す。ｍは０または１であり、ｎは２〜３０の整数を表す。＊は他の原子または基と結合していることを表す。）
【選択図】図１The present invention provides a curable composition capable of forming a cured film excellent in transparency and antifouling property, and an antireflection laminate comprising the cured film formed from the curable composition.
An anti-reflection laminate 100 comprises: (A) silica particles; (B-1) fluorine-containing (meth) acrylic esters and (B-2) Curing formed from a curable composition containing at least one selected from fluorine-containing polymers containing saturated groups and (C) a fluorine-containing compound having a structure represented by the following general formula (1) It has a membrane 30.

(In the formula (1), R ¹ represents alkylene having 2 to 4 carbon atoms, Rf represents a fluorocarbon group having ₃ to 20 carbon atoms having 2 to 10 CF ₃ groups, and L represents an aromatic ring. Represents a linking group having 6 to 12 carbon atoms that may be contained, m is 0 or 1, n represents an integer of 2 to 30, and * represents bonding to another atom or group. )
[Selection] Figure 1

Description

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

  In various display panels such as liquid crystal display panels, cold cathode ray tube panels, and plasma displays, an antireflection laminate in which an antireflection film composed of a low refractive index layer is laminated in order to improve the image quality by preventing reflection of external light. It has been proposed to use Such an antireflection laminate is required to have properties such as high hardness and scratch resistance, excellent transparency, and excellent antifouling properties from the viewpoint of being used in the applications described above. .

  As a conventional antireflection laminate, for example, for antireflection provided with a cured film obtained by curing a curable composition comprising a fluoropolymer, a (meth) acrylate compound, silica particles and a photopolymerization initiator. A laminate is known (see, for example, Patent Document 1 and Patent Document 2).

  In addition, from the viewpoint of imparting antifouling properties to the cured film, the use of fluorine-based additives such as perfluoropolyether (PFPE) and perfluoroalkyl in the curable composition is also performed.

JP 2004-45462 A JP 2006-30881 A

  However, since the fluoropolymers and fluorine-based additives as described above are excellent in water repellency and oil repellency, it can be expected to improve the antifouling property of the cured film, in particular, while having compatibility and affinity with other components. There was a decline. The cured film formed from such a curable composition not only loses transparency, but also may not exhibit the expected antifouling property sufficiently.

  Therefore, some embodiments according to the present invention are formed from a curable composition capable of forming a cured film excellent in transparency and antifouling property by solving the above-described problems, and the curable composition. The laminated body for reflection prevention provided with the hardened | cured film is provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

（式（１）中、Ｒ^１は炭素数２〜４のアルキレンを表し、Ｒｆは２〜１０個のＣＦ_３基を有する炭素数３〜２０のフッ化炭素基を表し、Ｌは芳香環を含んでいてもよい炭素数６〜１２の連結基を表す。ｍは０または１であり、ｎは２〜３０の整数を表す。＊は他の原子または基と結合していることを表す。） [Application Example 1]
One aspect of the antireflection laminate according to the present invention is:
On the transparent substrate,
(A) silica particles, (B-1) at least one selected from fluorine-containing polymers containing (meth) acrylic esters containing fluorine and (B-2) ethylenically unsaturated groups; C) It has the cured film formed from the curable composition containing the fluorine-containing compound which has a structure shown by following General formula (1), It is characterized by the above-mentioned.

(In the formula (1), R ¹ represents alkylene having 2 to 4 carbon atoms, Rf represents a fluorocarbon group having ₃ to 20 carbon atoms having 2 to 10 CF ₃ groups, and L represents an aromatic ring. Represents a linking group having 6 to 12 carbon atoms that may be contained, m is 0 or 1, n represents an integer of 2 to 30, and * represents bonding to another atom or group. )

[Application Example 2]
In the antireflection laminate of Application Example 1,
In the general formula (1), Rf may be a fluorocarbon group having 4 to 20 carbon atoms having _{3 to} 10 CF ₃ groups.

[Application Example 3]
In the antireflection laminate of Application Example 1 or Application Example 2,
When the mass of the entire cured film is 100% by mass, the content of the component (C) can be 1% by mass or more and 10% by mass or less.

[Application Example 4]
In the laminate for antireflection according to any one of Application Examples 1 to 3,
The (A) silica particles may contain at least one of hollow silica particles and porous silica particles.

[Application Example 5]
In the laminate for antireflection according to any one of Application Examples 1 to 4,
The curable composition may further contain (D) a radical polymerization initiator.

[Application Example 6]
In the laminate for antireflection according to any one of Application Examples 1 to 5,
A hard coat layer may be further provided between the transparent substrate and the cured film.

（式（１）中、Ｒ^１は炭素数２〜４のアルキレンを表し、Ｒｆは２〜１０個のＣＦ_３基を有する炭素数３〜２０のフッ化炭素基を表し、Ｌは芳香環を含んでいてもよい炭素数６〜１２の連結基を表す。ｍは０または１であり、ｎは２〜３０の整数を表す。＊は他の原子または基と結合していることを表す。） [Application Example 7]
One aspect of the curable composition according to the present invention is:
(A) silica particles;
(B) at least one selected from (B-1) fluorine-containing (meth) acrylic esters and (B-2) a fluorine-containing polymer containing an ethylenically unsaturated group;
(C) a fluorine-containing compound having a structure represented by the following general formula (1);
(D) a radical polymerization initiator;
It is characterized by containing.

(In the formula (1), R ¹ represents alkylene having 2 to 4 carbon atoms, Rf represents a fluorocarbon group having ₃ to 20 carbon atoms having 2 to 10 CF ₃ groups, and L represents an aromatic ring. Represents a linking group having 6 to 12 carbon atoms that may be contained, m is 0 or 1, n represents an integer of 2 to 30, and * represents bonding to another atom or group. )

[Application Example 8]
In the curable composition of Application Example 7,
In the general formula (1), Rf may be a fluorocarbon group having 4 to 20 carbon atoms having _{3 to} 10 CF ₃ groups.

