CN110730790B - Fluorine-containing monomer, fluorine-containing polymer, composition for forming pattern using same, and method for forming pattern using same - Google Patents

Fluorine-containing monomer, fluorine-containing polymer, composition for forming pattern using same, and method for forming pattern using same Download PDF

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CN110730790B
CN110730790B CN201880037295.6A CN201880037295A CN110730790B CN 110730790 B CN110730790 B CN 110730790B CN 201880037295 A CN201880037295 A CN 201880037295A CN 110730790 B CN110730790 B CN 110730790B
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fluorine
group
pattern
carbon atoms
formula
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CN110730790A (en
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兼子让
板仓翼
滩野亮
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Central Glass Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/22—Esters containing halogen
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/20—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

Abstract

The present invention provides a fluorine-containing polymer which is a pattern-forming material which exhibits water repellency after film formation and is rendered hydrophilic by an acid upon light irradiation when the fluorine-containing polymer is formed into a film together with a photoacid generator, and which does not contain a perfluoroalkyl group having 4 or more carbon atoms and imparts a pattern with high sensitivity and high resolution. The fluoropolymer of the present invention is characterized by containing a repeating unit represented by formula (1). (in the formula, R1Is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms, R2～R5Is hydrogen atom, alkyl group with 1-10 carbon atoms, X is single bond or 2-valent group, Y is fluorine-containing alkyl group with 1-3 carbon atoms or carboxylic ester group (-COOR), R is fluorine-containing alkyl group with 1-3 carbon atoms; less than 7 hydrogen atoms contained in these groups being optionally substituted by fluorine atoms)

