WO2007145288A1 - Composition de solution polymère contenant du fluor - Google Patents

Composition de solution polymère contenant du fluor Download PDF

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Publication number
WO2007145288A1
WO2007145288A1 PCT/JP2007/062031 JP2007062031W WO2007145288A1 WO 2007145288 A1 WO2007145288 A1 WO 2007145288A1 JP 2007062031 W JP2007062031 W JP 2007062031W WO 2007145288 A1 WO2007145288 A1 WO 2007145288A1
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group
fluorine
carbon atoms
atom
polymer
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PCT/JP2007/062031
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English (en)
Japanese (ja)
Inventor
Naoko Shirota
Shu-Zhong Wang
Osamu Yokokoji
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Asahi Glass Company, Limited
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Publication of WO2007145288A1 publication Critical patent/WO2007145288A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • 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

Definitions

  • the present invention relates to a fluoropolymer solution composition.
  • Patent Document As a polymerizable compound having a fluorine-containing polycyclic aliphatic hydrocarbon group, a compound having a polyfluoroadamantyl group (for example, a compound represented by the following formula) is known (Patent Document). See 1 and 2.)
  • a polymer containing a repeating unit formed by polymerization of the above compound has excellent light resistance and transparency against short-wavelength light, and therefore a photolithography method using F laser light as a light source.
  • Patent Document 3 describes a hydrocarbon solvent (ketones, esters, ethers or alcohols).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2006-131879
  • Patent Document 2 JP 2004-123687 A
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-182796
  • a polymer containing the repeating unit (particularly the repeating unit).
  • a polymer with a high content of repeat units. Did not form a stable polymer solution composition with low compatibility with the hydrocarbon solvent. Therefore, it was not easy to form the polymer thin film by applying the polymer solution composition onto a substrate and then drying it. Moreover, it was not easy to prepare a uniform polymer solution composition in which the polymer and other components were compatible.
  • an object of the present invention is to provide a specific material capable of imparting physical properties such as transparency, water / oil repellency (particularly dynamic water / oil repellency), heat resistance, mold releasability, and chemical resistance to the surface of a desired substrate. It is an object of the present invention to provide a stable fluorine-containing polymer solution composition containing a fluorine-containing organic solvent.
  • the present invention has the following gist.
  • Fluoropolymer solution composition comprising a fluorinated polymer (F) containing a repeating unit (A) having a fluorinated alicyclic saturated hydrocarbon group in the side chain, and a fluorinated organic solvent (S) .
  • the repeating unit (A) is selected from the following formula (1), formula (2), formula (3), formula (4) and formula (5) N-valent group obtained by removing n hydrogen atoms from one or more alicyclic saturated hydrocarbon compounds (where n represents an integer of 1 to 4), and 50% or more of the remaining hydrogen atoms
  • the residual hydrogen atom when there is a residual hydrogen atom that is not substituted with a fluorine atom in the group (G), the residual hydrogen atom contains an etheric oxygen atom.
  • Fluoro having 1 to 6 carbon atoms It contains a mouth alkyl group or an etheric oxygen atom! /, Or may be substituted with a fluoroalkoxy group having 1 to 6 carbon atoms.
  • R 1 an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.
  • R 2 and R 4 each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.
  • the fluorine atom in the group (G1) contains a perfluoroalkyl group having 1 to 6 carbon atoms which may contain an etheric oxygen atom or an etheric oxygen atom! / Substituted with a perfluoroalkoxy group having 1 to 6 carbon atoms!
  • the repeating unit (A) is a group force having a compound power represented by the following formula (all), the following formula (al2), the following formula (a2), and the following formula (a4).
  • Y a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 1 an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.
  • R 2 and R 4 each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.
  • the fluorine atom in the compound (a) contains a perfluoroalkyl group having 1 to 6 carbon atoms which may contain an etheric oxygen atom or an etheric oxygen atom! / ⁇ Substituted with a perfluoroalkoxy group having 1 to 6 carbon atoms!
  • the fluorinated polymer (F) is a fluorinated polymer containing 25 mol% or more of the repeating unit (A) based on all repeating units. Fluorine polymer solution composition.
  • a polymer comprising a repeating unit formed by polymerization of a polymerizable compound having a fluorine-containing polycyclic aliphatic hydrocarbon group (particularly a polymer having a high content of the repeating unit).
  • a stable fluorine-containing polymer solution composition is provided.
  • the fluoropolymer solution composition of the present invention a thin film excellent in transparency, water repellency, oil repellency, heat resistance, releasability, chemical resistance, especially dynamic water and oil repellency is efficiently formed. it can.
  • various functional materials can be easily prepared by dissolving or dispersing other materials in the fluoropolymer solution composition of the present invention.
