WO2010055758A1

WO2010055758A1 - Fluorine-containing polymer, curable resin composition composed of the fluorine-containing polymer, and anti-reflection film

Info

Publication number: WO2010055758A1
Application number: PCT/JP2009/068247
Authority: WO
Inventors: 恒雄山下; 洋介岸川; 知弘吉田; 正道森田; 義人田中
Original assignee: ダイキン工業株式会社
Priority date: 2008-11-13
Filing date: 2009-10-23
Publication date: 2010-05-20
Also published as: JP5556665B2; JPWO2010055758A1

Abstract

Disclosed is a novel fluorine-containing polymer which can be increased in hardness, while maintaining low refractive index. Also disclosed are a curable resin composition using the fluorine-containing polymer, and an anti-reflection film. The fluorine-containing polymer is represented by formula (I): -(M1)-(M2)-(N)- (wherein M1 represents a structural unit represented by formula (1-1), M2 represents a structural unit represented by formula (1-2), and N represents a structural unit derived from a monomer which is copolymerizable with monomers which respectively provide M1 and M2). The curable resin composition contains a film-forming material containing the fluorine-containing polymer, and an active energy ray-curing initiator.

Description

Fluoropolymer, curable resin composition and antireflection film comprising the fluoropolymer

The present invention relates to a fluorine-containing polymer, a curable resin composition comprising the fluorine-containing polymer, and an antireflection film obtained by curing the composition.

Along with the development of multimedia, it is becoming increasingly important to improve the visibility of various display devices (because of less reflection when viewed from an angle, also called “visibility”). Even in a large display device, it is required to make it easier to see, and this characteristic is a technical problem.

Conventionally, in order to improve the visibility of a display device, an antireflection film made of a low refractive material is coated on the substrate of the display device. As a method of forming the antireflection film, for example, a method of forming a thin film of a fluorine compound by vapor deposition is known. However, in the vapor deposition method, it is difficult to form a film on a large-screen substrate, and a vacuum apparatus is required, which increases the cost.

Under such circumstances, a method of forming an antireflection film by preparing a liquid composition in which a fluorine-containing polymer having a low refractive index is dissolved in an organic solvent and applying it to the surface of a substrate has been studied (for example, Patent Document 1).

However, in the method of applying the fluoropolymer solution, since the coating film hardness is insufficient, the coating film is scratched or peeled off due to abrasion, and the appearance of the display screen is impaired.

Thus, in addition to the low refractive index fluorine-containing polymer, after applying a composition in which a photocurable acrylic monomer such as a fluorine-containing acrylic monomer and a fluorine-containing polyfunctional acrylic compound is mixed, an acrylic monomer is applied. It has been studied to photocure the polymer (Patent Documents 2 to 4).

However, these are still insufficient in terms of hardness because the fluoropolymer itself, which is the main component, is uncrosslinked. In order to further improve the hardness, the amount of the acrylic monomer or polyfunctional acrylic compound may be increased. However, if this is done, the refractive index of the cured coating will be increased, and the intended antireflection effect will be reduced. Moreover, in this method, unreacted acrylic monomers and polyfunctional acrylic compounds are likely to remain in the coating film, which deteriorates the physical properties of the coated film after curing.

It has also been studied to apply a photopolymerizable functional group introduced into the side chain of a fluoropolymer with a mixture of an acrylic monomer or polyfunctional acrylic compound and photo-cured (patent) References 5-7).

Japanese Patent Laid-Open No. 6-115023 Japanese Unexamined Patent Publication No. 7-126552 JP-A-7-188588 JP-A-8-48935 Japanese Patent No. 2527186 Japanese Patent No. 2543903 International Publication No. 02/18457 Pamphlet

An object of the present invention is to provide a novel fluoropolymer capable of achieving high hardness while maintaining a low refractive index, a curable resin composition and an antireflection film using the same.

The present invention relates to a compound of formula (I):
-(M1)-(M2)-(N)-(I)
(Wherein M1 is a formula (1-1):

A structural unit represented by
M2 is a formula (1-2):

A structural unit represented by
N is a structural unit derived from a monomer copolymerizable with a monomer giving M1 and M2, and the structural unit M1 is 0.1 to 100 mol% and the structural unit M2 is 0 to 99.9 mol % And a structural unit N of 0 to 99.9 mol%, and a novel fluoropolymer (I) having a number average molecular weight of 500 to 1,000,000.

The present invention also provides (A) Formula (I):
-(M1)-(M2)-(N)-(I)
(Wherein M1 is a formula (1-1):

A structural unit represented by
M2 is a formula (1-2):

A structural unit represented by
N is a structural unit derived from a monomer copolymerizable with a monomer giving M1 and M2, and the structural unit M1 is 0.1 to 100 mol% and the structural unit M2 is 0 to 99.9 mol % And a structural unit N of 0 to 99.9 mol%, a film-forming material containing a fluorine-containing polymer (I) having a number average molecular weight of 500 to 1,000,000, and (B) curing containing an active energy ray curing initiator The present invention also relates to a functional resin composition.

In the curable resin composition of the present invention, the film-forming material (A) is further represented by the formula (II):
-(M3)-(N1)-(II)
(Wherein M3 is the formula (2):

(Wherein, Rf is ethylenic carbon Y ¹ (Y ¹ is terminated in the fluorine-containing alkyl group having ether bond of the fluorine-containing alkyl group or a 2 to 100 carbon atoms having 1 to 40 carbon atoms - carbon double bonds A structural unit represented by an organic group in which 1 to 3 monovalent organic groups having 2 to 10 carbon atoms are bonded, and a structure derived from a monomer copolymerizable with a monomer that gives M3 Unit)
A fluorine-containing polymer (II) containing 0.1 to 100 mol% of the structural unit M3, 0 to 99.9 mol% of the structural unit N1 and having a number average molecular weight of 500 to 1000000 may be contained.

These curable resin compositions may further contain a solvent (C).

The present invention also relates to an antireflection film obtained by photocuring the curable resin composition of the present invention.

According to the present invention, it is possible to provide a novel fluoropolymer capable of achieving high hardness while maintaining a low refractive index, a curable resin composition and an antireflection film using the fluoropolymer. .

The novel fluoropolymer of the present invention has the formula (I):
-(M1)-(M2)-(N)-(I)
(Wherein M1 is a formula (1-1):

A structural unit represented by
M2 is a formula (1-2):

A structural unit represented by
N is a structural unit derived from a monomer copolymerizable with a monomer giving M1 and M2, and the structural unit M1 is 0.1 to 100 mol% and the structural unit M2 is 0 to 99.9 mol % And structural unit N in an amount of 0 to 99.9 mol% and a number average molecular weight of 500 to 1,000,000.