Description

Fluorine-containing monomer, fluorine-containing polymer, composition for forming pattern using same, and method for forming pattern using same
Technical Field
The present invention relates to a fluorine-containing monomer, a fluorine-containing polymer, a composition for forming a pattern using the same, and a method for forming the pattern. In particular, the present invention relates to a fluorine-containing polymer and a fluorine-containing monomer as a precursor thereof, a composition for forming a pattern using the same, and a method for forming a pattern using the same, and the fluorine-containing polymer is used for a resist material used for photolithography in semiconductor manufacturing, or for an electronic circuit formed by an ink in electronic device manufacturing, for example, a Printed electronic technology (Printed electronics) in which a pattern circuit is formed by a conductive film ink on a glass or resin substrate by printing using a conductive ink.
Background
Fluoropolymers are known to have excellent properties due to the presence of fluorine atoms in their chemical structure. Fluoropolymers having water repellency, heat resistance, transparency, low refractive index, photosensitivity, and the like are used as resist materials in semiconductor manufacturing and pattern forming materials in printed electronics.
A resist film is formed by adding a photoacid generator to a fluorine-containing polymer having an acid-decomposable group used as a resist material in the production of semiconductors, and an acid is generated from the photoacid generator by light irradiation, whereby the acid-decomposable group is dissociated from the fluorine-containing polymer by the generated acid, whereby the property of being soluble or insoluble in a developing solution is changed, and a pattern can be formed on the resist film. In printed electronics, fluoropolymers are applied as materials for pattern forming films provided with a pattern that repels or does not repel ink.
In general, in the case of using a fluoropolymer having a fluorine-containing acid-decomposable group as a pattern forming material, the resulting fluoropolymer film exhibits high water repellency before light irradiation, and the irradiated portion is changed from water repellency to hydrophilicity by dissociation of the fluorine-containing acid-decomposable group after light irradiation.
In the printed electronics technology, when a film containing a pattern forming material is irradiated with light through a mask having a pattern formed thereon, a hydrophobic-hydrophilic pattern including a hydrophobic portion that has not been irradiated and a hydrophilic portion after irradiation is formed, to which the mask pattern has been transferred, and then, when ink is applied, the ink is repelled by the hydrophobic portion, thereby forming a pattern from the ink.
For example, patent documents 1 and 2 disclose, as a pattern forming material for printed electronics technology for imparting a lyophilic and lyophobic pattern, a resin having a long-chain perfluoroalkyl group having 6 or more carbon atoms for forming a high-definition pattern by suppressing wet diffusion and penetration of ink, and describe that patterns of a lyophilic portion and a lyophobic portion with respect to ink are formed by dissociation caused by irradiation of perfluoroalkyl gene light contained in these resins.
However, with respect to a resin having a long-chain perfluoroalkyl group, there is a fear that it is difficult to burn and decompose and accumulates in the environment. For example, perfluorooctanoic acid is indicated by the national environmental protection agency to accumulate in the environment and be required to be reduced in use. As described above, the fluorine compound having a perfluoroalkyl group having 6 or more carbon atoms is preferably avoided from the viewpoint of accumulation in the environment.
As a polymer having an acid-decomposable group used as a resist material in semiconductor production, a polymer having a cyclic acetal skeleton at an acid dissociation portion is known. Since a polymer having a cyclic acetal skeleton in an acid dissociation portion exhibits excellent acid dissociation properties, it has been developed particularly as a radiation-sensitive patterning composition in the field of electronic materials.
For example, patent document 3 discloses a pattern forming method using a radiation-sensitive resin composition containing a polymer containing a fluorine-free cyclic acetal monomer such as 2-tetrahydrofurfuryl methacrylate as an acid-dissociable monomer, and a photoacid generator. Patent document 4 discloses a positive photosensitive composition as a pattern forming material having high sensitivity, high resolution, and a large residual film ratio during development, the positive photosensitive composition including: a polymer obtained by copolymerizing a monomer having a cyclic acetal group not containing fluorine, a monomer having an acid-decomposable group, and a monomer having a crosslinkable group; and a radiation sensitive acid generator.
Patent document 5 discloses a fluoropolymer having a cyclic hemiacetal structure and a fluoromonomer as a precursor. Patent document 6 discloses that the cyclic hemiacetal structure of a fluorinated monomer having a cyclic hemiacetal structure is modified with a substituent and that the substituent is selected, whereby the water repellency, lipid solubility and acid decomposition properties of the fluorinated monomer when produced into a fluorinated polymer can be adjusted.
Documents of the prior art
Patent document
Patent document 1: booklet of international publication WO2014/178279
Patent document 2: japanese patent laid-open publication No. 2016-
Patent document 3: japanese laid-open patent publication No. 4-26850
Patent document 4: japanese patent laid-open No. 2012-42837
Patent document 5: japanese patent laid-open publication No. 2006-152255
Patent document 6: japanese laid-open patent application No. 2010-106138
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a fluorine-containing polymer that does not contain a perfluoroalkyl group having 4 or more carbon atoms, which exhibits water repellency after film formation and before light irradiation and becomes hydrophilic after light irradiation due to the action of an acid generated from a photoacid generator when a film containing the photoacid generator is formed in photoresists or printed electronics, and which has a high contact angle with water before light irradiation and a low contact angle after light irradiation, and which is a composition for pattern formation for imparting a highly sensitive and high-resolution pattern. Another object of the present invention is to provide a pattern-forming composition containing the fluoropolymer as a pattern-forming material, and a pattern-forming method using the pattern-forming composition. Further, an object of the present invention is to provide a fluoromonomer and a fluorinated compound which are precursors of the above-mentioned fluoropolymer, and a method for producing the same.