  • a compound represented by the formula (a) is referred to as a compound (a), and a group represented by the formula (1) is referred to as a group (1).
  • a group represented by the formula (1) is referred to as a group (1).
  • symbols in the group have the same meanings as above unless otherwise specified.
  • the fluoropolymer (F) in the present invention contains a repeating unit (A) having a fluorinated alicyclic hydrocarbon group in the side chain.
  • the fluorine-containing alicyclic hydrocarbon group is a group in which a fluorine atom is directly bonded to a carbon atom constituting the ring.
  • the fluorine-containing alicyclic hydrocarbon group is preferably a saturated group.
  • the fluorine-containing alicyclic hydrocarbon group is an m-valent group obtained by removing m hydrogen atoms from a cyclic saturated hydrocarbon compound (where m represents an integer of 1 to 4. m is preferably 1. And a fluorine-containing alicyclic hydrocarbon group in which 50% or more of the remaining hydrogen atoms are substituted with fluorine atoms.
  • the remaining hydrogen atoms in the fluorinated alicyclic hydrocarbon group 80% or more is preferably replaced with fluorine atoms, and all that are preferably replaced with fluorine atoms, in particular.
  • the residual hydrogen atom may contain an etheric oxygen atom, and may be a fluoroalkyl group having 1 to 6 carbon atoms or an etheric oxygen atom. Or may be substituted with a fluoroalkoxy group having 1 to 6 carbon atoms.
  • the remaining hydrogen atom may be a hydroxy group, a carboxy group, or a hydroxyalkyl group, an alkoxy group, an alkoxyalkoxy group, an alcohol.
  • Group power consisting of a xylcarbol group and an alkylcarbol group. One or more groups selected and having 1 to 10 carbon atoms are substituted!
  • the main chain of the fluoropolymer (F) is formed of carbon atoms or carbon atoms, or is preferably formed of carbon atoms or carbon atoms. Particularly preferred.
  • the main chain of the fluoropolymer (F) may further contain a carbon atom and an oxygen atom bond.
  • the repeating unit (A) is selected from the group power consisting of the compound represented by the following formula (1), the following formula (2), the following formula (3), the following formula (4), and the following formula (5).
  • N-valent group obtained by removing n hydrogen atoms from one or more alicyclic saturated hydrocarbon compounds (n has the same meaning as described above, the same shall apply hereinafter), and 50% or more of the remaining hydrogen atoms Is a repeating unit having a group (G) substituted with a fluorine atom.
  • the remaining hydrogen atoms in the group (G) are preferably substituted with fluorine atoms, and all of them are preferably substituted with fluorine atoms.
  • the residual hydrogen atom may contain an etheric oxygen atom, but may be a perfluoroalkyl group having 1 to 6 carbon atoms. Alternatively, it may be substituted with a C 1-6 perfluoroalkoxy group which may contain an etheric oxygen atom.
  • n is preferably 1.
  • the repeating unit (A) is a repeating unit having one or more groups (G1) selected from the following group (11), the following group (12), the following group (21) and the following group (41) (The symbols in the formula have the same meaning as above. The same shall apply hereinafter.) O
  • the fluorine atom in the group (Gl) may contain a perfluoroalkyl group having 1 to 6 carbon atoms or an etheric oxygen atom which may contain an etheric oxygen atom! /, Substituted with a perfluoroalkoxy group having 1 to 6 carbon atoms!
  • R 1 is preferably a methyl group or a trifluoromethyl group! /.
  • R 2 and R 4 each independently represent a hydrogen atom, a fluorine atom, a methyl group or trifluoro
  • a romethyl group is preferred.
  • the repeating unit (A) is formed by polymerization of one or more compounds (a) in which the following compound (al), the following compound (al2), the following compound (a2), and the following compound (a4) are selected.
  • the following compound (al) the following compound (al2), the following compound (a2), and the following compound (a4) are selected.
  • Y and Q have the same meaning as above, and so on).
  • the fluorine atom in the compound (a) may contain an etheric oxygen atom, or may contain a perfluoroalkyl group having 1 to 6 carbon atoms or an etheric oxygen atom! / Yo! /, Substituted with a perfluoroalkoxy group having 1 to 6 carbon atoms!
  • Y is preferably a hydrogen atom or a methyl group.
  • Q is preferably a divalent linking group — C (O) —, —SO — C (0) 0—, — C (0) S
  • the above divalent linking groups are more preferred —C (0) 0—, -C (0) OCH, -C (0) NHCH
  • the fluorine-containing polymer (F) in which Q is the divalent linking group the fluorine-containing cyclic saturated hydrocarbon group is considered to be more easily oriented on the outermost surface, and a material excellent in dynamic water repellency is used. In addition to being easy to prepare, there is an effect that the adhesion between the fluoropolymer (F) and the object to be treated is increased.
