WO2010055758A1 - Polymère à base de fluor, composition de résine durcissable constituée du polymère à base de fluor, et film antireflet - Google Patents

Polymère à base de fluor, composition de résine durcissable constituée du polymère à base de fluor, et film antireflet Download PDF

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Publication number
WO2010055758A1
WO2010055758A1 PCT/JP2009/068247 JP2009068247W WO2010055758A1 WO 2010055758 A1 WO2010055758 A1 WO 2010055758A1 JP 2009068247 W JP2009068247 W JP 2009068247W WO 2010055758 A1 WO2010055758 A1 WO 2010055758A1
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structural unit
fluorine
mol
formula
resin composition
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PCT/JP2009/068247
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English (en)
Japanese (ja)
Inventor
恒雄 山下
洋介 岸川
知弘 吉田
正道 森田
義人 田中
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ダイキン工業株式会社
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Priority to JP2010537744A priority Critical patent/JP5556665B2/ja
Publication of WO2010055758A1 publication Critical patent/WO2010055758A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials

Definitions

  • 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.
  • an antireflection film made of a low refractive material is coated on the substrate of the display device.
  • 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.
  • 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.
  • Patent Document 1 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).
  • 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.
  • 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.
  • 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.
  • Rf is ethylenic carbon Y 1 (Y 1 is terminated
  • 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.
  • 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.
  • the fluorinated polymer (I) 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.
  • the formula (1-2a) Fluoropolymer obtained by polymerizing 0.1 to 100 mol of hexafluoroalcohol ester of ⁇ -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 ⁇ -fluoroacrylic acid (CH 2 ⁇ CFCOOH) or its acid halide.
  • the proportion of M1 in the fluoropolymer (I) is determined by the reaction amount of ⁇ -fluoroacrylic acid.
  • 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%.
  • the structural unit M2 can be introduced by copolymerizing a hexafluoroalcohol ester (m2) of ⁇ -fluoroacrylic acid.
  • 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 ⁇ -fluoroacrylic acid hexafluoroalcohol ester (m2).
  • m2 ⁇ -fluoroacrylic acid hexafluoroalcohol ester
  • the following monomers can be preferably exemplified.
  • 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).
  • (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.
  • 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.
  • (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)
  • 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. .
  • 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.
  • 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.
  • the content ratio of the structural unit M1 may be 0.1 mol% or more with respect to all monomers constituting the fluoropolymer (I).
  • the content ratio of the structural unit M1 may be 0.1 mol% or more with respect to all monomers constituting the fluoropolymer (I).
  • it is 2.0 mol% or more, preferably 5 mol% or more. More preferably, the content is 10 mol% or more.
  • 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).
  • 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.
  • 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 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.
  • Rf is ethylenic carbon Y 1 (Y 1 is terminated
  • 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.
  • 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, ⁇ 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.
  • 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.
  • Thioxanthones Thioxanthone, Chlorothioxanthone, Methylthioxanthone, Diethylthioxanthone, Dimethylthioxanthone, etc. Others such as benzyl, ⁇ -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.
  • the initiator for curing the fluoropolymers (I) and (II) having a cation-reactive carbon-carbon double bond the following can be exemplified.
  • 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
  • the mode of using the solvent (C) is particularly preferable in the field where a thin layer coating (around 0.1 ⁇ m) 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 monoeth
  • a fluorine-based solvent may be used as necessary.
  • fluorine-based solvent examples 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.
  • 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.
  • 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.
  • those having at least one carbon-carbon unsaturated bond and capable of being polymerized with radicals or acids are preferable.
  • radically polymerizable monomers such as acrylic monomers, vinyl ether monomers and the like are used.
  • cationically polymerizable monomers are used. These monomers may be monofunctional having one carbon-carbon double bond or polyfunctional monomers having two or more carbon-carbon double bonds.
  • 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, ⁇ -fluoroacrylic acid, ⁇ -fluoroacrylic esters, maleic acid, maleic anhydride, maleic acid
  • esters (meth) acrylic acid esters having an epoxy group, a hydroxyl group, a carboxyl group, and the like are exemplified.
  • an acrylate monomer having a fluoroalkyl group is preferable.
  • 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 ⁇ -fluoroacrylate groups are generally known. .
  • 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 ⁇ -fluoroacrylate groups.
  • 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 ⁇ -fluoroacrylate group can be used. This is particularly preferable in that the refractive index of the cured product can be kept low.