In order to obtain the fluorinated polymer (I), generally, (i) a method (ii) once obtained by previously synthesizing and polymerizing a monomer (m1) having —C (═O) CF═CH ₂ In addition, there is a method of synthesizing a polymer having another functional group, converting the functional group to the polymer by a polymer reaction, and introducing —C (═O) CF═CH ₂ . The method (ii) does not require consideration of the curing reaction of the carbon-carbon double bond of —C (═O) CF═CH ₂ , and the carbon-carbon double bond having high curing reactivity. Is also a preferred method in that it can be introduced into the side chain.

Among the methods of (ii), for example, after synthesizing a fluorine-containing polymer containing a structural unit of a fluorine-containing monomer having a hydroxyl group or an organic group having a hydroxyl group, an unsaturated carboxylic acid or a derivative thereof is reacted. Thus, a method of introducing a carbon-carbon double bond into the end of the side chain of the polymer to obtain the curable fluorine-containing polymer of the present invention can be preferably employed.

Specifically, for example, in the fluoropolymer (I), the formula (1-2a):

Fluoropolymer obtained by polymerizing 0.1 to 100 mol of hexafluoroalcohol ester of α-fluoroacrylic acid represented by formula (m2) and 0 to 99.9 mol of monomer (n) giving structural unit N It can be easily obtained by polymerizing (Ia) with α-fluoroacrylic acid (CH ₂ ═CFCOOH) or its acid halide.

The proportion of M1 in the fluoropolymer (I) is determined by the reaction amount of α-fluoroacrylic acid. In the present invention, the proportion of M1 is 0.1 to 100 mol%, and the curability and solvent solubility are high. From a good point, it is preferably 10 to 90 mol%, more preferably 30 to 70 mol%.

In the above production method (i), the structural unit M2 can be introduced by copolymerizing a hexafluoroalcohol ester (m2) of α-fluoroacrylic acid. In the production method (ii), the structural unit M2 can be introduced. The acid (CH ₂ ═CFCOOH) or its acid halide can be introduced by controlling the rate of polymer reaction.

The structural unit M2 imparts characteristics such as solvent solubility, substrate adhesion, and curable crosslinking reaction point to the fluoropolymer (I).

The monomer (n) that gives the structural unit N, which is an arbitrary structural unit, includes the monomer (m1) that gives the structural unit M1, or the single unit that gives the structural unit M2 and thus the structural unit that can be converted into the structural unit M1. Monomers, for example, monomers that can be copolymerized with α-fluoroacrylic acid hexafluoroalcohol ester (m2). For example, in WO 02/18457, it is described as a monomer that gives structural unit A. What is being done.

Specifically, the following monomers can be preferably exemplified.

(I) Structural units derived from a fluorine-containing ethylenic monomer having a functional group These are adhesive units to the substrate while maintaining the refractive index of the fluorine-containing polymer (I) and its cured product low. It is preferable at the point which can provide the solubility to a solvent, especially a general purpose solvent, and is preferable at the point which can provide functions, such as crosslinkability.

The structural unit of a preferred fluorine-containing ethylenic monomer having a functional group is represented by the formula (3):

(Wherein X ¹¹ , X ¹² , X ¹³ are H, F or CH ₃ ; X ¹⁴ is H, F, CF ₃ ; CX ¹⁴ ₂ may be C═O; h is 0-2, i Rf ⁴ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms; Z ¹ is —OH, —CH ₂ OH, —COOH, carboxylic acid Derivatives, —SO ₃ H, sulfonic acid derivatives, epoxy groups, and cyano groups).

Specifically, the following monomers can be exemplified.

(Ii) Structural units derived from a fluorine-containing ethylenic monomer that does not contain a functional group. These are because the refractive index of the fluorine-containing polymer (I) or its cured product can be kept low, and the refractive index is further lowered. It is preferable in that it can be performed. In addition, the mechanical properties and glass transition point of the fluoropolymer (I) can be adjusted by selecting the monomer, and in particular, the glass transition point can be increased by copolymerizing with the structural units M1 and M2. It is preferable.

The structural unit of the fluorine-containing ethylenic monomer is represented by the formula (4):

(Wherein X ¹⁵ and X ¹⁶ are H or F; X ¹⁷ is H, F, CF ₃ , CH ₃ ; X ¹⁸ is H, F, CF ₃ ; CX ¹⁴ ₂ may be C═O; h1, i1, j are 0 or 1; Z ² is H, F or Cl; Rf ⁵ is a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group containing an ether bond having 2 to 100 carbon atoms) Can be given.

Specifically, the following monomers can be exemplified.

(Iii) Aliphatic cyclic structural unit having fluorine When these structural units are introduced, the transparency can be increased, the refractive index can be lowered, and the fluoropolymer (I) having a high glass transition point. Is preferable in that a further increase in hardness can be expected from the cured product.

As the fluorine-containing aliphatic cyclic structural unit, the formula (5):

Wherein X ¹⁹ , X ²⁰ , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ are the same or different H or F; X ²¹ , X ²² are the same or different H, F, Cl or CF ₃ ; Rf ⁶ is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 10 carbon atoms; n2 is an integer of 0 to 3; n1, n3, n4 and n5 are the same or different and 0 or An integer of 1 is preferable.

Specifically, the following monomers can be exemplified.

(Iv) Structural units derived from ethylenic monomers that do not contain fluorine Introducing structural units derived from ethylenic monomers that do not contain fluorine to the extent that the refractive index is not deteriorated (higher refractive index). Also good.

This is preferable because the solubility in general-purpose solvents can be improved and the compatibility with additives such as photocatalysts and curing agents added as necessary can be improved.

Specifically, the following monomers can be exemplified.
α-olefins:
Vinyl ether or vinyl ester monomers such as ethylene, propylene, butene, vinyl chloride, vinylidene chloride:
Allyl monomers such as CH ₂ = CHOR, CH ₂ = CHOCOR (R: hydrocarbon group having 1 to 20 carbon atoms):
Allyl ether monomers such as CH ₂ = CHCH ₂ Cl, CH ₂ = CHCH ₂ OH, CH ₂ = CHCH ₂ COOH, CH ₂ = CHCH ₂ Br, etc .:

Acrylic or methacrylic monomers such as:
In addition to acrylic acid, methacrylic acid, acrylic esters and methacrylic esters, maleic anhydride, maleic acid, maleic esters and the like can be mentioned.

