WO2007145288A1

WO2007145288A1 - Fluorine-containing polymer solution composition

Info

Publication number: WO2007145288A1
Application number: PCT/JP2007/062031
Authority: WO
Inventors: Naoko Shirota; Shu-Zhong Wang; Osamu Yokokoji
Original assignee: Asahi Glass Company, Limited
Priority date: 2006-06-16
Filing date: 2007-06-14
Publication date: 2007-12-21
Also published as: TW200815541A; JP2009203247A

Abstract

Disclosed is a fluorine-containing polymer solution composition. Disclosed is a fluorine-containing polymer solution composition comprising a fluorine-containing polymer (F) containing a repeating unit (A) having a fluorine-containing alicyclic hydrocarbon group in a side chain, and a fluorine-containing organic solvent (S). For example, the repeating unit (A) has a group (G) which is an n-valent group obtained by removing n hydrogen atoms (provided that n represents an integer of 1-4) from one or more cyclic saturated hydrocarbon compounds selected from the group consisting of compounds represented by the formula (1), formula (2), formula (3), formula (4) and formula (5) shown below and substituting not less than 50% of the remaining hydrogen atoms with fluorine atoms.

Description

Specification

Fluoropolymer solution composition

Technical field

[0001] The present invention relates to a fluoropolymer solution composition.

Background art

[0002] 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.)

[0003] [Chemical 1]

[0004] 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.

2

It is useful as a resist or the like to be used (see Patent Documents 1 and 3.) ₀

When the polymer is used for applications such as a resist, the polymer is usually dissolved in a solvent to prepare a polymer solution composition. As the solvent, 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

Disclosure of the invention

Problems to be solved by the invention

However, according to the study by the present inventors, 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.

Accordingly, 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.

Means for solving the problem

[0007] As a result of intensive studies, the present inventors have determined that a polymer containing a repeating unit formed by polymerization of a polymerizable compound having a fluorinated alicyclic hydrocarbon group (particularly, the content of the repeating unit is high). A stable fluoropolymer solution composition comprising a high polymer) and a specific fluorine-based organic solvent was found.

That is, the present invention has the following gist.

<1> 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) .

<2> 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 fluorine-containing polymer solution composition according to 1>, wherein is a repeating unit having a group (G) substituted with a fluorine atom.

[0009] [Chemical 2]

(1) (2) (3) (4) (5) However, 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. However, 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.

[0010] <3> The fluoropolymer solution composition according to <2>, wherein n is 1.

<4> Repeating unit (A) having one or more groups (G1) in which the group power consisting of the following formula (11), the following formula (12), the following formula (21) and the following formula (41) is also selected Unit 1-> 3

> The fluoropolymer solution composition according to any one of the above.

[0011] [Chemical 3]

However, the symbol in a formula shows the following meaning.

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.

In addition, 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!

[0012] <5> 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). The fluoropolymer solution composition according to any one of <1> to <4>, which is a repeating unit formed by polymerization of the compound (a).

[0013] [Chemical 4]

a ") However, the symbols in the formula have the following meanings.

Y: a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

Q: Single bond or divalent linking group.

Further, 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! /置換 Substituted with a perfluoroalkoxy group having 1 to 6 carbon atoms!

<6> 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.

<7> Fluorine Organic Solvent (S) 1S Fluorocarbon solvent, Fluoroether solvent Solvent group consisting of chlorofluorocarbon solvent and Hyde chlorofluorocarbon solvent One or more fluorinated organic solvents (S1) selected 1. The fluoropolymer solution composition according to any one of 1> to <6>.

<8> Fluorine organic solvent (S) 1S Hyde mouth fluorocarbon solvent, Hyde mouth fluoro mouth ether solvent and Noid mouth black mouth fluorocarbon solvent power Group force One or more kinds of fluorinated organic solvents (S 11) selected The fluoropolymer solution composition according to any one of <1> to <7>.

<9> Containing <0.05> -25% by mass of fluoropolymer (F) with respect to the total amount of fluoropolymer (F) and fluorinated organic solvent (S)! The fluorine-containing polymer according to claim Solution composition.