  • Compound (all2) is a novel compound.
  • the compound (al2) described later is preferably the following compound (al21) (wherein R 11 represents a methyl group or a trifluoromethyl group).
  • Compound (a22) is a novel compound.
  • Compound (a22) is preferably produced in the same manner except that the following compound (ma22) is used instead of compound (ma21).
  • the fluoropolymer (F) has a repeating unit (A) of 25 mol% or less based on all repeating units.
  • Preferred instrument repeating unit (A) only the force to include contain above preferred tool 75 mole 0/0 more than ing of (i.e., comprise 100 mole% repeating units (A) based on all repeating units.) Is particularly preferred.
  • the repeating unit (A) may have one kind of force, or two or more kinds of force.
  • the fluoropolymer (F) contains a repeating unit other than the repeating unit (A) (hereinafter also referred to as other units), the fluoropolymer (F) contains all the repeating units as other repeating units. particularly preferably contains 75 mol 0/0 less preferably fixture 25 mole 0/0 to include less against.
  • the other unit is preferably a repeating unit formed by polymerization of a polymerizable compound capable of forming another unit (hereinafter also referred to as compound (ot)).
  • the compound (ot) is appropriately selected according to the use of the fluoropolymer solution composition of the present invention (hereinafter also referred to as the composition of the present invention).
  • the compound (ot) is preferably a vinyl monomer.
  • the burable monomer may contain a polar group or a halogen atom.
  • polar group examples include — C (O) —, — SO—, — C (0) 0—, — C (0) S—, —
  • One or more monovalent electrodes selected from the group consisting of, -PO H, -SO H and -SO NH forces
  • the bully monomer examples include ethylene, propylene, vinyl acetate, halogenated bures (salts bules etc.), halogenated vinylidenes (salts bisulidenes etc.), styrene, acrylo -Tolyl, (meth) acrylamide, (meth) acrylic acid, (meth) acrylate.
  • (meth) acrylamide is a generic name for acrylamide and methacrylamide
  • (meth) acrylic acid is a generic name for acrylic acid and methacrylic acid
  • (meth) acrylate is a generic name for acrylate and methacrylate. (The same shall apply hereinafter.)
  • O The number of carbon atoms of the meta acrylate is preferably 4-22.
  • meta acrylate examples include n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl.
  • the weight average molecular weight of the fluoropolymer (F) is preferably 1000 to 1000000, more preferably 1000 to 30000, and particularly preferably 1000 to 1500,000 from the viewpoint of solubility in the fluorine-based solvent (S).
  • the preferred U and mode of the fluoropolymer (F) include a polymer having a weight average molecular weight of 1000 to 30000, which only has the repeating unit (A).
  • the repeating unit (A) in the above embodiment is preferably a repeating unit formed by polymerization of the compound (a).
  • the fluorinated organic solvent (S) in the present invention is one or more fluorinated organic solvents (S1) selected from a group force consisting of a fluorocarbon solvent, a fluorether solvent, and a fluorocarbon solvent power. From the standpoint of high compatibility with the preferred fluoropolymer (F) and good handling properties, the group strength of Hyde mouth fluorocarbon solvents, No, Ido mouth fluoro ether solvents and noisy mouth chloro mouth fluorocarbon solvents Particularly preferred is one or more fluorinated organic solvents (S 11) selected.
  • the fluorocarbon solvent is a fluorine atom and a carbon atom alone, or a hydrogen atom, a fluorine atom and a carbon atom alone, which is a liquid at 25 ° C and has a boiling point. It is a fluorine-containing compound having a temperature of 40 ° C or higher. Fluorocarbon solvents that only have fluorine and carbon atoms are called perfluorocarbon solvents! /, Fluorocarbon solvents that only have hydrogen, fluorine, and carbon atoms are called Hyde mouth fluorocarbon solvents. The carbon atoms may form an alicyclic or aromatic ring.
  • perfluorocarbon solvents include CF (CF) CF, CF (CF) CF
  • Examples include perfluorodecalin and perfluorobenzene.
  • hyde mouth fluorocarbon solvent examples include CF CHFCHFCF CF, CF
  • the fluoroether solvent means that only etheric oxygen atoms and fluorine atoms and carbon atoms, or only etheric oxygen atoms, hydrogen atoms, fluorine atoms, and carbon atoms can be heated to 25 ° C. It is a fluorinated compound that is liquid and has a boiling point of 40 ° C or higher. Fluoroether solvents that only have etheric oxygen atoms, fluorine atoms, and carbon atoms are perfluoroether solvents, and fluorether solvents that only have etheric oxygen atoms, hydrogen atoms, fluorine atoms, and carbon atoms Ido mouth fluoroether solvent.