(V) Structural unit derived from alicyclic monomer As further copolymerization component, more preferably structural units M1 and M2 and the above-mentioned fluorine-containing ethylenic monomer or non-fluorine ethylenic monomer (described above) In addition to the structural units of (iii) and (iv)), an alicyclic monomer structural unit may be introduced as the third component, which is preferable because a high glass transition point and high hardness can be achieved. .

Specific examples of alicyclic monomers include

A norbornene derivative represented by (m: 0 to 3, A, B, C, D is H, F, Cl, COOH, CH ₂ OH, perfluoroalkyl having 1 to 5 carbon atoms, etc.)

And alicyclic monomers such as these, and derivatives obtained by introducing substituents into these.

In the fluoropolymer (I), the combination and composition ratio of the structural units M1 and M2 and N are determined from the above examples, the intended use, physical properties (particularly glass transition point, hardness, etc.), function (transparency, refractive index). ) And the like.

The fluoropolymer (I) used in the present invention contains the structural unit M1 as an essential component, and the structural unit M1 itself maintains a low refractive index and is hardened to a cured product by a function and curing to impart transparency. In addition, it has the feature of having a function that can impart solvent resistance. Therefore, the fluoropolymer (I) can maintain a low refractive index even if it is a polymer comprising a large amount of the structural unit M1 and extremely composed of only the structural unit M1 (100 mol%). At the same time, a cured product having a high cured (crosslinked) density is obtained, which is preferable in that a high-hardness film can be obtained.

Furthermore, in the case of a copolymer comprising the structural unit N of a monomer copolymerizable with the structural units M1 and M2 of the present invention, by selecting the structural unit N from the above-mentioned examples, a higher hardness (higher Glass transition point) and a polymer that gives a cured product having a low refractive index.

In the copolymer of the structural unit M1 and the structural units M2 and N, the content ratio of the structural unit M1 may be 0.1 mol% or more with respect to all monomers constituting the fluoropolymer (I). However, in order to obtain a cured product having high hardness, excellent wear resistance and scratch resistance by curing (crosslinking), and excellent chemical resistance and solvent resistance, it is 2.0 mol% or more, preferably 5 mol% or more. More preferably, the content is 10 mol% or more. In particular, in the use of an antireflection film that requires the formation of a cured film having excellent scratch resistance and scratch resistance, it is preferably contained in an amount of 10 mol% or more, preferably 20 mol% or more, and more preferably 50 mol% or more.

The fluoropolymer (I) is particularly preferable for use in an antireflection film because the antireflection effect does not decrease even if the proportion of the structural unit M1 is increased (even if the curing site is increased).

Further, when transparency is required, such as for use in an antireflection film, a fluorine-containing polymer having a combination and composition in which the combination of the structural unit M1 and the structural units M2 and N can be amorphous is preferable.

The molecular weight of the fluoropolymer (I) can be selected, for example, from the range of 500 to 1000000 in terms of the number average molecular weight, but is preferably selected from the range of 1000 to 500000, particularly 2000 to 200000.

If the molecular weight is too low, mechanical properties are likely to be insufficient even after curing, and in particular, the cured product and the cured film tend to be brittle and insufficient in strength. If the molecular weight is too high, the solvent solubility is deteriorated, the film forming property and leveling property are liable to be deteriorated particularly during the formation of the thin film, and the storage stability of the fluoropolymer (I) is liable to be unstable. As the coating application, the number average molecular weight is most preferably selected from the range of 5000 to 100,000.

The refractive index of the fluoropolymer (I) can be variously determined depending on the type of the structural unit M1, the content, and the type of the copolymer structural unit M2 or N used as necessary, but the fluoropolymer (I) ( The refractive index before curing is preferably 1.45 or less, more preferably 1.40 or less, and particularly preferably 1.38 or less. Although it changes depending on the type of the base material or the base, it can be preferable as a base polymer for an antireflection film by maintaining these low refractive indexes and allowing curing (crosslinking).

The curable resin composition of the present invention using such a novel fluoropolymer (I) is
(A) A film-forming material containing a fluoropolymer (Ia), and (B) an active energy ray curing initiator.

The effect of the fluoropolymer (I) as the film forming material (A) in the curable resin composition of the present invention is as described above.

In the present invention, the film forming material (A) is further represented by the formula (II):
-(M3)-(N1)-(II)
(Wherein M3 is the formula (2):

As such a fluorine-containing polymer (II) having a fluoroether chain having an ethylenic carbon-carbon double bond at its terminal in the side chain, for example, a polymer described in WO 02/18457 can be preferably used. .

As a preferable specific example of the monomer that gives the structural unit M3,

For more details,

Etc.

Among these, as the fluorine-containing polymer (II), the following are preferable from the viewpoint of good refractive index, transparency, solvent solubility, and film formability.

Examples of the structural unit N1 include those exemplified as the structural unit N of the fluoropolymer (I), including preferred ones.

The mixing ratio ((I) / (II) mass ratio) of the fluoropolymer (I) and the fluoropolymer (II) in the film-forming material (A) is 100/0 to 10/90. The refractive index and the hardness are preferable from the viewpoint of goodness, and from the viewpoint of improving the hardness, 100/0 to 30/70, more preferably 100/0 to 40/60 are preferable.

The active energy ray curing initiator (B) which is the other component of the curable resin composition of the present invention will be described.

The active energy ray curing initiator (B), for example, generates radicals and cations only when irradiated with electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X rays, γ rays, and the like. It functions as a catalyst for initiating the curing (crosslinking reaction) of the carbon-carbon double bond of the polymer. Usually, those that generate radicals and cations with ultraviolet light, particularly those that generate radicals are used.

According to this curable fluorine-containing resin composition, a curing reaction can be easily started by the active energy ray, and there is no need for heating at a high temperature, and a curing reaction is possible at a relatively low temperature. This is preferable in that it can be applied to a base material that is easily deformed, decomposed or colored by heat, such as a transparent resin base material.

The active energy ray curing initiator (B) in the composition of the present invention comprises the type of carbon-carbon double bond (radical) in the side chain in the fluoropolymer (I) or (II) of the film-forming material (A). Reactive or cationic reactive), the type of active energy ray to be used (wavelength range, etc.) and irradiation intensity, etc., are selected as appropriate, but generally radical reactive carbon-carbon using active energy rays in the ultraviolet region Examples of the initiator for curing the fluorine-containing polymers (I) and (II) having a double bond include the following.