[Application Example 9]
In the curable composition of Application Example 7 or Application Example 8,
The (A) silica particles may contain at least one of hollow silica particles and porous silica particles.

  According to the curable composition concerning this invention, since surface free energy can be reduced by containing (C) component, the cured film excellent in antifouling property can be formed. Moreover, the compatibility thru | or affinity of the whole curable composition can be improved by combining (B) component and (C) component. Thereby, while ensuring the stability of a curable composition, the cured film excellent in transparency (low haze) can be formed.

  Moreover, according to the antireflection laminate of the present invention, since it has a cured film formed from the curable composition described above, not only an antireflection effect is obtained, but also transparency (low haze) and antifouling are obtained. It is also excellent in properties.

It is sectional drawing which showed typically the laminated body for reflection which concerns on this Embodiment.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included.

1. Curable composition The curable composition according to the present embodiment comprises (A) silica particles, (B) a fluorine-based binder having a reactive group, and (C) a fluorine-containing compound having a specific structure. It is characterized by containing. The curable composition according to the present embodiment includes (D) radical polymerization initiator, (E) (meth) acrylate compound, (F) surface modifier, (G) organic solvent, and (H) other additives. One or more selected from agents can also be contained. Hereinafter, each component of the curable composition which concerns on this Embodiment is demonstrated in detail. In the present specification, the materials (A) to (H) may be abbreviated as components (A) to (H), respectively.

1.1. (A) Silica particle The curable composition which concerns on this Embodiment contains (A) silica particle. (A) It does not specifically limit as a silica particle, Any of a solid silica particle, the hollow silica particle which has a cavity in particle | grains, a porous silica particle, etc. can be used. Among these, it is preferable to contain hollow silica particles or porous silica particles. This is because hollow silica particles and porous silica particles have cavities inside thereof, and therefore can have a lower refractive index than solid silica particles. Moreover, it is more preferable to contain a hollow silica particle at the point which has abrasion resistance.

  (A) The number average particle diameter of the silica particles is preferably in the range of 1 nm to 100 nm, and more preferably in the range of 5 nm to 80 nm. The number average particle diameter in this specification is measured by a transmission electron microscope. If it is less than 1 nm, the refractive index may be high, and if it exceeds 100 nm, the transparency of the cured film may be reduced.

  As the hollow silica particles, known particles can be used, and the shape thereof is not limited to spherical but may be indefinite. The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferable. These organic solvents can be used alone or in combination of two or more as a dispersion medium.

  Examples of commercially available hollow silica particles include “Thruria 4320” (number average particle diameter of 40 to 50 nm, solid content of 20% by mass, methyl ethyl ketone hollow silica sol determined by a transmission electron microscope) manufactured by JGC Catalysts & Chemicals Co., Ltd. Can be mentioned.

Further, the surface of the hollow silica particles can be subjected to a surface treatment such as chemical modification, for example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule or a hydrolyzate thereof. 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. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule are, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl having NH ₂ groups as reactive groups. Trimethoxysilane or the like having an OH group, bis (2-hydroxyethyl) -3-aminotripropylmethoxysilane or the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane or the like having a thiocyanate group As those having an thiol group such as (3-glycidoxypropyl) trimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as those having an epoxy group such as 3-thiocyanate propyltrimethoxysilane, 3-mercaptopropyltrimeth Examples of those having a (meth) acryloyl group such as xylsilane include 3- (meth) acryloxypropyltrimethoxysilane. Preferable compounds include 3- (meth) acryloxyptopropyltrimethoxysilane. It is also preferable to modify with a compound described in JP-A-9-100111.

  The content of the component (A) in the curable composition according to the present embodiment is in the range of 5% by mass to 80% by mass when the total of the components excluding the solvent is 100% by mass. Is preferable, and it is more preferably within a range of 5% by mass or more and 70% by mass or less. If it is less than 5% by mass, the blended effect may not be obtained, and if it exceeds 80% by mass, the resulting cured film may be brittle. In addition, content of (A) component means the amount of solid content, and when particle | grains are used with the form of solvent dispersion | distribution sol, the quantity of a solvent is not included in the content.

1.2. (B) Fluorine-based binder having a reactive group The curable composition according to the present embodiment contains (B) a fluorine-based binder having a reactive group. Since (B) component has high affinity with (C) component mentioned later, it can improve compatibility thru | or affinity of the whole curable composition. Thereby, while ensuring the stability of a curable composition, the cured film excellent in transparency (low haze) can be formed. Moreover, by having a fluorine atom in a molecule | numerator, a cured film can be made into a low refractive index and the antifouling property of the obtained cured film can be improved. By having a reactive group in the molecule, it can be cross-linked with other radical polymerizable compounds in the curable composition, and a cured film having better scratch resistance can be obtained. The reactive group means a functional group capable of radical polymerization.

  (B) It is preferable that the fluorine content in a component is 20 mass% or more and 60 mass% or less. If the fluorine content is less than 20% by mass, the resulting cured film may have a high refractive index. The upper limit of the fluorine content is 70% by mass. This is because if the fluorine content exceeds 70% by mass, the affinity with the component (C) described later is lowered, and the applicability of the curable composition may be deteriorated.

  The content of the component (B) in the curable composition according to the present embodiment is in the range of 5% by mass to 80% by mass when the total of the components excluding the solvent is 100% by mass. Is preferable, and it is more preferable that it is in the range of 10 mass% or more and 80 mass% or less. When the content of the component (B) is within the above range, the compatibility or affinity of the entire curable composition can be increased. Thereby, while being able to ensure the stability of a curable composition, the cured film excellent in transparency can be formed. If it is less than 5% by mass, the refractive index of the resulting cured film may increase, and the transparency of the cured film may decrease due to the loss of the affinity of the entire curable composition. When it exceeds 80 mass%, there exists a possibility that the film | membrane intensity | strength of the cured film obtained may fall.

  The component (B) is at least one selected from (B-1) fluorine-containing (meth) acrylic esters and (B-2) a fluorine-containing polymer containing an ethylenically unsaturated group. Hereinafter, the component (B-1) and the component (B-2) will be described in this order.