The invention's effect

[0015] According to the present invention, 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. By using 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. Moreover, various functional materials can be easily prepared by dissolving or dispersing other materials in the fluoropolymer solution composition of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present specification, 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). The same applies to compounds represented by other formulas and groups represented by other formulas. Further, 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.

[0017] 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.

[0018] Among 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. Liked! / ヽ. When there is a residual hydrogen atom that is not substituted with a fluorine atom in the group, 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!

[0019] Whether 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.

[0020] 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.

[0021] [Chemical 5]

(1) (2) (3) (4) (5)

[0022] It is particularly preferable that 80% or more of the remaining hydrogen atoms in the group (G) are preferably substituted with fluorine atoms, and all of them are preferably substituted with fluorine atoms. When there is a residual hydrogen atom that is not substituted with a fluorine atom in the group (G), 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

[0023] [Chemical 6]

(11) (12)

[0024] 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

si.

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. Are particularly preferred (Y and Q have the same meaning as above, and so on).

[0025] [Chemical 7]

[0026] 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

2

— OC (0) NH—, — C (0) NH— and — PO (O) —a kind selected from the group of forces

2 The above divalent linking groups are more preferred —C (0) 0—, -C (0) OCH, -C (0) NHCH

2

—Or— OC (0) NH—is particularly preferred—C (0) 0—or—C (0) OCH—

2 2 Most preferred. In 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.

As the compound (al 1), the following compound (al 11) or the following compound (al 12) is preferred,

[0027] [Chemical 8]

Compound (all2) is a novel compound. In the production method of the compound (all2), the compound (al2) described later is preferably the following compound (al21) (wherein R ¹¹ represents a methyl group or a trifluoromethyl group).

[0029] [Chemical 9]

As the compound (a2), the following compound (a21) or the following compound (a22) is preferred. [0030] [Chemical Formula 10] [0031]

[0032]

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).

[0033] [Chemical 12]

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.

[0034] When 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)).

[0035] 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.

[0036] Specific examples of the polar group include — C (O) —, — SO—, — C (0) 0—, — C (0) S—, —

2

OC (0) NH—, — C (0) NH— and — PO (O) —

2

On the divalent polar group, 1 OH, 1 SH, 1 COOH, -CONH, 1 NH, 1 CN, 1 NCO

twenty two

One or more monovalent electrodes selected from the group consisting of, -PO H, -SO H and -SO NH forces

3 3 2 2

Sex groups.

[0037] Specific examples of the bully monomer 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. However, (meth) acrylamide is a generic name for acrylamide and methacrylamide, (meth) acrylic acid is a generic name for acrylic acid and methacrylic acid, and (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.

[0038] Specific examples of the meta acrylate include n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl. (Meth) Atalylate, Tolyl (Meth) Atalylate, 3,3-Dimethylbutyl (Meth) Atalylate, (2,2-Dimethyl-1-methyl) propyl (Meth) Atalylate, Cyclopenty (Meth) acrylate, 2-ethyl hexyl (meth) acrylate, t-butyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, bearyl (meth) ate Alkyl (meth) acrylates such as glycidyl (meth) acrylate, hydroxyalkyl (meth) acrylates such as hydroxyalkyl (meth) acrylate, phenol (meth) acrylate, benzyl (meth) acrylate Can be mentioned.

[0039] 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).

[0040] 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 Noid mouth chloro mouth fluorocarbon solvents Particularly preferred is one or more fluorinated organic solvents (S 11) selected.

[0041] In the present specification, 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.

[0042] Specific examples of perfluorocarbon solvents include CF (CF) CF, CF (CF) CF

3 2 4 3 3 2 6

, CF CF (CF) CF (CF) CF CF (CF) CF CF, perfluorocyclohexane,

3 3 3 3 2 3 2 3

Examples include perfluorodecalin and perfluorobenzene.

Specific examples of the hyde mouth fluorocarbon solvent include CF CHFCHFCF CF, CF

3 2 3 3

(CF) H, CF (CF) CH CH, CF (CF) CH CH, CF (CF) CH CH, 1, 3 Bis (trifluoromethyl) benzene, 1,4 bis (trifluoromethyl) benzene.

[0043] In this specification, 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.

[0044] A specific example of the perfluoroether solvent is perfluoro (2-butyltetrahydrofuran).