Acetophenone acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, etc.
Benzoin benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.
Benzophenone benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone, etc.
Thioxanthones Thioxanthone, Chlorothioxanthone, Methylthioxanthone, Diethylthioxanthone, Dimethylthioxanthone, etc.
Others such as benzyl, α-acyl oxime ester, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, anthraquinone, etc. If necessary, light from amines, sulfones, sulfines, etc. An initiation aid may be added.

As the initiator for curing the fluoropolymers (I) and (II) having a cation-reactive carbon-carbon double bond, the following can be exemplified.

Onium salt iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt, etc.
Sulfone compounds β-ketoester, β-sulfonylsulfone and their α-diazo compounds, etc.
Sulfonic acid esters Alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, etc.
Other sulfonimide compounds, diazomethane compounds, etc.

Another embodiment of the curable resin composition of the present invention is an embodiment in which the solvent (C) is used, and various substrates can be coated by dissolving or dispersing in the solvent (C) to form a coating film. It is preferable in that it can be efficiently cured by irradiation with active energy rays after the coating film is formed, and a cured film can be obtained.

The solvent (C) is a material in which the film-forming material (A), the active energy ray curing initiator (B), and additives such as a curing agent, leveling agent, and light stabilizer that are added as necessary are uniformly dissolved or dispersed. If it is, there will be no restriction | limiting in particular, Especially the thing which melt | dissolves a film forming material (A) uniformly is preferable. The mode of using the solvent (C) is particularly preferable in the field where a thin layer coating (around 0.1 μm) is required such as an antireflection coating, and is highly transparent and can obtain a uniform coating with good productivity.

Examples of the solvent (C) include cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate , Ester solvents such as amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol solvents such as teracetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; ketone solvents such as 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; methanol, ethanol, propanol, isopropanol, butanol, etc. Examples of the alcohol solvent include aromatic hydrocarbons such as toluene and xylene, or a mixed solvent of two or more of these.

Furthermore, in order to improve the solubility of the film forming material (A), a fluorine-based solvent may be used as necessary.

Examples of the fluorine-based solvent include CH ₃ CCl ₂ F (HCFC-141b), CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF mixture (HCFC-225), perfluorohexane, perfluoro (2-butyltetrahydrofuran). , Methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, etc.

Fluorine alcohols such as
Examples thereof include benzotrifluoride, perfluorobenzene, perfluoro (tributylamine), ClCF ₂ CFClCF ₂ CFCl _{2 and the} like.

These fluorinated solvents may be used alone or as a mixed solvent of fluorinated solvents with each other, or one or more of non-fluorinated and fluorinated solvents.

Of these, ketone solvents, acetate solvents, alcohol solvents, aromatic solvents and the like are preferable in terms of paintability and coating productivity.

A curing agent may be further added to the curable resin composition of the present invention as necessary.

As the curing agent, those having at least one carbon-carbon unsaturated bond and capable of being polymerized with radicals or acids are preferable. Specifically, radically polymerizable monomers such as acrylic monomers, vinyl ether monomers and the like are used. And cationically polymerizable monomers. These monomers may be monofunctional having one carbon-carbon double bond or polyfunctional monomers having two or more carbon-carbon double bonds.

These so-called curing agents having a carbon-carbon unsaturated bond react with radicals and cations generated by the reaction of the active energy ray curing initiator (B) in the composition of the present invention with active energy rays such as light, The fluoropolymers (I) and (II) in the composition of the present invention can be cross-linked by copolymerization with the carbon-carbon double bond in the side chain.

Monofunctional acrylic monomers include acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, α-fluoroacrylic acid, α-fluoroacrylic esters, maleic acid, maleic anhydride, maleic acid In addition to esters, (meth) acrylic acid esters having an epoxy group, a hydroxyl group, a carboxyl group, and the like are exemplified.

Among them, in order to keep the refractive index of the cured product low, an acrylate monomer having a fluoroalkyl group is preferable.

A compound represented by (X is H, CH ₃ or F, and Rf is a fluorine-containing alkyl group having 2 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms) is preferable.

In particular,

Etc.

As polyfunctional acrylic monomers, compounds in which the hydroxyl groups of polyhydric alcohols such as diols, triols, and tetraols are replaced with acrylate groups, methacrylate groups, or α-fluoroacrylate groups are generally known. .

Specifically, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol, neopetyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Examples thereof include compounds in which two or more hydroxyl groups of polyhydric alcohols are replaced with acrylate groups, methacrylate groups or α-fluoroacrylate groups.

In addition, a polyfunctional acrylic monomer in which two or more hydroxyl groups of a polyhydric alcohol having a fluorine-containing alkyl group or a fluorine-containing alkylene group are replaced with an acrylate group, a methacrylate group, or an α-fluoroacrylate group can be used. This is particularly preferable in that the refractive index of the cured product can be kept low.

As a specific example

Preferred are those having a structure in which two or more hydroxyl groups of fluorine-containing polyhydric alcohols represented by general formulas such as are replaced with acrylate groups, methacrylate groups or α-fluoroacrylate groups.

In addition, when these exemplified monofunctional and polyfunctional acrylic monomers are used in the composition of the present invention as a curing agent, an α-fluoroacrylate compound is particularly preferable in terms of good curing reactivity.

In the composition of the present invention, the amount of the active energy ray curing initiator (B) added is the content of the carbon-carbon double bond in the fluoropolymers (I) and (II), and the use of the curing agent. Depending on the presence / absence and amount of curing agent used, as well as the initiator used, the type of active energy rays, and the amount of irradiation energy (strength and time, etc.), the fluoropolymer is used when no curing agent is used. (I) + (II) 0.01 to 30 parts by mass, further 0.05 to 20 parts by mass, and most preferably 0.1 to 10 parts by mass with respect to 100 parts by mass.

Specifically, it is 0.05 to 50 mol%, preferably 0.1 to 20 mol, based on the content (number of moles) of the carbon-carbon double bond contained in the fluoropolymers (I) and (II). %, Most preferably 0.5 to 10 mol%.

When a curing agent is used, the content of carbon-carbon double bonds (in moles) contained in the fluoropolymers (I) and (II) and the number of moles of carbon-carbon unsaturated bonds in the curing agent. It is 0.05 to 50 mol%, preferably 0.1 to 20 mol%, most preferably 0.5 to 10 mol%, based on the total number of moles.