1.2.1. (B-1) (Meth) acrylic esters containing fluorine Fluorine-containing (meth) acrylic esters are (meth) acrylic esters and are compounds having fluorine. As described above, the component (B-1) preferably has a fluorine content of 20% by mass to 60% by mass. Moreover, it is preferable that it is a compound which has several (meth) acryloyl group. Specific examples of the component (B-1) include perfluoro-1,6-hexanediol di (meth) acrylate, tri (meth) acryloylheptadecafluorononenylpentaerythritol, octafluorooctane-1,6-di ( (Meth) acrylate, reaction product of octafluorooctanediol and 2- (meth) acryloyloxyethyl isocyanate, reaction product of octafluorooctanediol and 2- (meth) acryloyloxypropyl isocyanate, octafluorooctanediol and 1,1 Examples include a reaction product with-(bisacryloyloxymethyl) ethyl isocyanate. These can be used individually by 1 type or in combination of 2 or more types.

1.2.2. (B-2) Fluoropolymer containing an ethylenically unsaturated group The ethylenically unsaturated group-containing fluoropolymer is a polymer of a fluoroolefin. The component (B-2) can be obtained, for example, by reacting a hydroxyl group-containing fluoropolymer with a compound having a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. By adding the component (B-2), it can be co-crosslinked with the radically polymerizable (meth) acrylic compound, and the scratch resistance is improved.

(1) A compound containing a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group As a compound containing a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group, the compound contains an ethylenically unsaturated group in the molecule. The compound is not particularly limited as long as it has a functional group capable of reacting with the hydroxyl group of the fluoropolymer. Moreover, as a compound containing the said ethylenically unsaturated group, since a curable composition can be hardened more easily, the compound which has a (meth) acryloyl group is more preferable. Such compounds include (meth) acrylic acid, (meth) acryloyl chloride, anhydrous (meth) acrylic acid, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1- One kind of bisacryloyloxymethyl ethyl isocyanate or a combination of two or more kinds may be mentioned. In addition, as a commercial item of the (meth) acrylate which has an isocyanate group, Karenz MOI, AOI, BEI (above, Showa Denko KK make) etc. are mentioned, for example.

  Such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate. As examples of diisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are preferred. As examples of the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable. In addition, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, for example, HEA (Osaka Organic Chemical Co., Ltd.); KAYARAD DPHA, PET-30 (above, Nippon Kayaku Co., Ltd.); , M-233, M-305, M-400 (manufactured by Toagosei Co., Ltd.) and the like.

(2) Hydroxyl group-containing fluoropolymer The hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a) and (b).
(A) A structural unit represented by the following formula (2).
(B) A structural unit represented by the following formula (3).

（式（２）中、Ｒ^２はフッ素原子、フルオロアルキル基または−ＯＲ^３で表される基（Ｒ^３はアルキル基またはフルオロアルキル基を示す）を示す。）

(In formula (2), R ² represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ³ (R ³ represents an alkyl group or a fluoroalkyl group).)

（式（３）中、Ｒ^４は水素原子またはメチル基を、Ｒ^５は水素原子またはヒドロキシアルキル基を、ｖは０または１の数を示す。）

(In formula (3), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1.)

(I) Structural unit (a)
In the formula (2), examples of the fluoroalkyl group represented by R ² and R ³ include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorocyclohexyl group. A C1-C6 fluoroalkyl group is mentioned. Moreover, as an alkyl group of R < ³ >, C1-C6 alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, are mentioned.

  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 of such fluorine-containing vinyl monomers include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; Perfluoro (alkyl vinyl ethers) such as fluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (propoxypropyl vinyl ether) One perfluoro (alkoxyalkyl vinyl ether) such as a single compound or a combination of two or more compounds. 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, as for the content rate of a structural unit (a), 20-70 mol% is preferable when the total amount of the structural unit in a hydroxyl-containing fluoropolymer is 100 mol%. This is because when the content is less than 20 mol%, it may be difficult to develop a low refractive index. On the other hand, when the content exceeds 70 mol%, the organic group of the hydroxyl group-containing fluoropolymer is organic. This is because solubility in a solvent, transparency, or adhesion to a substrate may be lowered. For these reasons, the content of the structural unit (a) is more preferably 25 to 65 mol%, and more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

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

  The structural unit (b) 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 (b) shall be 5-70 mol% when the total amount of the structural unit in a hydroxyl-containing fluoropolymer is 100 mol%. 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 such reasons, the content of the structural unit (b) is more preferably 5 to 40 mol%, and preferably 5 to 30 mol%, based on the total amount of the structural unit of the hydroxyl group-containing fluoropolymer. More preferably.

(Iii) Other structural units The hydroxyl group-containing fluoropolymer is a structural unit represented by the following general formula (4), a polysiloxane structure, or a poly (alkylene oxide) chain as long as the effects of the present invention are not impaired. The structure derived from the monomer which has can also be comprised.

（式（４）中、Ｒ^６は水素原子またはメチル基を、Ｒ^７はアルキル基、−ＣＨ_２ｘ−ＯＲ^８もしくは−ＯＣＯＲ^８で表される基（Ｒ^８はアルキル基またはグリシジル基を、ｘは０または１の数を示す）、カルボキシル基またはアルコキシカルボニル基を示す。）

(In Formula (4), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group, a group represented by —CH _2x —OR ⁸ or —OCOR ⁸ (R ⁸ represents an alkyl group or a glycidyl group, x Represents a number of 0 or 1, and represents a carboxyl group or an alkoxycarbonyl group.)

In the formula (4), examples of the alkyl group represented by R ⁷ or R ⁸ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group. Examples of the carbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

(Iv) 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 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.

1.3. (C) Fluorine-containing compound having a specific structure The curable composition according to the present embodiment contains (C) a fluorine-containing compound having a structure represented by the following general formula (1).