  • the carbon atom may form an alicyclic ring or an aromatic ring, and the etheric oxygen atom and the carbon atom may form a heterocyclic ring. Two or more etheric oxygen atoms may be present.
  • perfluoroether solvent is perfluoro (2-butyltetrahydrofuran).
  • hydrated fluoroether solvent examples include CF CF CF CF OCH, (CF
  • the black fluorocarbon solvent is a fluorine-containing compound consisting of only a chlorine atom, a fluorine atom and a carbon atom, which is liquid at 25 ° C and has a boiling point of 40 ° C or higher. is there.
  • the carbon atoms may form an alicyclic or aromatic ring.
  • a hydrated fluorocarbon-based solvent is composed of only hydrogen atoms, chlorine atoms, fluorine atoms, and carbon atoms, and is a liquid at 25 ° C and has a boiling point of 40 ° C or higher. It is a fluorine-containing compound.
  • the carbon atoms may form an alicyclic or aromatic ring.
  • Hyde mouth black mouth fluorocarbon examples include CC1 FCH, CC1F CF CHC1F
  • fluorinated organic solvent (S) one type may be used, or two or more types may be used. Usually, one type is used.
  • the specific gravity of the fluorine-based organic solvent (S) is 1.8 gZcm 3 or less at 25 ° C. from the viewpoint of handling the fluoropolymer solution composition of the present invention (hereinafter also referred to as the composition of the present invention).
  • Preferred Shigu 1. 6 gZcm 3 or less is particularly preferable.
  • the lower limit of specific gravity is usually 1.3 g / cm 3 or more at 25 ° C.
  • the boiling point of the composition of the present invention is preferably 60 to 200 ° C. from the viewpoint of handling the polymer solution composition.
  • fluoroalcohol solvents can be mentioned.
  • the fluoroalcohol solvent refers to a fluorine-containing compound having a hydroxyl group that is liquid at 25 ° C and has a boiling point of 0 ° C or higher.
  • fluoroalcohol solvents include CHF CF CH OH, CF CF CF C
  • the composition of the present invention contains 0.05 to 25% by mass of the fluoropolymer (F) with respect to the total amount of the fluoropolymer (F) and the fluorinated organic solvent (S).
  • the content of 0.1 to 20% by mass is particularly preferable.
  • the fluorinated polymer (F) and the fluorinated organic solvent (S) are mixed, and the fluorinated polymer (F) is used as the fluorinated organic solvent (S). There is a method of dissolving.
  • the composition of the present invention comprises a fluorine-containing polymer (F) excellent in transparency, water repellency, oil repellency, heat resistance, releasability and chemical resistance, and particularly excellent in dynamic water and oil repellency. It is a stable solution composition containing.
  • the composition of the present invention is added to a coating agent used to form a film of a fluoropolymer (F) on the surface of a desired substrate, or to other materials to add a fluorine-containing polymer to other materials. It is useful as an additive used to form composite (F) composite materials.
  • the composition of the present invention is applied to the surface of a desired substrate, and then the substrate is dried to obtain a fluorinated organic solvent.
  • (S) is distilled off to form a film of the fluoropolymer (F) on the surface of the substrate.
  • the composition of the present invention is sprayed on the surface of the desired substrate to form a film of the fluoropolymer (F) on the surface of the substrate, and the desired substrate is immersed in the composition of the present invention.
  • a film of the fluoropolymer (F) is formed on the surface of the substrate by drying after the formation.
  • the substrate is not particularly limited, and examples thereof include lenses (glasses lenses, optical lenses, etc.), light emitting diodes, displays (eg, PDP, LCD, FED, organic EL, etc.), semiconductor elements, and the like. It is.
  • the coating method is not particularly limited, and examples thereof include a roll coating method, a casting method, a dip method, a spin coating method, a water casting method, a die coating method, and a Langmuir's mouth jet method.
  • the substrate is preferably dried at a temperature equal to or higher than the boiling point of the fluorinated organic solvent (S).
  • the film thickness of the fluoropolymer (F) film formed on the surface of the substrate is not particularly limited, and is usually from 0.01 ⁇ to 1000 / ⁇ m. Since the composition of the present invention is a stable solution composition even when the concentration of the fluoropolymer (F) is high, it has a high film thickness and excellent thin film properties (surface flatness, etc.). F) film can be formed.
  • composition of the present invention When the composition of the present invention is used as an additive, a preferred embodiment is that the composition of the present invention and other materials are mixed to obtain a mixture, and then the mixture is dried to obtain a fluorine-based composition.