Specific examples of the hydrated fluoroether solvent include CF CF CF CF OCH, (CF

3 2 2 2 3

) CFCF (CF) CF OCH, CF CH OCF CHF, CHF CF OCH

3 2 3 2 3 3 2 2 2 2 2 3

[0045] In the present specification, 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.

As used herein, 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.

[0046] Specific examples of Hyde mouth black mouth fluorocarbon include CC1 FCH, CC1F CF CHC1F

2 3 2 2

CHC1 CF CF force S.

2 2 3

As the 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.

[0047] As other fluorine-based organic solvents, fluoroalcohol solvents can be mentioned. In this specification, 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.

Specific examples of fluoroalcohol solvents include CHF CF CH OH, CF CF CF C

2 2 2 3 2 2

HFCF CH OH, CHF CF CF CF CH OH, CF CH OH, CF CH (OH) CF

2 2 2 2 2 2 2 3 2 3 3

[0048] 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.

[0049] As a method for producing the composition of the present invention, 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.

[0050] 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.

[0051] In a preferred embodiment when the composition of the present invention is used as a coating agent, 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. There is an embodiment in which (S) is distilled off to form a film of the fluoropolymer (F) on the surface of the substrate. Further, an embodiment in which 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. Another example is an embodiment in which a film of the fluoropolymer (F) is formed on the surface of the substrate by drying after the formation.

[0052] 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.

[0053] 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 μπι to 1000 / ζ 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.

[0054] 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.

[0055] 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.

[0058] 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.

[0059] 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. In addition, 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)! /.

[0060] [Chemical 13]

However, the symbol in a formula shows the following meaning.

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! / ヽ.

Y ^P : a hydrogen atom, a fluorine atom, a hydroxy group or a hydroxyalkyl group, and the three Υ ^Ρ 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.

[0061] The six Q ^p, all of the at least four Q ^p is difluoromethyl O b methylene is and even preferable instrument six groups Q ^P is difluoromethyl O b methylene group is particularly preferred.

It is preferable that three Y ^p are two Υ ^ρ are fluorine atoms and the remaining one Υ ^フッ^素 is a fluorine atom, a hydroxy group or a hydroxyalkyl group! /.

The polymerizable I匕合compound (a ^P), and even following compound (a ^P ll) and more preferably tool following compound (a ^P l 10) or the following compound (a ^P l 11) Especially preferred.

[0062] [Chemical 14]

However, the symbols in the formulas have the following meanings.

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.

: 0 or 1.

When 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.

In each compound, 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.

[0063] 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):

- 2) was obtained, and then the compound (a ^P l 11 - 2) and H- is reacted with CHO to give the following compound (a ^P l 1 11), then compound (a ^P lll- 1 ) And the formula CH = CR ^P C (0) C1

2 It can be manufactured by reacting a product.

[0064] [Chemical 15]

However, the symbol in a formula shows the following meaning.

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.

Specific examples of the polymerizable compound (a ^P ) include the following compounds.

[0065] [Chemical 16]

[0066] 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 ). Well! /

[0067] 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).

[0068] 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.

As a preferred embodiment of the polymer (A ^p ), 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.

[0069] 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.

[0070] 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.

The definition, preferred embodiments, and specific examples of the fluorinated solvent (S ^p ) are the same as those of the fluorinated organic solvent (S).

The 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 ).

[0071] 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.

(S ^p) by mixing, a method of dissolving the polymer (A ^p) a fluorine-based solvent (S ^p) and the like. 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. A stable solution composition, a coating agent used to form a polymer (A ^P ) film on the surface of a desired substrate; Alternatively, it is useful as an additive that is added to other materials to form a composite material of other materials and a polymer (A ^p ).

[0072] Preferably, when the composition (p) of the present invention is 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).

[0073] 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 μm to 1000 μm. 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.

[0074] 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.

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.

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.

1, 1, 2 Trichrome mouth 1, 2, 2 Trifluoroethan is written as R113.

In order to produce the fluoropolymer (F), the following compound i ¹ ), the following compound (al ² ), the following compound (& 2 ¹ ), the following compound (& 4 ¹ ) or the following compound (ot ¹ ) was used.