In the general formula (1), Rf is a fluorocarbon group having ₃ to 20 carbon atoms and having 2 to 10 CF ₃ groups. Rf is preferably a fluorocarbon group having 4 to 20 carbon atoms having _{3 to} 10 CF ₃ groups. If Rf is a fluorocarbon group having 3 to 20 carbon atoms and having 2 to 10 CF ₃ groups, as compared with the case Rf is a perfluoroalkyl group containing perfluoropolyether groups or straight-chain CF ₃ The number of bases increases and the surface tension can be lowered. That is, since the component (C) can be easily transferred to the coating film surface, the surface free energy on the coating film surface can be lowered. For these reasons, the curable composition according to the present embodiment can form a cured film having excellent antifouling properties.

  Examples of such Rf include groups represented by the following formulas (5) to (9).

In addition, since the component (C) has a large number of CF ₃ groups, the fluorine content becomes high, and as a result, the water and oil repellency becomes strong. If it does so, since the compatibility thru | or affinity with the other component in a curable composition will fall, the transparency of a cured film may be impaired. However, the curable composition which concerns on this Embodiment can improve compatibility thru | or affinity of the whole curable composition by combining (B) component and (C) component. Thereby, while ensuring the stability of a curable composition, the cured film excellent in transparency (low haze) can be formed.

In the general formula (1), R ¹ is alkylene having 2 to 4 carbon atoms. Examples of R ¹ include ethylene, propylene, isopropylene, and butylene, and ethylene is preferable. n is an integer of 2 to 30, and preferably 3 to 15. By setting n within the above range, high antifouling properties can be obtained. L is a linking group having 6 to 12 carbon atoms which may contain an aromatic ring. L is a group that may be introduced for the purpose of facilitating the production or adjusting the solubility in a solvent. Examples of L include residues obtained by removing two OH groups from phenylene and salicylic acid, residues obtained by removing two OH groups from phthalic acid, and the like. m is 0 or 1. * Represents bonding to another atom or group.

  The component (C) is not particularly limited as long as it is a fluorine-containing compound having a structure represented by the general formula (1), and examples thereof include compounds represented by the following formulas (10) to (13). Can do.

前記式（１０）〜（１３）中、Ｒｆ、Ｒ^１、Ｌ、ｍ、およびｎは前述の通りである。式（１０）中、Ｒ^９は水素原子、メチル基またはエチル基を表す。

In the formulas (10) to (13), Rf, R ¹ , L, m, and n are as described above. In formula (10), R ⁹ represents a hydrogen atom, a methyl group or an ethyl group.

  (C) component can be manufactured by a well-known method. That is, it can be produced by mixing a compound having a polyalkylene glycol chain and a hydroxyl group with a fluorocarbon compound corresponding to the Rf and reacting with a weak base compound such as potassium t-butoxide or potassium carbonate as a catalyst. it can. The compound corresponding to Rf is a compound bonded to fluorine at the Rf bonding moiety. In addition, it is preferable that the fluorocarbon compound used here has a carbon-carbon double bond and fluorine is directly bonded to the carbon forming the double bond, because the reaction selectivity is increased.

  The content of the component (C) in the curable composition according to the present embodiment is within the range of 1% by mass or more and 20% by mass or less when the total of the components excluding the solvent is 100% by mass. Is preferable, and it is more preferably in the range of 2% by mass or more and 10% by mass or less. If it is less than 1% by mass, the antifouling property of the obtained cured film may be insufficient, and if it exceeds 20% by mass, the transparency of the obtained cured film may be impaired.

1.4. (D) Radical polymerization initiator The curable composition which concerns on this Embodiment may contain the (D) radical polymerization initiator in order to accelerate | stimulate hardening. Examples of such (D) radical polymerization initiator include a compound that thermally generates active radical species (thermal polymerization initiator) and a compound that generates active radical species by radiation (light) irradiation (radiation (light And general-purpose products such as polymerization initiators). Among these, a radiation (photo) polymerization initiator is preferable.

  The radiation (light) radical polymerization initiator is not particularly limited as long as it can be decomposed by radiation (light) irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxy Cyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4 '-Dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropa -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2) -Propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1) -(4- (1-methylvinyl) phenyl) propanone) and the like It is.

  Examples of commercially available radiation (photo) radical polymerization initiators include, for example, Irgacure (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, and CG24 manufactured by BASF Japan Ltd. -61, Darocur 1116, 1173, Lucyrin TPO, 8893, Ubekril P36 manufactured by UCB, Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B manufactured by Lamberti.

  The thermal radical polymerization initiator is not particularly limited as long as it is decomposed by heating to generate radicals to initiate polymerization, and examples thereof include peroxides and azo compounds. Specific examples include: Examples include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyronitrile.

  The content of the component (D) in the curable composition according to the present embodiment is within a range of 0.01% by mass or more and 20% by mass or less when the total of components excluding the solvent is 100% by mass. It is preferable to be within a range of 0.1% by mass or more and 10% by mass or less. By containing the component (D) within the above range, a cured film with high hardness can be formed.

1.5. (E) (Meth) acrylate Compound A (meth) acrylate compound other than the component (B) may be added to the curable composition according to the present embodiment as necessary. The (meth) acrylate compound is used for improving the scratch resistance of a cured film obtained by curing the curable composition.

  The (meth) acrylate compound is not particularly limited as long as it is a compound having at least one (meth) acryloyl group in the molecule, but is a compound having two or more (meth) acryloyl groups. Is preferred.

  Examples of the compound having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol Cyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanate Nurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, pro Renoxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether at both ends (meth) acrylic acid Adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, Polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate , Caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di ( (Meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, PO modified hydrogenated bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, etc. It can be illustrated. Commercially available products of these polyfunctional monomers include, for example, SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat 300, biscoat 360, biscoat. GPT, biscoat 400, biscoat 700, biscoat 540, biscoat 3000, biscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R -604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA-2 , DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R -011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M-309, M-310, M-315, M-325, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA DCP-A (above, manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), A F-400 (manufactured by Nippon Steel Chemical Co., Ltd.), lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Polymer Co., Ltd.), NK ester A-BPE-4 (made by Shin-Nakamura Chemical Co., Ltd.) etc. are mentioned.