  • a mode in which a composite material of the fluoropolymer (F) and another material is formed by distilling off the organic solvent (S) can be mentioned. Since the composite material contains the fluorinated polymer (F), it is excellent in transparency, water repellency, oil repellency, heat resistance, releasability, chemical resistance, particularly dynamic water and oil repellency.
  • the other materials are not particularly limited, and may be inorganic materials or organic materials!
  • the organic material may be a non-polymer or a polymer.
  • the polymer may be rosin or rubber.
  • One specific embodiment of the present invention includes a repeating unit (A P ) formed by polymerization of a polymerizable compound (a P ) having a fluorine-containing polycyclic aliphatic hydrocarbon group.
  • a polymer (A p ) containing 25 mol% or more of all repeating units and a fluorinated solvent (S p ), and the total amount of the polymer (A p ) and the fluorinated solvent (S p ) And a polymer solution composition containing 0.05 to 25% by mass of the polymer (A p ) (hereinafter also referred to as the composition (P) of the present invention).
  • the polymerizable compound (a P ) is not particularly limited as long as it is a compound having a polymerizable group and a fluorine-containing polycyclic aliphatic hydrocarbon group.
  • the fluorine-containing polycyclic aliphatic hydrocarbon group refers to a group in which a fluorine atom is directly bonded to a carbon atom constituting a ring.
  • the polymerizable group and the fluorine-containing polycyclic aliphatic hydrocarbon group may be bonded via a linking group which may be directly bonded.
  • the fluorine content of the polymerizable compound (a P ) is preferably 30% by mass or more, and 50% by mass or more. Is particularly preferred.
  • the fluorine content is preferably 76% by mass or less.
  • the polymerizable group is particularly preferably a polymerizable carbon atom, a group containing a double bond or a group containing an epoxy group, which is preferably an addition polymerizable group or a ring-opening polymerizable group.
  • the fluorine-containing polycyclic aliphatic hydrocarbon group is not particularly limited as long as it is a fluorine-containing polycyclic aliphatic hydrocarbon group having a fluorine atom bonded to a carbon atom constituting the ring.
  • Polyfluoradamantyl group which is preferably a fluorine-containing bridged cyclic hydrocarbon group, which is preferably a polycyclic hydrocarbon group, is particularly preferred.
  • the carbon number of a fluorine-containing polycyclic aliphatic hydrocarbon group is preferably 520. Mashi 5 12 is more preferred.
  • the carbon atom in the fluorine-containing polycyclic aliphatic hydrocarbon group includes a hydroxy group, a carboxy group, or a hydroxyalkyl group, an alkoxy group, an alkoxyalkoxy group, an alkoxycarbo yl group, and an alkylcarbolo group. Any group of one or more groups selected for both strength and group power and having 1 to 10 carbon atoms may be bonded! /.
  • the polymerizable compound (a P ) is preferably the following compound (a P l)! /.
  • X P a monovalent organic group having 2 10 carbon atoms having a polymerizable group.
  • Q p monofluoromethylene group or difluoromethylene group, and 6 Q p may be the same or different! / ⁇ .
  • Y P a hydrogen atom, a fluorine atom, a hydroxy group or a hydroxyalkyl group, and the three ⁇ ⁇ may be the same or different! /!
  • Chi [rho has a number of carbon containing monovalent organic group or an epoxy group with a carbon number of 2 10 containing a polymerizable carbon atoms carbon atoms double bonds 2: monovalent organic group L0 is preferably the formula CG Pl G p2 CTC (O) O 3 monovalent organic group having 3 to 10 carbon atoms (where G Pl and G p2 are each independently a hydrogen atom or a fluorine atom, T is a hydrogen atom, a fluorine atom, or a carbon atom) No al A kill group or a fluoroalkyl group having 1 to 3 carbon atoms is shown. Is particularly preferred. G pl and G p2 are preferably hydrogen atoms.
  • three Y p are two ⁇ ⁇ are fluorine atoms and the remaining one ⁇ ⁇ ⁇ ⁇ is a fluorine atom, a hydroxy group or a hydroxyalkyl group! /.
  • R P A hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms.
  • Z p pp is 0, it is a fluorine atom or a hydroxy group, and when pp is 1, it is a fluorine atom or a hydroxymethyl group.
  • Z Pl ° a fluorine atom or a hydroxy group.
  • Z p fluorine atom or a hydroxymethyl group.
  • a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group is preferred, and a hydrogen atom or a methyl group is particularly preferred.
  • the compound (a P l 11) is obtained by reacting the following compound (a P l 11-3) with water to produce the following compound (a P l 11):
  • z pl11 a fluorine atom or a hydroxymethyl group.
  • z PLL2 a group corresponding to z p111, z pl12 is hydrogen z pl12 corresponding to z PL11 is a fluorine atom corresponding to z P111 fluorine atom, a hydroxymethyl group.