[0076] [Chemical 17]

[0077] [Example 1 1 (Reference Synthesis Example)] Production Example of Compound (al ² )

To 0 ° and held at C flask, the following compound ^{(a P lll- 31) (27.} 46g), was stirred placed NaF (3. 78) Contact and acetone (lOOmL). Next, water (1.14 g) was dropped into the flask, and the inside of the flask was sufficiently stirred. The flask the solution recovered by filtration to give the crude product obtained was dried and purified by sublimation of the following compound ^{(a p ll 1- 21) (} 22. Olg).

[0078] Then, potassium hydroxide (1.00 g) and a formalin aqueous solution (20 mL) were added to a mixture of the compound (a ^P l 11-21) (2.03 g) and dimethyl sulfoxide (50 mL). The reaction was carried out at 75 ° C. After completion of the reaction, the reaction solution was extracted with dichloro port penta full O b propane to obtain the following compound ^{(a P lll- 11) (1.} 58g).

[0079] In the same manner, the resulting compound ^{(a P ll 1- 11) (} 6. Olg) and dichloro port penta full O Ropuro pan (103 g) and placed in a flask, then the Toryechiruamin (1. 68 g) CH = C (CH)

twenty three

COCKl. 58 g) was added, and the flask was stirred at 25 ° C for 2 hours. The crude product obtained by concentrating the solution in the flask was purified by column chromatography to obtain the compound (al ² ).

[0080] [Chemical 18]

(a ^p 111-31) (a ^p 111-21) (a ^p 111-11) The NMR data of the compound (al ² ) are shown below.

'H-NMROOO.4MHZ, solvent: CDCl, standard: Si (CH)) δ (ppm): 1. 96 (s, 3

3 3 "4 '

H), 5.06 (s, 2H), 5.71 (s, 1H), 6.19 (s, 1H)

F-NMR (282.7MHz, solvent: CDCl, standard: CFC1) δ (ppm): — 113.6 (6F

3 3

), -121.1 (6F), -219.4 (3F).

[0081] [Example 1 2 (Reference Synthesis Example)] Production Example of Compound (& 2 ¹ )

According to the production route of the following formula, the compound (& 2 ¹ ) was produced from the following compound (ma21). R ^F1 represents F (CF) OCF (CF) CFOCF (CF)-.

2 3 3 2 3

[0082] [Chemical 19]

A compound (ma21) (15 g), black mouth form (100 g) and NaF (7.02 g) were placed in a flask under a nitrogen gas atmosphere, and F (CF) OCF (CF) COF (7

2 3 3

9 g) was added dropwise, and the inside of the flask was further stirred. After removing insoluble solids in the flask contents by pressure filtration, saturated aqueous sodium hydrogen carbonate solution (103 g) was added to the flask, and the organic layer was recovered and concentrated to obtain compound (n ^ l ¹ ) (74 g).

[0083] Next, R113 (313 g) was added to an autoclave in which a NaF pellet packed bed was installed at the gas outlet, and nitrogen gas was added to the autoclave for 1 hour while stirring the autoclave at 25 ° C. After blowing, fluorine gas diluted to 20% volume with nitrogen gas was blown. While the fluorine gas was blown as it was, a solution in which the compound (n ^ l ¹ ) (67 g) was dissolved in R113 (299 g) was introduced into the autoclave under a pressure of 0. IMPa. After completion of the introduction, the autoclave contents were collected and concentrated to obtain a compound (0 & 21 ¹ ).

Next, the compound (oaSl ¹ ) (80 g) and powdered KF (0.7 g) were placed in a flask under a nitrogen gas atmosphere, and after heating the flask for 6 hours, the flask contents were subjected to a distillation method using a cold trap. Purification by recrystallization gave compound (pa21) (38 g).

[0084] Next, a round bottom flask under a nitrogen gas atmosphere was charged with NaBH (1. lg) and tetrahydrofuran (

Four

30 g) was added. While stirring the flask on ice, a dichloropentafluoropropane solution (48 g) containing 22% by mass of the compound (pa21) was added dropwise to the flask. After completion of the dropwise addition, the flask was further stirred, and the solution obtained by neutralizing the solution in the flask with 0.1 mol ZL aqueous hydrochloric acid (150 mL) was washed with water and purified by distillation to obtain compound (qa21). Obtained.