  • an ⁇ -fluoroacrylate compound is particularly preferable in terms of good curing reactivity.
  • 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.
  • the fluoropolymer is used when no curing agent is used.
  • 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%.
  • 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 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.
  • composition of the present invention may contain various additives as necessary in addition to the above-mentioned compounds.
  • additives examples include leveling agents, viscosity modifiers, light stabilizers, moisture absorbers, pigments, dyes, and reinforcing agents.
  • 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.
  • the surface of the inorganic fine particle compound may be modified in advance using various coupling agents.
  • 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.
  • 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.
  • the coating method a known coating method can be adopted as long as the film thickness can be controlled.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the paintability smoothness, film thickness uniformity
  • 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).
  • 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.
  • 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 ⁇ m, preferably 0.07 to 0.2 ⁇ m. More preferably, the thickness is 0.08 to 0.12 ⁇ m. 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 is not particularly limited.
  • 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.
  • 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.
  • 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.
  • transparent resin base materials such as acrylic resin, polycarbonate, cellulose resin, polyethylene terephthalate, and polyolefin resin
  • 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 ⁇ m.
  • 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. .
  • a self-repairing undercoat as exemplified in JP-A-7-168005 may be used.
  • a paint generally called a hard coat may be used for protecting the substrate.
  • 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.
  • acrylic resins and epoxy resins the light (ultraviolet) curing method is preferred in terms of productivity.
  • an additive for imparting conductivity to the undercoat layer and / or the topcoat layer as described above.
  • 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.
  • an antistatic agent 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.
  • additives include metal oxide fine particles, fluoroalkoxysilanes, surfactants (anionic, cationic, amphoteric, nonionic, etc.) in addition to the above-mentioned additives that impart conductivity.
  • 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
  • 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.
  • the refractive index can be easily adjusted, so that the antireflection effect can be enhanced by using these additives.
  • the thickness of the undercoat layer is preferably about submicron so as not to prevent light transmission.
  • 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 ⁇ m 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.
  • 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.
  • 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.
  • 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. .
  • a fluorine-containing polyether compound can be added to impart antifouling properties to the antireflection layer.
  • 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).
  • 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 ⁇ -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.
  • 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%.
  • treating the substrate surface with a silane compound is also effective for improving adhesion.
  • the silane compound since the silane compound hardly increases the refractive index of the cured film, the adverse effect on the antireflection effect is very small.
  • Refractive index A refractive index is measured about the light of a wavelength of 550 nm at 25 degreeC using an Abbe refractometer.
  • 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 ⁇ -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)
  • MIBK methyl isobutyl ketone
  • 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.
  • 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 ⁇ -fluoroacrylic acid fluoride: CH 2 ⁇ CFCOF was used.
  • 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 ⁇ -fluoroacrylic acid fluoride: CH 2 ⁇ CFCOF was used.
  • 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 ⁇ -fluoroacrylic acid fluoride: CH 2 ⁇ CFCOF was used.
  • 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.
  • 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.
  • 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.
  • Example 1 Preparation of curable resin composition After measuring the solid content of the MIBK solution of the fluoropolymer (I-1) having an ⁇ -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.
  • Irgacure 127 manufactured by Ciba Japan Co., Ltd.
  • Ciba Japan Co., Ltd. 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.
  • 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 ⁇ -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 ⁇ -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 ⁇ -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 Preparation of curable resin composition After measuring the solid content of the MIBK solution of the fluoropolymer (I-1) having an ⁇ -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.
  • 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 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 ⁇ -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 ⁇ -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 ⁇ -fluoroacryloyl group obtained in Synthesis Example 6 was used instead of the fluoropolymer (I).
  • the fluoroether-containing fluoropolymer (II-1) having an ⁇ -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.