  • z PLL 3 a group corresponding to z p112, z pl13 z pl13 is corresponding to z pl12 fluorine atom, a hydrogen atom corresponding to z pl12 a fluorine atom Furuorokarubo - Le group.
  • polymerizable compound (a P ) examples include the following compounds.
  • the polymer (A p) is the repeating unit (A p) a is preferably of a polymer containing 75 mol% or more based on all repeating units instrument repeating unit (A p) only the force becomes polymer ( That is, a polymer containing 100 mol% of repeating units (A P ) based on all repeating units is particularly preferable.
  • the repeating unit (A P ) may be formed by polymerization of one kind of polymerizable compound (a P ), or may be formed by polymerization of two or more kinds of polymerizable compounds (a P ).
  • the polymer (A P ) is a repeating unit formed by polymerization of a polymerizable compound other than the polymerizable compound (a P ) (hereinafter also referred to as other polymerizable compound) (hereinafter simply referred to as other unit).
  • the polymer (A P ) preferably contains not more than 75 mol% of other repeating units, particularly preferably not more than 25 mol%, based on all repeating units.
  • the other polymerizable compound is not particularly limited, and examples thereof include a compound (ot).
  • the polymer (A P ) has a weight average molecular weight of 1,000,000 to 100,000, or a fluorine-based solvent (3 From the viewpoint of solubility in P ), 1000 to 30000 force S is more preferable, and 1000 to 15000 force S is particularly preferable.
  • a polymer having a weight average molecular weight of 1000 to 30000 consisting only of the repeating unit (A p ) can be mentioned.
  • the preferred, repeating units of (A p) is in the embodiment, preferred repeating units formed by polymerization of the compound (a p l 1),.
  • the polymer (A p ) is preferably produced by polymerizing the polymerizable compound (a P ) in the presence of a polymerization initiator.
  • the polymerization initiator is not particularly limited, and benzoyl peroxide, diisopropyl baroxy dicarbonate, di-tert-butylenoperoxydicarbonate, tert-butylenoperoxy pinoleate, perflurane.
  • examples include peracid compounds such as olobutyryl peroxide and perfluorobenzoyl peroxide; azoiso compounds such as azoisobisbutyoxy-tolyl; persulfate and the like.
  • the polymerization method is not particularly limited, and a Balta polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used.
  • the polymerizable compound (a P ) may be polymerized in the presence of a solvent.
  • Solvents include pentane, hexane, heptane, methanol, ethanol, n-propanol, isopropanol, acetone, diethylene glycol dimethyl ether, 1,4 dioxane, toluene, xylene, methylene chloride, chloroform, fluorine solvent ( S P ) and the like.
  • the reaction temperature and reaction pressure in the polymerization are not particularly limited.
  • fluorinated solvent (S p ) are the same as those of the fluorinated organic solvent (S).
  • composition (P) of the present invention preferably contains 0.1 to 20% by mass of the polymer (A p ) based on the total amount of the polymer (A p ) and the fluorinated solvent (S p ).
  • the method for producing the composition (p) of the present invention is not particularly limited, and the polymer (A p ) and the fluorinated solvent are used.
  • the composition (p) of the present invention contains a polymer (A P ) that is excellent in transparency, water repellency, oil repellency, heat resistance, releasability, chemical resistance, and particularly excellent in dynamic water repellency and oil repellency.
  • the composition (P) of the present invention when used as a coating agent, the composition (P) of the present invention is applied to the surface of a desired substrate, and then the substrate is dried. Then, there is an embodiment in which the fluorine-based solvent (S p ) is distilled off to form a polymer (A p ) film on the surface of the substrate. Further, an embodiment in which the composition (p) of the present invention is sprayed onto the surface of a desired substrate to form a polymer (A P ) film on the surface of the substrate, and the desired substrate is used as the composition of the present invention. Another example is an embodiment in which a film of polymer (A P ) is formed on the surface of the base material by drying after being immersed in (p).
  • the substrate is not particularly limited, and examples thereof include lenses (glasses lenses, optical lenses, etc.), light emitting diodes, displays (eg, PDP, LCD, FED, organic EL, etc.), semiconductor elements, and the like.
  • the coating method is not particularly limited, and examples thereof include a roll coating method, a casting method, a dip method, a spin coating method, a water casting method, a die coating method, and a Langmuir's mouth jet method.
  • the substrate is preferably dried at a temperature equal to or higher than the boiling point of the fluorinated solvent (S P ).
  • the film thickness of the polymer (A P ) film formed on the surface of the substrate is not particularly limited, and is usually 0.01 ⁇ m to 1000 ⁇ m. Since the composition (p) of the present invention is a stable solution composition even when the concentration of the polymer (A P ) is high, it is a polymer having a high film thickness and excellent thin film properties (such as surface flatness). A P ) film can be formed.