Next, the flask was charged with compound (qa21) (2.2 g), tetrahydrofuran (10 g), aluminum salt of N-trosophenylhydroxylamine (2 mg) and triethylamine (1.2 g). While the flask was cooled with ice and stirring, CH = C (CH) C (0) C1 (1.2 g) was added to the flask.

twenty three

A solution dissolved in tetrahydrofuran (7.3 g) was added dropwise. After completion of the dropwise addition, the flask was further stirred, and an aqueous sodium hydrogen carbonate solution was added. The extract obtained by extracting the solution in the flask with dichloropentafluoropropane was dried and concentrated. The resulting concentrate was purified by silica gel column chromatography to obtain compound (& 2 ¹ ) (2.7 g) Got.

The NMR data of the compound (& 2 ¹ ) are shown below.

'H-NMROOO.4MHZ, solvent: CDC1, standard: TMS) δ (ppm): 6. 31 (1H), 5

Three

.88 (1H), 5.84 (1H), 2.01 (3H).

1 ⁹ F-NMR (282.7 MHz ゝ solvent: CDC1, standard: CFC1) δ (ppm): — 104.6 (IF

3 3

), -120.5 (IF), -122.4 (1F), --124.2 (1F), --124.6 (IF), --126.5 (1 F), -132.7 to-132.8 (2F), --214.8 (IF), --223.2 (1F).

[0086] [Example 2] Production example of fluoropolymer solution composition

[Example 2-1] Production example of compositions 1-11

Fluoropolymers obtained by homopolymerizing the compound (al ¹ ) (Mw6200, Mn4000) ( Hereinafter referred to as 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). !

[0087] polymer as fluoropolymer (F) (A1) or the compound (al ²⁾ and by homopolymerizing resulting et a fluoropolymer (Mw6000, Mn2700) (hereinafter referred to as polymer (A2). ) And 1,3-bis (trifluoromethyl) benzene, F (CF) OCH, F (

2 4 3

CF) OCH, dichloropentafluoropropane (CC1F CF CHC1F and CHC1 CF CF

A mixture of 2 6 3 2 2 2 2. ), F (CF) CH CH or CF CH OCF CHF

3 2 6 2 3 3 2 2 2

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. However, 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. The value to be

[0088] [Table 1]

[0089] [Example 2-2] Production Example of Composition 12

Prepared by dissolving a fluorine-containing polymer (Mw7400) obtained by homopolymerizing the compound (& 2 ¹ ) (hereinafter referred to as polymer (A3)) in 1,3-bis (trifluoromethyl) benzene. The solution is further filtered through a filter (made of polytetrafluoroethylene; the same shall apply hereinafter) to give a heavy weight to the total mass of the polymer (A3) and 1,3-bis (trifluoromethyl) benzene. Merge (A A fluoropolymer solution composition (Composition 12) containing 3.8% by mass of 3) was produced.

[0090] [Example 2-3] Production Example of Composition 13

Prepared by dissolving a fluorine-containing polymer (Mw8000) obtained by homopolymerizing the compound (& 4 ¹ ) (hereinafter referred to as polymer (A4)) in 1,3-bis (trifluoromethyl) benzene. The solution is filtered through a filter and contains 3.8% by mass of polymer (A4) with respect to the total mass of polymer (A4) and 1,3-bis (trifluoromethyl) benzene. A fluoropolymer solution composition (Composition 13) was produced.

[0091] [Example 2-4] Production Example of Composition 14

Compound (al ²⁾ and the compound (ot ¹⁾ by radical copolymerization, repetition of compound to total repeating units (al ²⁾ repeating units containing 88 mole ^_0/0, the compound (ot ¹⁾ A fluoropolymer (Mw9600) (hereinafter referred to as polymer (A5)) containing 12 mol% of units was produced. A solution obtained by dissolving the polymer (A5) in 1,3-bis (trifluoromethyl) benzene is filtered through a filter, and the polymer (A5) and 1,3-bis (trifluoromethyl) are filtered. ) A fluoropolymer solution composition (Composition 14) containing 5.7 mass% of the polymer (A5) based on the total mass of benzene was produced.

[0092] [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.