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un nouveau polymère à base de fluor dont la dureté peut être augmentée, tout en maintenant un faible indice de réfraction. L'invention concerne également une composition de résine durcissable utilisant le polymère à base de fluor, et un film antireflet. Le polymère à base de fluor est représenté par la formule (I) : -(M1)-(M2)-(N)- (où M1 représente un motif structural représenté par la formule (1-1), M2 représente un motif structural représenté par la formule (1-2), et N représente un motif structural dérivé d'un monomère qui est copolymérisable avec les monomères qui fournissent respectivement M1 et M2). La composition de résine durcissable renferme un matériau filmogène contenant le polymère à base de fluor, et un initiateur de durcissement sous l'effet d'un rayonnement d'énergie active.
PCT/JP2009/068247 2008-11-13 2009-10-23 Polymère à base de fluor, composition de résine durcissable constituée du polymère à base de fluor, et film antireflet WO2010055758A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2012053453A1 (fr) * 2010-10-18 2012-04-26 ダイキン工業株式会社 Composition fluorée pour la réalisation d'une couche de revêtement isolante, couche isolante, et transistor en couches minces
JP2013205656A (ja) * 2012-03-28 2013-10-07 Asahi Kasei E-Materials Corp ペリクル枠体
WO2013181059A1 (fr) * 2012-06-01 2013-12-05 Qualcomm Mems Technologies, Inc. Guide de lumière pourvu de réflecteurs de fresnel
JP2014105271A (ja) * 2012-11-27 2014-06-09 Kyoeisha Chem Co Ltd 活性エネルギー線硬化型ハードコート用樹脂組成物、ハードコート被覆熱可塑性シート及び光学部材
JP2021110951A (ja) * 2020-01-08 2021-08-02 ダイキン工業株式会社 ディスプレイ保護膜

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WO2002018457A1 (fr) * 2000-08-29 2002-03-07 Daikin Industries, Ltd. Fluoropolymère durcissable, composition de résine durcissable le contenant, et film antireflet

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T. YAMASHITA ET AL.: "Synthesis of Novel a-Fluoroacrylates and Related Polymers for Immersion Lithography", JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY, vol. 21, no. 5, 1 July 2008 (2008-07-01), pages 673 - 677 *
T. YAMASHITA ET AL.: "Synthesis of novel a-fluoroacrylates and related polymers for immersion lithography", PROCEEDINGS OF SPIE (2008), 6923(PT. 1, ADVANCES IN RESIST MATERIALS AND PROCESSING TECHNOLOGY XXV), vol. 6923, no. 69231Z, 10 July 2008 (2008-07-10), pages 1 - 7 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012053453A1 (fr) * 2010-10-18 2012-04-26 ダイキン工業株式会社 Composition fluorée pour la réalisation d'une couche de revêtement isolante, couche isolante, et transistor en couches minces
JP2012109542A (ja) * 2010-10-18 2012-06-07 Daikin Ind Ltd 塗布型絶縁膜形成用含フッ素組成物、絶縁膜、及び薄膜トランジスタ
JP2013205656A (ja) * 2012-03-28 2013-10-07 Asahi Kasei E-Materials Corp ペリクル枠体
WO2013181059A1 (fr) * 2012-06-01 2013-12-05 Qualcomm Mems Technologies, Inc. Guide de lumière pourvu de réflecteurs de fresnel
CN104364684A (zh) * 2012-06-01 2015-02-18 高通Mems科技公司 具有嵌入式菲涅耳反射器的光导
JP2014105271A (ja) * 2012-11-27 2014-06-09 Kyoeisha Chem Co Ltd 活性エネルギー線硬化型ハードコート用樹脂組成物、ハードコート被覆熱可塑性シート及び光学部材
JP2021110951A (ja) * 2020-01-08 2021-08-02 ダイキン工業株式会社 ディスプレイ保護膜
JP7326358B2 (ja) 2020-01-08 2023-08-15 ダイキン工業株式会社 ディスプレイ保護膜

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