  In addition, it is more preferable to add the compound containing 3 or more (meth) acryloyl groups in a molecule | numerator among these to the curable composition which concerns on this Embodiment. Examples of the compound having three or more (meth) acryloyl groups include tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds and hexa (meth) acrylate compounds exemplified above. You can choose from. Each of the above compounds can be used alone or in combination of two or more.

  The content of the (meth) acrylate compound in the curable composition according to the present embodiment is in the range of 5% by mass to 50% by mass when the total of components excluding the solvent is 100% by mass. Preferably, it is in the range of 5% by mass or more and 40% by mass or less. By containing the (meth) acrylate compound within the above range, the scratch resistance of a cured film obtained by curing the curable composition can be improved.

1.6. (F) Surface modifier A surface modifier may be further added to the curable composition according to the present embodiment as necessary. Examples of the surface modifier include compounds having a polydimethylsiloxane skeleton. The compound having a polydimethylsiloxane skeleton can improve the surface slipperiness of the cured film, improve the scratch resistance, and improve the antifouling property.

  The compound having a polydimethylsiloxane skeleton preferably further has a reactive group such as a (meth) acryloyl group or a hydroxyl group. Specific examples thereof include Silaplane FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411, FM-0425, FM-DA11, FM-DA21, FM -DA26, FM-0711, FM-0721, FM-0725, TM-0701, TM-0701T (above, trade name, manufactured by Chisso Corporation), UV3500, UV3510, UV3530 (above, trade name, BIC Chemie Japan, Inc.) Product), BY16-004, SF8428 (above, trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.), VPS-1001 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), and the like.

  The content of the surface modifier in the curable composition according to the present embodiment is within a range of 0.01% by mass or more and 20% by mass or less when the total of components excluding the solvent is 100% by mass. It is preferable to be within a range of 0.1% by mass or more and 10% by mass or less.

1.7. (G) Organic solvent The density | concentration of a curable composition can be adjusted to the curable composition which concerns on this Embodiment by adding an organic solvent as needed. Thereby, handling of the curable composition may be facilitated, and a cured film having a uniform film thickness can be easily formed.

  Specific examples of the organic solvent include ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; propylene glycol monomethyl ether, methanol and ethanol , Sec-butanol, t-butanol, 2-propanol, isopropanol, and other alcohols; benzene, toluene, chlorobenzene, and other aromatics; hexane, cyclohexane, and other aliphatic groups, and the like. It is done.

  The addition amount of the organic solvent is not particularly limited, but is preferably 100 parts by mass or more and 100,000 parts by mass or less when the total of components excluding the solvent is 100 parts by mass.

1.8. (H) Other additives In the curable composition according to the present embodiment, inorganic particles other than silica particles, a photosensitizer, a polymerization inhibitor, and a polymerization start, as long as the object and effect of the present invention are not impaired. Add additives such as auxiliaries, leveling agents, wettability improvers, antifoaming agents, plasticizers, UV absorbers, antioxidants, antistatic agents, silane coupling agents, pigments, dyes, slip agents, etc. Also good.

1.9. Manufacturing method of curable composition The curable composition which concerns on this Embodiment adds the said (A) component thru | or said (C) component, and (D) component thru | or (H) component as needed, It can be produced by mixing at room temperature or under heating conditions. Specifically, it can be produced using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when a thermal polymerization initiator is used as the component (D), when mixing under heating conditions, it is necessary to mix at or below the decomposition start temperature of the thermal polymerization initiator.

2. Anti-reflection laminate 2.1. Configuration The antireflection laminate according to the present embodiment has a cured film formed from the curable composition (hereinafter, also simply referred to as “cured film”) on a transparent substrate. Furthermore, the antireflection laminate according to the present embodiment may have a hard coat layer between the transparent substrate and the cured film. By forming the hard coat layer, the hardness of the entire antireflection laminate can be increased, and the structure is stabilized. Further, for the purpose of reducing the reflectance, a high refractive index layer may be provided adjacent to the substrate side of the cured film. By forming the high refractive index layer, the antireflection effect can be enhanced.

  According to the antireflection laminate of the present embodiment, since it has a cured film formed from the curable composition described above, not only an antireflection effect is obtained, but also transparency (low haze) and antifouling are obtained. It is also excellent in properties.

  FIG. 1 is a cross-sectional view schematically showing an antireflection laminate 100 according to the present embodiment. As shown in FIG. 1, the antireflection laminate 100 is laminated on a transparent substrate 10 in the order of a hard coat layer 20 and a cured film 30. Note that the cured film 30 may be formed directly on the transparent substrate 10 without forming the hard coat layer 20.

  Although the kind in particular of the transparent base material 10 is not restrict | limited, For example, the base material which consists of glass, a polycarbonate resin, a polyester resin, an acrylic resin, a triacetyl cellulose resin etc. is mentioned. By using an antireflection laminate containing these transparent substrates, excellent antireflection in a wide range of applications such as camera lens units, television (CRT) screen display units, and color filters in liquid crystal display devices. An effect can be obtained.

  The material of the hard coat layer 20 is not particularly limited, and examples thereof include one kind of siloxane resin, acrylic resin, melamine resin, and epoxy resin, or a combination of two or more kinds. The hard coat layer 20 preferably contains inorganic oxide particles such as silica particles as described above. By containing the inorganic oxide particles, the hardness of the hard coat layer 20 can be increased.

  The thickness of the hard coat layer 20 is not particularly limited, but is preferably 1 to 100 μm, more preferably 3 to 30 μm. If the thickness of the hard coat layer 20 is less than 1 μm, the hardness may be insufficient. On the other hand, if the thickness exceeds 100 μm, it becomes difficult to form a homogeneous film, or the curling of the laminate increases. This is because it may become difficult.

  The cured film 30 is formed by curing the curable composition. The curable composition is as described in the section “1. Curable composition”, and a specific description thereof will be omitted here.