An attempt was made to prepare a polymer solution composition using a non-fluorinated solvent selected from propylene glycol monomethyl ether acetate, ethyl lactate, and methyl amyl ketone instead of cyclopentanone. It did not dissolve in the fluorinated solvent.

[0093] Further, an attempt was made to dissolve the polymer (A4) in one kind of non-fluorinated organic solvent in which cyclopentanone, propylene glycol monomethyl ether acetate, ethyl lactate, isobutyl alcohol, and methyl amyl ketone power are also selected. However, the polymer (A4) did not sufficiently dissolve in the non-fluorinated organic solvent.

[0094] [Example 3] Coating example using the fluoropolymer solution composition (Part 1)

[Example 3-1]

After 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 °.

[0095] [Example 3-2]

After 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 °.

[Example 4] Example of coating using fluoropolymer solution composition (Part 2)

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.

[0096] For the measurement, a contact angle meter (trade name: DropMaster700, manufactured by Kyowa Interface Science Co., Ltd.) was used. However, 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. In addition, 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.

[0097] [Table 2]

[Example 5] Example of addition of fluoropolymer (F) to other resin materials

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.

Industrial applicability

According to the present invention, 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. Is provided. By using 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. Furthermore, the composite material having the physical properties can be easily prepared. In addition, the specification, claims and summary of Japanese Patent Application 2006-167562 filed on June 16, 2006 and Japanese Patent Application 2007-039816 filed on February 20, 2007 The entire contents of this document are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

The scope of the claims

[1] A fluorine-containing polymer solution composition comprising a fluorine-containing polymer containing a repeating unit (A) having a fluorine-containing alicyclic saturated hydrocarbon group in the side chain, and a fluorine-based organic solvent (S).

[2] The repeating unit (A) is selected from the following formula (1), formula (2), formula (3), formula (4) and formula (5). N groups 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 are The fluorine-containing polymerization liquid composition according to claim 1, which is a repeating unit having a group (G) substituted with a fluorine atom.

[Chemical 1] υ

(1) (2) (3) (4) (5) However, when there is a residual hydrogen atom not substituted with a fluorine atom in the group (G), the residual hydrogen atom contains an etheric oxygen atom. However, it may contain a fluorinated alkyl 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. .

[3] The fluoropolymer solution composition according to claim 2, wherein n is 1.

[4] Repeating unit (A) force A repeating unit having one or more groups (G1) selected from the group force consisting of the following formula (11), the following formula (12), the following formula (21) and the following formula (41): The fluorine-containing polymer solution composition according to any one of claims 1 to 3.

[Chemical 2]

(11) 12 (41) However, the symbols in the formula have the following meanings. R: 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.

[5] Repeating unit (A) force One or more compounds selected from the group consisting of compounds represented by the following formula (al), the following formula (al2), the following formula (a2) and the following formula (a4) (a 5) The fluoropolymer solution composition according to any one of claims 1 to 4, which is a repeating unit formed by polymerization.

[Chemical 3]

However, the symbol in a formula shows the following meaning.

Y: a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

Q: Single bond or divalent linking group.

R ¹ : an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.

6. The fluoropolymer solution according to any one of claims 1 to 5, wherein the fluoropolymer (F) force is a fluoropolymer containing 25 mol% or more of the repeating unit (A) based on all repeating units. Composition. [7] The fluorine-based organic solvent (S) is one or more fluorine-based organic solvents selected from the group consisting of a fluorocarbon solvent, a fluoroether solvent, a fluorofluorocarbon solvent, and a hydrochlorofluorocarbon solvent ( The fluoropolymer solution composition according to any one of claims 1 to 6, which is S1).

[8] Fluorine organic solvent (S) 1S Hyde mouth fluorocarbon solvent, Hyde mouth fluoroether solvent and Noid mouth black fluorocarbon solvent power One or more fluorinated organic solvents selected (SI 1) The fluorine-containing polymer solution composition according to any one of claims 1 to 7.

[9] The fluorinated polymer (F) according to any one of claims 1 to 8, comprising 0.05 to 25% by mass of the fluorinated polymer (F) with respect to the total amount of the fluorinated polymer (F) and the fluorinated organic solvent (S). Fluoropolymer solution composition.