The content of the solvent (C) in the curable resin composition of the present invention depends on the type of solid content to be dissolved, the presence or absence of use of a curing agent, the use ratio, the type of substrate to be applied, the target film thickness, etc. It is selected as appropriate, but it is preferably blended so that the total solid content in the composition is 0.5 to 70% by mass, preferably 1 to 50% by mass.

The composition of the present invention may contain various additives as necessary in addition to the above-mentioned compounds.

Examples of such additives include leveling agents, viscosity modifiers, light stabilizers, moisture absorbers, pigments, dyes, and reinforcing agents.

The composition of the present invention can also contain inorganic compound fine particles for the purpose of increasing the hardness of the cured product.

The inorganic compound fine particles are not particularly limited, but compounds having a refractive index of 1.5 or less are preferable. Specifically, magnesium fluoride (refractive index 1.38), silicon oxide (refractive index 1.46), aluminum fluoride (refractive index 1.33-1.39), calcium fluoride (refractive index 1.44) Fine particles such as lithium fluoride (refractive index 1.36 to 1.37), sodium fluoride (refractive index 1.32 to 1.34), thorium fluoride (refractive index 1.45 to 1.50) are desirable. . The particle diameter of the fine particles is desirably sufficiently smaller than the wavelength of visible light in order to ensure the transparency of the low refractive index material. Specifically, it is preferably 100 nm or less, particularly 50 nm or less.

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

In the curable resin composition of the present invention, the film-forming material (A) or the additive may be a dispersion or solution in the solvent (C), but in order to form a uniform thin film, Moreover, it is preferable that it is a uniform solution at the point which can form into a film at comparatively low temperature.

As the coating method, a known coating method can be adopted as long as the film thickness can be controlled.

For example, roll coating method, gravure coating method, micro gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method, dip coating method, etc. can be adopted. Can be selected considering the controllability and controllability of the film thickness.

The film obtained by applying the curable resin composition of the present invention to a substrate and then drying can be photocured by irradiating active energy rays such as ultraviolet rays, electron beams or radiation.

When photocured, the carbon-carbon double bonds in the fluoropolymers (I) and (II) are polymerized between molecules, and the carbon-carbon double bonds in the polymer are reduced or eliminated. As a result, the resin hardness is increased, the mechanical strength is improved, the wear resistance, the scratch resistance is improved, and further, the resin becomes insoluble in the solvent dissolved before curing, It becomes insoluble in many other types of solvents.

The present invention also relates to an antireflection film obtained by curing the curable resin composition of the present invention.

The antireflection film of the present invention has a carbon-carbon unsaturated bond that can be cured (crosslinked) in the fluoropolymers (I) and (II) itself, and has a low refractive index by itself. Completed based on the knowledge of the present inventors that an antireflection film having an antireflection effect and high hardness, wear resistance, and scratch resistance can be obtained by applying and curing a transparent substrate with a predetermined film thickness. It has been done. When such a fluoropolymer (I) is used, the paintability (smoothness, film thickness uniformity) is also good, and the monomer component having a low molecular weight hardly remains in the cured film. It is excellent in coating film performance without any tackiness.

Curing can take measures such as heat and light (in a system containing an initiator), but when an antireflection film is applied to a transparent resin substrate, applying a high temperature may cause thermal degradation or thermal deformation of the substrate. It is not preferable because it is easy to cause. Accordingly, curing by photocuring is preferable, and the fluoropolymer used in the present invention is preferably a carbon-carbon unsaturated bond capable of photocuring (for example, photopolymerization).

As a method for obtaining the antireflection film of the present invention, a curable resin composition containing a film forming material (A), an active energy ray curing initiator (B) and a solvent (C) is prepared, applied to a substrate, After forming a coating (uncured) by drying, etc., a method of obtaining a cured coating by irradiating active energy rays such as ultraviolet rays, electron beams, radiation, etc. is adopted. Light irradiation is inactive in air, nitrogen, etc. It may be performed under any conditions under a gas stream.

Further, the fluoropolymers (I) and (II) having an acid-polymerizable carbon-carbon double bond can be used in combination with an initiator that generates an acid upon irradiation with active energy rays. In that case, it is less affected by air (oxygen) at the time of light irradiation, which is preferable in that a curing reaction can be achieved.

The antireflective film of the present invention has a refractive index of 1.49 or less, preferably 1.45 or less, and more preferably 1.40 or less. Most preferably, it is 1.38 or less, and the lower one is more advantageous as an antireflection effect.

The preferred film thickness of the antireflection film applied to various substrates varies depending on the refractive index of the film and the refractive index of the base, but is selected from the range of 0.03 to 0.5 μm, preferably 0.07 to 0.2 μm. More preferably, the thickness is 0.08 to 0.12 μm. If the film thickness is too low, the reduction in reflectance due to light interference in visible light will be insufficient, and if it is too high, the reflectance will depend only on the reflection at the interface between the air and the film. There is a tendency that the reduction of the reflectance due to is insufficient. In particular, it is preferable to set the film thickness so that the wavelength that indicates the minimum reflectance of the article after the antireflection film is applied is usually 420 to 720 nm, preferably 520 to 620 nm.

The antireflection film of the present invention can be applied to various substrate surfaces to provide an antireflection treatment article.

The article to which the antireflection film of the present invention is applied, that is, the type of the substrate is not particularly limited. For example, inorganic materials such as glass, stone, concrete, tile; cellulose resins such as vinyl chloride resin, polyethylene terephthalate, triacetyl cellulose, polycarbonate resin, polyolefin resin, acrylic resin, phenol resin, xylene resin, urea resin, melamine Synthetic resins such as resin, diallyl phthalate resin, furan resin, amino resin, alkyd resin, urethane resin, vinyl ester resin, polyimide resin; metal such as iron, aluminum, copper; wood, paper, printed matter, photographic paper, painting, etc. I can give you. In addition, the decorativeness of the article can be improved by applying an antireflection film to a part other than the specific part of the article and causing the shape of the specific part to be raised by reflected light.

Among the base materials, it is preferably applied to transparent resin base materials such as acrylic resin, polycarbonate, cellulose resin, polyethylene terephthalate, and polyolefin resin, and can effectively exhibit antireflection effect.