  The refractive index of the cured film 30 is preferably 1.50 or less, more preferably 1.48 or less, and particularly preferably 1.45 or less. This is because if the refractive index exceeds 1.50, the antireflection effect may be significantly reduced. In addition, “refractive index” in the present specification means a refractive index of Na-D line (wavelength 589 nm) at a measurement temperature of 25 ° C.

  The thickness of the cured film 30 is preferably in the range of 50 to 250 nm, more preferably 50 to 200 nm, and particularly preferably 70 to 150 nm. By setting the thickness of the cured film 30 within the above range, an antireflection effect can be obtained.

  The material of the high refractive index layer is not particularly limited, and examples thereof include siloxane resins, acrylic resins, melamine resins, and epoxy resins in which inorganic oxide particles other than silica are dispersed. The refractive index of the high refractive index layer is not particularly limited as long as the refractive index is higher than that of the cured film 30, but is preferably 1.50 to 1.70, more preferably 1.52 to 1.65. is there. The thickness of the high refractive index layer is preferably 50 to 250 nm, more preferably 50 to 200 nm, and particularly preferably 70 to 150 nm. By setting the refractive index and thickness of the high refractive index layer within the above ranges, the antireflection effect can be enhanced as compared with the case where there is no high refractive index layer.

2.2. Manufacturing Method The antireflection laminate according to the present embodiment is formed on the transparent base material (when a hard coat layer and / or a high refractive index layer are formed, the hard coat layer and the high refractive index layer, respectively). It can manufacture by making it harden | cure after apply | coating the made curable composition.

  The method for applying the curable composition to the transparent substrate is not particularly limited. For example, bar coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip coating Known methods such as coating, die coating, dip coating, offset printing, flexographic printing, and screen printing can be used.

  The curing conditions of the curable composition described above are not particularly limited. Specifically, the curable composition is applied on a transparent substrate, and preferably the volatile component is dried at 0 to 200 ° C. Then, the antireflection laminate according to the present embodiment can be formed by performing a curing treatment with radiation and / or heat.

A preferable condition for curing with heat is 20 to 150 ° C., and is performed in a range of 10 seconds to 24 hours. When curing with radiation, it is preferable to use ultraviolet rays or electron beams. Irradiation light amount of the ultraviolet rays is preferably 0.01 to 10 J / cm ^2, more preferably 0.1~2J / cm ^2. Moreover, the irradiation conditions of an electron beam are a pressurization voltage of 10-300 kV, an electron density of 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount of 1-10 Mrad.

3. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

3.1. Production examples 3.1.1. (B-2) Synthesis of fluorinated polymer containing ethylenically unsaturated group After replacing a stainless steel autoclave with an internal volume of 1.0 L with a magnetic stirrer sufficiently with nitrogen gas, 600 g of ethyl acetate, perfluoro (propyl vinyl ether) ) 138.5 g, ethyl vinyl ether 37.5 g, hydroxyethyl vinyl ether 45.9 g, lauroyl peroxide 1.5 g, azo group-containing polydimethylsiloxane (trade name “VPS1001” manufactured by Wako Pure Chemical Industries, Ltd.) 9.0 g and 45 g of a nonionic reactive emulsifier (trade name “ER-30” manufactured by Asahi Denka Kogyo Co., Ltd.) was charged, cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.

Next, 85.9 g of hexafluoropropylene was charged and the temperature increase was started. The pressure when the temperature in the auto claim reached 55 ° C. was 4.1 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure decreased to 2.0 × 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 30.0%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 250 g of a hydroxyl group-containing fluoropolymer.

  Next, 50.0 g of the hydroxyl group-containing fluoropolymer obtained above was placed in a 1 L separable flask equipped with an electromagnetic stirrer, a glass condenser, and a thermometer, and 2,6-di- 0.01 g of t-butylmethylphenol and 359 g of methyl isobutyl ketone (MIBK) were charged and stirred at 20 ° C. until the hydroxyl group-containing fluoropolymer was dissolved in MIBK and the solution became transparent and uniform.

  Next, 13.4 g of 2-methacryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.1 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer was obtained by maintaining the temperature at 65 ° C. and continuing the stirring for 5 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.0% by mass.

3.1.2. (C) Synthesis 1 of a fluorine-containing compound having the structure represented by the general formula (1)
In a 100 mL three-necked flask equipped with a condenser and a dropping funnel, 5.4 g (12 mmol) of a compound represented by the following formula (14), 4.0 g (10 mmol) of polyethylene glycol monomethyl ether (average molecular weight 400) and Tetrahydrofuran 15g was charged. Further, a solution prepared by dissolving 1.3 g (12 mmol) of potassium t-butoxide in 15 g of tetrahydrofuran was put into a dropping funnel, and the solution was gradually dropped into the above flask contents with stirring over about 30 minutes. After completion of the dropwise addition, stirring was continued for 12 hours at room temperature.

  Next, potassium t-butoxide was filtered off from the obtained reaction product, the filtrate was transferred to a 100 mL round bottom flask, the solvent was evaporated using a rotary evaporator, and a compound represented by the following formula (15) (hereinafter, “ 6.0 g was also obtained. The appearance of the resulting fluorinated additive 1 was a colorless liquid.

（式（１５）中、Ｒｆは下記式（１６）で表される構造であり、ｎは平均で８．４である。）

(In Formula (15), Rf is a structure represented by following formula (16), and n is 8.4 on average.)

（式（１６）中、＊は結合部位を示す。）

(In formula (16), * indicates a binding site.)

3.1.3. (C) Synthesis 2 of a fluorinated compound having the structure represented by the general formula (1)
In a 100 mL three-necked flask equipped with a condenser and a dropping funnel, 10.8 g (24 mmol) of the compound represented by the formula (14), 4.0 g (10 mmol) of polyethylene glycol (average molecular weight 400) and 15 g of tetrahydrofuran. Was introduced. Further, a solution prepared by dissolving 2.6 g (24 mmol) of potassium t-butoxide in 15 g of tetrahydrofuran was put into a dropping funnel, and the solution was gradually added dropwise to the above flask contents with stirring over about 30 minutes. After completion of the dropwise addition, stirring was continued for 12 hours at room temperature.