  • composition (p) of the present invention When the composition (p) of the present invention is used as an additive, a preferred embodiment is that the composition (p) of the present invention and other materials are mixed to obtain a mixture, and then the mixture is used.
  • a mode of forming a composite material of the polymer (A p ) and other materials by drying and distilling off the fluorine-based solvent (S p ) can be mentioned. Since the composite material includes a polymer (A p ), the composite material is excellent in transparency, water repellency, oil repellency, heat resistance, release property, chemical resistance, and particularly dynamic water repellency and oil repellency.
  • the materials are not particularly limited, and may be inorganic materials or organic materials.
  • the organic material may be a non-polymer or a polymer.
  • the polymer may be rosin or rubber.
  • Example [0075] The present invention is described in detail below, but the present invention is not construed as being limited thereto.
  • the weight average molecular weight is denoted by Mw, and the number average molecular weight is denoted by Mn.
  • R F1 represents F (CF) OCF (CF) CFOCF (CF)-.
  • Fluoropolymers obtained by homopolymerizing the compound (al 1 ) (Mw6200, Mn4000) ( Hereinafter referred to as polymer (Al).
  • polymer (Al) 0.5 parts of) and 9.5 parts of 1,3-bis (trifluoromethyl) benzene are mixed, and the polymer (A1) is dissolved in 1,3-bis (trifluoromethyl) benzene.
  • a solution composition containing 5.0% by mass of the polymer (A1) with respect to the total mass of the polymer (A1) and 1,3-bis (trifluoromethyl) benzene (hereinafter referred to as the composition 1). !
  • the body (F) and the fluorinated organic solvent were appropriately selected to obtain a plurality of fluoropolymer solution compositions (Composition 2 to Composition 11).
  • the composition of each fluoropolymer solution composition is summarized in Table 1 below.
  • the polymer amount in the table means the mass% of the fluoropolymer (F) with respect to the total mass of the fluoropolymer (F) and the fluorosoluble organic medium in the fluoropolymer solution composition.
  • Example 2-5 (Comparative example)] Example in which fluorinated polymer (F) was dissolved in a non-fluorinated organic solvent 0.5 part of polymer (A2) and 9.5 parts of cyclopentanone The force polymer (A2) tried to mix with did not dissolve in cyclopentanone.
  • composition 1 is applied onto a silicon substrate by spin coating, the silicon substrate is A heat treatment was carried out at 100 ° C. for 90 seconds to obtain a silicon substrate having a thin film (film thickness: 0.21 111) of polymer (A1) formed on the surface.
  • the contact angle of the thin film with respect to decalin was 46 °.
  • composition 7 was applied onto a silicon substrate by spin coating, the silicon substrate was heat-treated at 100 ° C. for 90 seconds to form a polymer (A2) thin film (film thickness 0.20 / 20 on the surface). A silicon substrate on which zm) was formed was obtained. The contact angle of the thin film with respect to decalin was 49 °.
  • composition 12 After applying composition 12 to the surface of the silicon substrate by spin coating, the silicon substrate was heated at 130 ° C for 1 minute to distill away 1,3-bis (trifluoromethyl) benzene, and the silicon substrate A polymer (A3) film was formed on the surface of the substrate, and a silicon substrate having the surface coated with the composition 12 was produced.
  • Table 2 shows the measurement results of the contact angle, the falling angle and the receding angle of the film formed on the surface of the silicon substrate. Table 2 also shows the measurement results of the contact angle, the falling angle and the receding angle of the polymer (A4) or (A5) film formed by using composition 13 or 14 V.
  • a contact angle meter (trade name: DropMaster700, manufactured by Kyowa Interface Science Co., Ltd.) was used.
  • the contact angle refers to the contact angle of water droplets on the membrane when water droplets (2 L) are formed on the membrane surface and the substrate is held horizontally.
  • the falling angle is the tilt angle of the substrate just before the water droplet falls when the water droplet (50 / z L) is formed on the surface of the film and the substrate is tilted.
  • the receding angle is the contact angle of the water droplet on the opposite side of the falling direction.
  • Composition 8 (1.3 g) was mixed with a cyclopentanone solution (3.3 g) containing 8% by mass of a metatalylate polymer (Mw6600, Mn2900) to obtain a uniform solution composition.
  • the solution composition is applied onto a silicon substrate using a spin coating method, and then the silicon substrate is heated at 100 ° C. for 90 seconds to form a thin resin film (film thickness 0.22 m) on the surface. Silicon base I got a plate.