The present invention is effective when applied to an article having the following form.
Optical components such as prisms, lens sheets, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, rear projection display screens, optical fibers and optical couplers;
Transparent protective plates such as show window glass, showcase glass, advertising covers, photo stand covers, etc .;
Protection plates such as CRT, liquid crystal display, plasma display, rear projection display;
Optical recording media represented by magneto-optical disks, read-only optical disks such as CD / LD / DVD, phase transition optical disks such as PD, hologram recording, etc .;
Photolithography-related members during semiconductor manufacturing, such as photoresists, photomasks, pellicles, and reticles;
Protective covers for illuminants such as halogen lamps, fluorescent lamps and incandescent lamps;
A sheet or film for attaching to the article.

The antireflection film of the present invention may be formed by directly applying the curable resin composition of the present invention to a substrate and irradiating with light to form a cured film having a thickness of about 0.1 μm. One or a plurality of layers may be formed as an undercoat, and an antireflection film may be formed thereon as a topcoat.

The effect of the undercoat is roughly divided into three, and is to enhance the antireflection effect by increasing the scratch resistance of the topcoat, protecting the base material, and adding a layer having a higher refractive index than the base material. . In order to improve the scratch resistance of the top coat, a self-repairing undercoat as exemplified in JP-A-7-168005 may be used. Further, a paint generally called a hard coat may be used for protecting the substrate. Examples of the hard coat include curable acrylic resins and epoxy resins, cured products of silicon alkoxide compounds, and cured products of metal alkoxide compounds. The thermosetting method can be applied to all of these. For acrylic resins and epoxy resins, the light (ultraviolet) curing method is preferred in terms of productivity.

In a CRT or plasma display, static electricity tends to accumulate on the surface as a characteristic of the device. Therefore, it is preferable to mix an additive for imparting conductivity to the undercoat layer and / or the topcoat layer as described above. Examples of the additive include —COO—, —NH ₂ , —NH ₃ ⁺ , —NR ¹¹ R ¹² R ¹³ (where R ¹¹ , R ¹² and R ¹³ are, for example, methyl group, ethyl group, n-propyl group) , N-butyl group, etc.), polymers containing ionic groups such as —SO ₃ —, silicone compounds, inorganic electrolytes (eg NaF, CaF ₂ etc.) and the like.

In addition, for the purpose of preventing the adhesion of dust, it is preferable to add an antistatic agent to the undercoat layer and / or the topcoat layer of the antireflection film. Examples of additives include metal oxide fine particles, fluoroalkoxysilanes, surfactants (anionic, cationic, amphoteric, nonionic, etc.) in addition to the above-mentioned additives that impart conductivity.

As an antistatic agent added to the undercoat layer, the effect is permanent, the effect is not easily affected by humidity, the antistatic effect is high, the transparency and the refractive index are high, and the refractive index of the substrate is For the reason that the antireflection effect can be enhanced because it can be adjusted, fine particles of metal oxide, specifically, antimony-doped tin oxide (ATO) and indium-containing tin oxide (ITO) are preferable. ATO is preferable in terms of transparency, and ITO is preferable in terms of antistatic effect or conductivity. Further, even when the antistatic effect is not required, the refractive index can be easily adjusted, so that the antireflection effect can be enhanced by using these additives.

In addition, since ATO and ITO easily scatter and absorb light, the thickness of the undercoat layer is preferably about submicron so as not to prevent light transmission. In order to reduce the wavelength dependence of the antireflection effect and enhance the antireflection effect over all wavelengths, the film thickness is 0.05 to 0, depending on the refractive index of the cured product of the curable resin composition of the present invention. .3 μm is preferred. The optimum refractive index also depends on the refractive index of the curable resin composition of the present invention, but is preferably 1.55 to 1.95.

If the antireflection film is provided with antistatic properties, an alkoxysilane-based antistatic agent is preferable from the viewpoint that the refractive index is difficult to increase and the antireflection effect is less adversely affected. Fluoroalkoxysilane is more preferable because the action of increasing the refractive index is further reduced and the effect of improving the surface characteristics can be expected.

Further, as a method completely different from the method of modifying a part of the film as described above, a surfactant having a film thickness that does not adversely affect the antireflection performance as disclosed in JP-A-8-142280. There is a method of forming the layer. When applied to the present invention, there is an effect of improving antifouling properties such as prevention of dust adhesion. The same effect can be obtained when a hard coat layer is formed.

The hard coat layer can be formed by applying a solution of alkoxysilane or polysilazane, followed by heating and curing. Further, an ultraviolet curable acrylic paint or a cured film of melamine crosslinking can be used.

The antireflection film of the present invention has a high fluorine content and a low surface contact angle, and itself has water repellency, non-adhesiveness, and antifouling properties, and can have both antireflection and antifouling layers. .

Furthermore, a fluorine-containing polyether compound can be added to impart antifouling properties to the antireflection layer. In that case, it is necessary to determine the addition amount in consideration of deterioration of mechanical properties and white turbidity due to phase separation from the film forming material (A). If the terminal is a carboxyl group, a blocked carboxyl group, a hydroxyl group, an epoxy group, an alkoxysilane group, a (meth) acryloyl group, or an α-fluoroacryloyl group, it is easily fixed in the film. The same effect can be obtained by applying the same polyether compound to the surface of the antireflection film formed in advance.

In the present invention, a silane compound may be added in order to improve the adhesion of the antireflection film to the substrate. The amount of the silane compound added to the film may be about several mass%. In addition, treating the substrate surface with a silane compound is also effective for improving adhesion. In any case in the present invention, since the silane compound hardly increases the refractive index of the cured film, the adverse effect on the antireflection effect is very small.

Next, the present invention will be described based on examples, but the present invention is not limited only to these examples.

The various physical properties of the present invention were measured by the following methods.

(1) NMR
NMR measuring device: manufactured by BRUKER
¹ H-NMR measurement conditions: 400 MHz (tetramethylsilane = 0 ppm)
¹⁹ F-NMR measurement conditions: 376 MHz (trichlorofluoromethane = 0 ppm)

(2) IR
Measured at room temperature with a Fourier transform infrared spectrophotometer 1760X manufactured by PERKIN ELMER.

(3) Number average (weight average) molecular weight:
By gel permeation chromatography (GPC), using GPC HLC-8020 manufactured by Tosoh Corporation, one column by Shodex (one GPC KF-801, one GPC KF-802, and two GPC KF-806M) This is calculated from data measured by flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min.

(4) Refractive index A refractive index is measured about the light of a wavelength of 550 nm at 25 degreeC using an Abbe refractometer.

(5) Total light transmittance, haze value Measured according to ASTM D1003 using a haze card II manufactured by Toyo Seiki Seisakusho.