  Next, potassium t-butoxide was filtered off from the obtained reaction product, the filtrate was transferred to a 100 mL round bottom flask, the solvent was evaporated using a rotary evaporator, and a compound represented by the following formula (17) (hereinafter, “ 9.0 g (also referred to as “fluorine additive 2”) was obtained. The appearance of the resulting fluorinated additive 2 was a colorless liquid.

（式（１７）中、Ｒｆは前記式（１６）で表される構造であり、ｎは平均で８．７である。）

(In Formula (17), Rf is a structure represented by said Formula (16), and n is 8.7 on an average.)

3.1.4. (C) Synthesis of a fluorine-containing compound having the structure represented by the general formula (1) 3
In a 100 mL three-necked flask equipped with a condenser and a dropping funnel, 11.5 g (10 mmol) of a compound represented by the following formula (18), 4.1 g (30 mmol) of potassium carbonate, and 40 ml of tetrahydrofuran were placed. 13.5 g (30 mmol) of the compound represented by the formula (14) was gradually added dropwise with stirring over about 30 minutes. After completion of the dropwise addition, stirring was continued for 12 hours at room temperature.

（式（１８）中、ｎは平均で８である。）

(In formula (18), n is 8 on average.)

  Next, potassium carbonate was filtered off from the obtained reaction product, the filtrate was transferred to a 100 mL round bottom flask, the solvent was evaporated using a rotary evaporator, and a compound represented by the following formula (19) (hereinafter referred to as “fluorine-based”). 9.0 g of additive 3 ”) was obtained. The appearance of the resulting fluorinated additive 3 was a colorless liquid.

（式（１９）中、Ｒｆは前記式（１６）で表される構造であり、ｎは平均で８である。）

(In Formula (19), Rf is a structure represented by said Formula (16), and n is 8 on average.)

3.1.5. (C) Synthesis of fluorine-containing compound having the structure represented by the general formula (1) 4
In a three-necked flask with a capacity of 100 mL equipped with a condenser and a dropping funnel, 10.5 g (10 mmol) of a compound represented by the following formula (20), 5.5 g (40 mmol) of potassium carbonate, and 40 ml of tetrahydrofuran were placed. 18 g (40 mmol) of the compound represented by the formula (14) was gradually added dropwise with stirring over about 30 minutes. After completion of the dropwise addition, stirring was continued for 12 hours at room temperature.

（式（２０）中、ｎは平均で８である。）

(In formula (20), n is 8 on average.)

  Next, potassium carbonate was filtered off from the obtained reaction product, the filtrate was transferred to a 100 mL round bottom flask, the solvent was evaporated using a rotary evaporator, and the compound represented by the following formula (21) (hereinafter referred to as “fluorine-based”). 22.6 g) was obtained. The appearance of the resulting fluorine-based additive 4 was a colorless liquid.

（式（２１）中、Ｒｆは前記式（１６）で表される構造であり、ｎは平均で８である。）

(In Formula (21), Rf is a structure represented by said Formula (16), and n is 8 on average.)

3.1.6. Preparation of silica particle-containing composition for hard coat layer In a container shielded from ultraviolet rays, silica particles (manufactured by Nissan Chemical Co., Ltd., trade name “MEK-ST-L”, solid content concentration 30%, number average particle diameter 50 nm) As a solid content, 30 parts by mass, 65 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 44 parts by mass of methyl isobutyl ketone The composition was stirred for 2 hours at 50 ° C. to obtain a uniform hard coat layer composition. 2 g of this composition was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 1 hour, and weighed to determine the solid content, which was 50% by mass.

3.1.7. Preparation of substrate for coating curable composition Containing silica particles prepared in “3.1.6. Preparation of silica particle-containing hard coat layer composition” on a triacetyl cellulose (TAC) film (thickness 50 μm). The composition for hard coat layers was applied with a wire bar coater (manufactured by Matsuo Sangyo Co., Ltd., No. 3, wire diameter 12 mil) so that the thickness after drying was about 5 μm. Then, it was dried at 80 ° C. for 2 minutes using a drying oven. Furthermore, ultraviolet rays were irradiated under a light irradiation condition of 300 mJ / cm ² using a high-pressure mercury lamp in the air to prepare a curable composition coating substrate.

3.2. Preparation of curable composition 3.2.1. Example 1
As shown in Table 1, 50 parts by mass of hollow silica particles (manufactured by JGC Catalysts & Chemicals, trade name “Thruria 4320”, component (A)), and solid content, fluorine-containing (meth) acrylate (Kyoeisha Chemical Co., Ltd.) Product name “LINC-3A”, (B) component) 40 parts by mass, 3.1.2. 7 parts by mass of the fluorine-based additive 1 (component (C)) synthesized as described above, 3 parts by mass of a photopolymerization initiator (manufactured by BASF Japan, trade name “Irgacure 127”, component (D)), and methyl isobutyl 1600 parts by mass of ketone and 750 parts by mass of propylene glycol monomethyl ether acetate were charged into a glass separable flask equipped with a stirrer and stirred at room temperature for 2 hours to obtain a uniform curable composition. Further, 2 g of this composition was weighed on an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 4% by mass.

3.2.2. Examples 2-10, Comparative Examples 1-2
Except having changed into the composition shown in Table 1, it carried out similarly to Example 1, and obtained the curable composition which concerns on Examples 2-10 and Comparative Examples 1-2. In the table, the blending amount is an amount as a solid content, and when blended as a solution or dispersion, the solvent or dispersion medium is not included.