  • a fluoropolymer solution composition comprising a fluoropolymer that is excellent in transparency, water repellency, oil repellency, heat resistance, releasability, chemical resistance, particularly dynamic water and oil repellency.
  • the fluoropolymer solution composition of the present invention the surface of the desired substrate is transparent, water and oil repellency (particularly dynamic water and oil repellency), heat resistance, releasability and chemical resistance. Etc. can be given.
  • the composite material having the physical properties can be easily prepared.

Abstract

L'invention concerne une composition de solution polymère contenant du fluor. La composition selon l'invention comprend un polymère contenant du fluor (F) contenant une unité de répétition (A) comportant un groupement hydrocarboné alicyclique contenant du fluor dans une chaîne latérale et un solvant organique contenant du fluor (S). L'unité de répétition (A) comporte par exemple un groupement (G) qui est un groupement n-valent obtenu en retirant n atomes d'hydrogène (à condition que n représente un entier compris entre 1 et 4) d'un ou de plusieurs composés hydrocarbonés cycliques saturés choisis dans le groupe comprenant les composés représentés par la formule (1), la formule (2), la formule (3), la formule (4) et la formule (5) ci-dessous et en remplaçant une proportion supérieure ou égale à 50 % des atomes d'hydrogène restants par des atomes de fluor.
PCT/JP2007/062031 2006-06-16 2007-06-14 Composition de solution polymère contenant du fluor WO2007145288A1 (fr)

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JP2006167562 2006-06-16
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JP2007039816A JP2009203247A (ja) 2006-06-16 2007-02-20 含フッ素重合体溶液組成物

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US8134033B2 (en) 2006-07-11 2012-03-13 Asahi Glass Company, Limited Fluorocompound having highly fluorinated norbornane structure, fluoropolymer, and their production processes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3333229A1 (fr) * 2016-12-08 2018-06-13 3M Innovative Properties Company Compositions de fluoropolymères et enrobages

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JPS63301266A (ja) * 1985-12-24 1988-12-08 ソシエテ　シミツク　デ　シヤルボナ−ジユ　エス．ア− 保護ワニス
JPH02129254A (ja) * 1988-11-10 1990-05-17 Asahi Glass Co Ltd コーティング用含フッ素重合体組成物
JPH0497508A (ja) * 1990-08-14 1992-03-30 Neos Co Ltd 付着防止剤
JPH06222623A (ja) * 1992-09-18 1994-08-12 Minnesota Mining & Mfg Co <3M> パーフッ素化溶媒を用いる液体トナー
WO1997035919A1 (fr) * 1996-03-22 1997-10-02 Nippon Zeon Co., Ltd. Liquide contenant un polymere lubrifiant et technique de formation d'une pellicule de polymere lubrifiant
JPH10273615A (ja) * 1997-03-31 1998-10-13 Hitachi Chem Co Ltd 光学用ポリマーワニス及びこれを用いた光学素子
JP2004506810A (ja) * 2000-08-18 2004-03-04 スリーエム　イノベイティブ　プロパティズ　カンパニー フルオロアルキル（メタ）アクリレートコポリマーコーティング組成物
JP2007086731A (ja) * 2005-08-24 2007-04-05 Asahi Glass Co Ltd レジスト保護膜用組成物

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JPS63301266A (ja) * 1985-12-24 1988-12-08 ソシエテ　シミツク　デ　シヤルボナ−ジユ　エス．ア− 保護ワニス
JPH02129254A (ja) * 1988-11-10 1990-05-17 Asahi Glass Co Ltd コーティング用含フッ素重合体組成物
JPH0497508A (ja) * 1990-08-14 1992-03-30 Neos Co Ltd 付着防止剤
JPH06222623A (ja) * 1992-09-18 1994-08-12 Minnesota Mining & Mfg Co <3M> パーフッ素化溶媒を用いる液体トナー
WO1997035919A1 (fr) * 1996-03-22 1997-10-02 Nippon Zeon Co., Ltd. Liquide contenant un polymere lubrifiant et technique de formation d'une pellicule de polymere lubrifiant
JPH10273615A (ja) * 1997-03-31 1998-10-13 Hitachi Chem Co Ltd 光学用ポリマーワニス及びこれを用いた光学素子
JP2004506810A (ja) * 2000-08-18 2004-03-04 スリーエム　イノベイティブ　プロパティズ　カンパニー フルオロアルキル（メタ）アクリレートコポリマーコーティング組成物
JP2007086731A (ja) * 2005-08-24 2007-04-05 Asahi Glass Co Ltd レジスト保護膜用組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8134033B2 (en) 2006-07-11 2012-03-13 Asahi Glass Company, Limited Fluorocompound having highly fluorinated norbornane structure, fluoropolymer, and their production processes

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