(6) Reflectance The antireflection film with the back side shaved with steel wool and painted with black magic is set in a visible UV spectrometer equipped with a 5 ° specular reflection unit, and the average reflectance (%) and minimum reflectance (%) Is measured. U-4000 / SPECTROMETER manufactured by Hitachi High-Technology Co., Ltd. is used for the measurement.

(7) Pencil hardness Measured according to JIS K5400.

Synthesis Example 1 (Synthesis of homopolymer of 1,1,1-trifluoro-2-trifluoromethyl-2-hydroxypropyl ester of α-fluoroacrylic acid)
A 50 ml three-necked flask equipped with a nitrogen inlet tube, vacuum line, thermometer, septum rubber cap and stirrer chip was dried and α-fluoroacrylic acid 1,1,1-trifluoro-2-trifluoromethyl- 2-hydroxypropyl ester:
CH ₂ = CFCOOCH ₂ C (CF ₃ ) ₂ OH
3.0 g (11 mmol) and 15 ml of THF were added and cooled in a dry ice-acetone bath. After adding 60 mg (0.4 mmol) of azoisobutyronitrile (AIBN), deoxygenation was performed under reduced pressure while stirring. After replacing with nitrogen, the mixture was heated to 70 ° C. in a water bath and stirred for 3 hours. After returning to room temperature and stirring for 20 hours, the reaction mixture was added to 300 ml of n-hexane with stirring, and the desired fluoropolymer (Ia) was obtained by reprecipitation. Yield 2.7 g (90% yield).

This polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis. As a result, it was a fluoropolymer having only a structural unit of the α-fluoroacrylate ester and having a hydroxyl group at the side chain end. . The number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 5746, and the weight average molecular weight was 7706.

Synthesis Example 2 (Synthesis of fluoropolymer (I-1))
In a 50 ml three-necked flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel, 5.0 ml of methyl isobutyl ketone (MIBK), 1.0 g of the homopolymer of the fluoropolymer obtained in Synthesis Example 1, and pyridine 320 mg was charged and ice-cooled to 5 ° C. or lower.

While stirring under a nitrogen stream, a solution of 170 mg of α-fluoroacrylic acid fluoride: CH ₂ ═CFCOF dissolved in 0.5 ml of methyl isobutyl ketone was added dropwise.

After completion of dropping, the temperature was raised to room temperature and stirring was continued for 12 hours.

After the reaction, the MIBK solution was put into a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water, and then dried over anhydrous magnesium sulfate, and then the MIBK solution was separated by filtration.

When this MIBK solution was examined by ¹⁹ F-NMR analysis, it was found that a fluorine-containing polymer containing 40 mol% of a unit having a terminal —C (═O) CF═CH ₂ and 60 mol% of a unit having a terminal hydroxyl group ( I-1) was confirmed. The number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 6144, and the weight average molecular weight was 8397.

The refractive index of this fluoropolymer (I-1) was 1.37.

Synthesis Example 3 (Synthesis of fluoropolymer (I-2))
A fluoropolymer (MIBK solution) was synthesized in the same manner as in Synthesis Example 2 except that 250 mg of α-fluoroacrylic acid fluoride: CH ₂ ═CFCOF was used.

^{According to 19} F-NMR, it was found to be a fluoropolymer (I-2) containing 50 mol% of units having —C (═O) CF═CH ₂ at the end and 50 mol% of units having a terminal hydroxyl group. confirmed. The number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 6213, and the weight average molecular weight was 8504.

The refractive index of this fluoropolymer (I-2) was 1.37.

Synthesis Example 4 (Synthesis of fluoropolymer (I-3))
A fluoropolymer (MIBK solution) was synthesized in the same manner as in Synthesis Example 2 except that 50 mg of α-fluoroacrylic acid fluoride: CH ₂ ═CFCOF was used.

^{By 19} F-NMR, it was confirmed that the fluorine-containing polymer (I-3) contained 10 mol% of units having —C (═O) CF═CH ₂ at the end and 90 mol% of units having a terminal hydroxyl group. confirmed. The number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 5115, and the weight average molecular weight was 8080.

The refractive index of this fluoropolymer (I-3) was 1.36.

Synthesis Example 5 (Synthesis of fluoropolymer (I-4))
A fluoropolymer (MIBK solution) was synthesized in the same manner as in Synthesis Example 2 except that 350 mg of α-fluoroacrylic acid fluoride: CH ₂ ═CFCOF was used.

^{By 19} F-NMR, it was confirmed that the fluorine-containing polymer (I-4) contained 70 mol% of the unit having —C (═O) CF═CH ₂ at the end and 30 mol% of the unit having the terminal hydroxyl group. confirmed. The number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 6430, and the weight average molecular weight was 8,900.

The refractive index of this fluoropolymer (I-4) was 1.38.

Synthesis Example 6 (Synthesis of fluoroether-containing fluoropolymer (II-1))
In a 100 ml glass four-necked flask equipped with a stirrer and a thermometer, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) was added.

20.4g

After adding 21.2 g of the 8.0 wt% perfluorohexane solution and sufficiently purging with nitrogen, the mixture was stirred at 20 ° C. for 24 hours under a nitrogen stream to produce a highly viscous solid.

A solution obtained by dissolving the obtained solid in diethyl ether was poured into perfluorohexane, separated and vacuum dried to obtain 17.6 g of a colorless and transparent polymer.

This polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis. As a result, it was a fluorine-containing polymer comprising only the structural unit of the fluorine-containing allyl ether and having a hydroxyl group at the side chain end. The number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 9000, and the weight average molecular weight was 22,000.

Into a 200 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel, 80 ml of MIBK, 5.0 g of the hydroxyl group-containing fluorine-containing allyl ether homopolymer obtained above and 1.0 g of pyridine were charged. Ice-cooled to 5 ° C or lower.

While stirring under a nitrogen stream, 1.0 g of α-fluoroacrylic acid fluoride: CH ₂ ═CFCOF dissolved in 20 ml of diethyl ether was added dropwise over about 30 minutes.

After completion of dropping, the temperature was raised to room temperature and stirring was continued for 4.0 hours.

After the reaction, the MIBK solution was placed in a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water, dried over anhydrous magnesium sulfate, and then separated by filtration.

When this MIBK solution was examined by ¹⁹ F-NMR analysis, it was found to contain 40 mol% of allyl ether units whose terminal is —C (═O) CF═CH ₂ and 60 mol% of allyl ether units whose terminal is a hydroxyl group. It was confirmed to be a fluoropolymer (II-1).