Each component in Table 1 is as follows.
Component (A): hollow silica particles (manufactured by JGC Catalysts & Chemicals, trade name “Thruria 4320”, methyl isobutyl ketone hollow silica sol, number average particle size 40-50 nm, solid content concentration 20%)
Component (B-1): fluorine-containing (meth) acrylic ester (manufactured by Kyoeisha Chemical Co., Ltd., trade name “LINC-3A”, triacryloylheptadecafluorononenyl pentaerythritol 65% by mass and pentaerythritol tetraacrylate 35% by weight of mixture)
-Component (B-2): fluorinated polymer containing an ethylenically unsaturated group (synthesized in Production Example 3.1.1.)
Component (C): Fluorine-based additive 1 to 4 (synthesized in the above production example)
Component (C ′): Conventionally used linear perfluoroalkyl-containing fluorine additive (manufactured by DIC Corporation, trade name “Megafac F-444”, perfluoroalkyl group-containing polyoxyethylene ether)
Component (D): radical polymerization initiator (BASF Japan, trade name “Irgacure (registered trademark) 127”, 2-hydroxy-1- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Phenyl-2-methyl-propan-1-one)
PET-30: (meth) acrylic esters not containing fluorine (Nippon Kayaku Co., Ltd., trade name “PET-30”, pentaerythritol triacrylate)

3.3. Evaluation test 3.3.1. Evaluation of Haze (Turbidity) of Cured Film Wire each curable composition on the curable composition coating substrate prepared in “3.1.7. Preparation of curable composition coating substrate”. Using a bar coater (manufactured by Matsuo Sangyo Co., Ltd., No. 1, wire diameter of 3 mils), coating was performed so that the thickness after drying was about 100 nm. Then, it was dried at 80 ° C. for 1 minute using a drying oven. Then, it was hardened by irradiating with ultraviolet rays under light irradiation conditions of 600 mJ / cm ² using a high-pressure mercury lamp under a nitrogen flow. About the obtained cured film, turbidity was measured with the transmission type | mold measuring method by a color haze meter (Suga Test Instruments Co., Ltd. make, model "SC-3H"). The evaluation criteria are as follows. The results are also shown in Table 1.
○: Less than 0.40 ×: 0.40 or more

3.3.2. Evaluation of antifouling property A fingerprint is attached to the cured film obtained in the above “3.3.1. Evaluation of haze (turbidity) of cured film”, and tissue paper (trade name “Napier Tissue, manufactured by Oji Napier Co., Ltd.) is used. ]). The fingerprint wiping property at this time was evaluated according to the following criteria. The results are also shown in Table 1.
A: The fingerprint was completely wiped off at least once and no more than 10 times.
○: The fingerprint was completely wiped off 11 times or more and 20 times or less.
X: Fingerprint traces remained on the surface of the cured film without being wiped off.

3.4. Evaluation Results From the results in Table 1, it was found that the cured films obtained by curing the curable compositions of Examples 1 to 10 had a turbidity of less than 0.40 and excellent transparency. It was also found that the antifouling property was excellent from the result of fingerprint wiping.

  In the curable composition of Comparative Example 1, the component (B) was not added. In the cured film obtained by curing the curable composition of Comparative Example 1, the antifouling resistance was at an acceptable level, but it was found that the transparency was significantly impaired. Although the curable composition of Comparative Example 1 contains the component (C) but does not contain the component (B), the compatibility or affinity of the entire curable composition is impaired. Conceivable.

  Further, in the curable composition of Comparative Example 2, the component (C ′) (perfluoroalkyl-containing fluorine additive used conventionally) was used instead of the component (C). In the cured film obtained by curing the curable composition of Comparative Example 2, the transparency was at an acceptable level, but the antifouling resistance was insufficient. From the above, it became clear that the antifouling resistance of the cured film obtained by curing the curable composition containing the component (C) is improved.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 10 ... Transparent base material, 20 ... Hard-coat layer, 30 ... Cured film, 100 ... Laminated body for reflection prevention

Claims (9)

On the transparent substrate,
(A) Silica particles, (B-1) a fluorine-containing (meth) acrylic ester or (B-2) a hydroxyl group-containing fluoropolymer, a group capable of reacting with a hydroxyl group, and an ethylenically unsaturated group And a fluorine-containing polymer obtained by reacting the compound, or both, and (C) a fluorine-containing compound having a structure represented by the following general formula (1). An antireflection laminate having a cured film.

(In the formula (1), R ¹ represents alkylene having 2 to 4 carbon atoms, Rf represents a fluorocarbon group having ₃ to 20 carbon atoms having 2 to 10 CF ₃ groups, and L represents an aromatic ring. Represents a linking group having 6 to 12 carbon atoms that may be contained, m is 0 or 1, n represents an integer of 2 to 30, and * represents bonding to another atom or group. ) The laminate for antireflection according to claim 1, wherein, in the general formula (1), Rf is a fluorocarbon group having 4 to 20 carbon atoms having _{3 to} 10 CF ₃ groups.   The laminate for antireflection according to claim 1 or 2, wherein the content of the component (C) is 1% by mass or more and 10% by mass or less when the mass of the entire cured film is 100% by mass. .   The laminate for antireflection according to any one of claims 1 to 3, wherein the (A) silica particles contain at least one of hollow silica particles and porous silica particles.   The laminate for antireflection according to any one of claims 1 to 4, wherein the curable composition further contains (D) a radical polymerization initiator.   The laminate for antireflection according to any one of claims 1 to 5, further comprising a hard coat layer between the transparent substrate and the cured film. (A) silica particles;
(B) (B-1) (meth) acrylic esters containing fluorine or (B-2) a hydroxyl group-containing fluoropolymer, a group containing a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group, A fluorine-containing polymer obtained by reacting or both,
(C) a fluorine-containing compound having a structure represented by the following general formula (1);
(D) a radical polymerization initiator;
A curable composition comprising:

(In the formula (1), R ¹ represents alkylene having 2 to 4 carbon atoms, Rf represents a fluorocarbon group having ₃ to 20 carbon atoms having 2 to 10 CF ₃ groups, and L represents an aromatic ring. Represents a linking group having 6 to 12 carbon atoms that may be contained, m is 0 or 1, n represents an integer of 2 to 30, and * represents bonding to another atom or group. ) In the general formula (1), Rf is a fluorocarbon group having 4 to 20 carbon atoms having from 3 to 10 CF ₃ group, the curable composition according to claim 7.   The curable composition according to claim 7 or 8, wherein the (A) silica particles contain at least one of hollow silica particles and porous silica particles.

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