Example 1
(1) Preparation of curable resin composition After measuring the solid content of the MIBK solution of the fluoropolymer (I-1) having an α-fluoroacryloyl group obtained in Synthesis Example 2 by loss on drying, it is diluted with MIBK. As a result, the polymer concentration was adjusted to 15% by mass.

0.75 parts by mass of Irgacure 127 (manufactured by Ciba Japan Co., Ltd.) is added as an active energy ray curing initiator to 100 parts by mass of the polymer, and the curable resin of the present invention is added. A composition was obtained.

(2) Preparation of antireflection film The obtained curable resin composition was coated on untreated triacetylcellulose (TAC) with a bar coater (# 7) at room temperature and dried at 70 ° C for 1 minute. At this time, the film thickness after drying was adjusted to 100 nm.

A high-pressure mercury lamp was used for the dried film, and ultraviolet light was irradiated at room temperature with an intensity of 1 J / cm ² for photocuring to produce an antireflection film.

The obtained antireflection film (cured film) was examined for refractive index, total light transmittance, haze value, average visibility reflectance, minimum reflectance, and pencil hardness. The results are shown in Table 1.

Example 2
A curable resin composition was obtained in the same manner as in Example 1 except that the fluoropolymer (I-2) having an α-fluoroacryloyl group obtained in Synthesis Example 3 was used in place of the fluoropolymer (I-1). The preparation of the product, the production of the antireflection film, and the evaluation of the characteristics were performed. The results are shown in Table 1.

Example 3
A curable resin composition was obtained in the same manner as in Example 1 except that the fluoropolymer (I-4) having an α-fluoroacryloyl group obtained in Synthesis Example 5 was used in place of the fluoropolymer (I-1). The preparation of the product, the production of the antireflection film, and the evaluation of the characteristics were performed. The results are shown in Table 1.

Comparative Example 1
Instead of the fluoropolymer (I-1), the same procedure as in Example 1 was used except that the fluoroether-containing fluoropolymer (II-1) having an α-fluoroacryloyl group obtained in Synthesis Example 6 was used. Preparation of a curable resin composition, production of an antireflection film, and evaluation of properties were performed. The results are shown in Table 1.

Example 4
(1) Preparation of curable resin composition After measuring the solid content of the MIBK solution of the fluoropolymer (I-1) having an α-fluoroacryloyl group obtained in Synthesis Example 2 by loss on drying, it is diluted with MIBK. As a result, the polymer concentration was adjusted to 15% by mass.

0.75 parts by mass of Irgacure 127 (manufactured by Ciba Japan Co., Ltd.) as an active energy ray curing initiator and dipentaerythritol hexaacrylate as a curing agent with respect to 100 parts by mass of the polymer in the obtained polymer solution. 3 parts by mass of (A-DPH) was added to obtain a curable resin composition of the present invention.

(2) Production of antireflection film The obtained curable resin composition was coated on untreated TAC by a bar coater (# 7) at room temperature and dried at 70 ° C for 1 minute. At this time, the film thickness after drying was adjusted to 100 nm.

The obtained antireflection film (cured film) was examined for refractive index, total light transmittance, haze value, average visibility reflectance, minimum reflectance, and pencil hardness. The results are shown in Table 2.

Example 5
A curable resin composition was obtained in the same manner as in Example 4 except that the fluoropolymer (I-2) having an α-fluoroacryloyl group obtained in Synthesis Example 3 was used in place of the fluoropolymer (I-1). The preparation of the product, the production of the antireflection film, and the evaluation of the characteristics were performed. The results are shown in Table 2.

Example 6
The curable resin composition was the same as in Example 4 except that the fluoropolymer (I-4) having an α-fluoroacryloyl group obtained in Synthesis Example 5 was used in place of the fluoropolymer (I-1). The preparation of the product, the production of the antireflection film and the evaluation of the characteristics were performed. The results are shown in Table 2.

Comparative Example 2
Curability was the same as in Example 4 except that the fluoroether-containing fluoropolymer (II-1) having an α-fluoroacryloyl group obtained in Synthesis Example 6 was used instead of the fluoropolymer (I). Preparation of a resin composition, production of an antireflection film, and evaluation of properties were performed. The results are shown in Table 2.

From the results in Tables 1 and 2, it can be seen that it is possible to provide a curable resin composition and an antireflection film that can achieve high hardness while maintaining a low refractive index.

Claims

Formula (I):
-(M1)-(M2)-(N)-(I)
(Wherein M1 is a formula (1-1):

A structural unit represented by
M2 is a formula (1-2):

A structural unit represented by
N is a structural unit derived from a monomer copolymerizable with a monomer giving M1 and M2, and the structural unit M1 is 0.1 to 100 mol% and the structural unit M2 is 0 to 99.9 mol % And a structural unit N of 0 to 99.9 mol%, and a number average molecular weight of 500 to 1,000,000.
(A) Formula (I):
-(M1)-(M2)-(N)-(I)
(Wherein M1 is a formula (1-1):

A structural unit represented by
M2 is a formula (1-2):

A structural unit represented by
N is a structural unit derived from a monomer copolymerizable with a monomer giving M1 and M2, and the structural unit M1 is 0.1 to 100 mol% and the structural unit M2 is 0 to 99.9 mol % And a structural unit N of 0 to 99.9 mol%, a film-forming material containing a fluorine-containing polymer (I) having a number average molecular weight of 500 to 1,000,000, and (B) curing containing an active energy ray curing initiator Resin composition.
The film forming material (A) is further represented by the formula (II):
-(M3)-(N1)-(II)
(Wherein M3 is the formula (2):

(Wherein, Rf is ethylenic carbon Y 1 (Y 1 is terminated in the fluorine-containing alkyl group having ether bond of the fluorine-containing alkyl group or a 2 to 100 carbon atoms having 1 to 40 carbon atoms - carbon double bonds A structural unit represented by an organic group in which 1 to 3 monovalent organic groups having 2 to 10 carbon atoms are bonded, and a structure derived from a monomer copolymerizable with a monomer that gives M3 Unit)
The curability according to claim 2, comprising a fluoropolymer (II) containing 0.1 to 100 mol% of the structural unit M3, 0 to 99.9 mol% of the structural unit N1 and having a number average molecular weight of 500 to 1000000. Resin composition.
The curable resin composition of Claim 2 or 3 containing a solvent (C).
An antireflection film obtained by photocuring the curable resin composition according to any one of claims 2 to 4.