Means for solving the problems
As shown in examples of the present specification, the present inventors newly synthesized a fluoropolymer (hereinafter, sometimes referred to as fluoropolymer (1)) containing a repeating unit (1) having an acid-decomposable group having a fluorine-containing cyclic acetal skeleton in which a trifluoromethyl group is bonded to a specific position (1). Next, a film is formed by spreading the composition for pattern formation containing the fluoropolymer (1) of the present invention on a substrate.
Figure GDA0003005189880000031
(in the formula, R1Is a hydrogen atom, a fluorine atom or a straight-chain alkyl group having 1 to 10 carbon atoms. R2～R5Is a hydrogen atom or a straight chain alkyl group having 1 to 10 carbon atoms. X is a single bond or a 2-valent group. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and R is a C1-3 fluoroalkyl group. )
Next, each pattern-forming composition is prepared by adding a photoacid generator, a solvent, and the like to the fluoropolymer (1) of the present invention, the fluoropolymer containing the repeating unit (a) described in patent document 6 shown below, the fluoropolymer containing the repeating unit (B) described in patent document 3, or the fluoropolymer containing the repeating unit (C) known as a general-purpose resist material, and then the resulting composition is developed on a substrate, film-formed, and heat-cured.
Thus, the film comprising the fluoropolymer (1) showed a higher contact angle of about 10 ° with water as compared with the films comprising the fluoropolymer (a) and the fluoropolymer (B) (see examples 1 to 7 and comparative examples 1 to 2 in [ table 3] of the example). Further, as a result of measuring the etching sensitivity, the resist film containing the fluoropolymer (1) showed higher sensitivity than the resist film containing the fluoropolymer containing the repeating unit (a) or the resist film containing the repeating unit (B). The resist film containing the fluoropolymer (1) exhibits higher sensitivity than the resist films containing the copolymer having the repeating unit (A), the copolymer having the repeating unit (B) and the copolymer having the repeating unit (C) (refer to resists 1 to 3 and comparative resists 1 to 3 in [ Table 4] of the examples). Since the resist film containing the fluoropolymer (1) exhibits higher sensitivity than the resist film containing the fluoropolymer having the repeating unit (a), it is presumed that: the fluoropolymer (1) of the present invention has a cyclic acetal structure containing fluorine, and has higher acid decomposability than the fluoropolymer (a) containing a repeating unit (a).
Figure GDA0003005189880000041
Next, a mask having a pattern of lines and spaces (line and space) of 30nm was prepared, and each film was irradiated with ultraviolet light through the mask, and as a result, it was found that a resist pattern formed from a composition for pattern formation containing a fluoropolymer which is the fluoropolymer (1) of the present invention had high sensitivity and high resolution as compared with a resist pattern formed from another composition for pattern formation which is not the scope of the present invention. (resists 1 to 3 and comparative resists 1 to 3 in [ Table 4] of reference example)
As described above, the present inventors have confirmed that a fluorine-containing polymer containing no perfluoroalkyl group having 4 or more carbon atoms exhibits high water repellency before light irradiation after film formation when a film containing a photoacid generator is formed in photolithography and printed electronics, and becomes hydrophilic by the action of an acid generated from the photoacid generator after light irradiation, whereby the contact angle with water before light irradiation is high and the contact angle after light irradiation is low, and thus a pattern-forming composition for imparting a highly sensitive and highly precise pattern is obtained.
That is, the present invention includes the following inventions 1 to 16.
[ invention 1]
A fluorine-containing polymer comprising a repeating unit represented by the formula (1).
Figure GDA0003005189880000051
(in the formula, R1Is a hydrogen atom, a fluorine atom, or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atomsAnd (4) generation. R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. X is a single bond or a 2-valent group, and 7 or less hydrogen atoms included in the 2-valent group are optionally substituted by fluorine atoms. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. )
[ invention 2]
The fluoropolymer according to claim 1, wherein R in the formula (1)2、R4、R5Is a hydrogen atom.
[ invention 3]
The fluoropolymer according to claim 2, wherein Y in the formula (1) is a trifluoromethyl group.
[ invention 4]
A resist pattern-forming composition comprising the fluoropolymer according to inventions 1 to 3, an acid generator, a basic compound and a solvent.
[ invention 5]
A method of forming a resist pattern, comprising the steps of:
a film formation step of coating the composition for resist pattern formation according to invention 4 on a substrate to form a film;
an exposure step of irradiating electromagnetic waves or high-energy rays having an exposure wavelength of 300nm or less through a mask to transfer a pattern of the mask onto the film; and
and a developing step of developing the film with a developer to obtain a pattern.
[ invention 6]
An ink pattern-forming composition containing the fluoropolymer according to inventions 1 to 3, an acid generator, and a solvent.
[ invention 7]
A method of forming an ink pattern, comprising the steps of:
a film forming step of coating the composition for forming an ink pattern according to invention 6 on a substrate to form a film;
an exposure step of irradiating the film with light having an exposure wavelength of 150nm to 500nm through a mask to transfer a pattern of the mask onto the film, thereby obtaining a pattern-forming film having a lyophobic portion and a lyophilic portion; and
a pattern forming step of coating ink on the obtained pattern forming film.
[ invention 8]
An ink pattern forming method, comprising the steps of:
a film forming step of applying the composition for ink pattern formation according to invention 6 on a substrate and heating (prebaking) the obtained coating film;
a pattern forming step of subsequently scanning the film with light having an exposure wavelength of 150nm or more and 500nm or less by a drawing device, drawing a pattern on the film, obtaining a pattern forming film having a lyophobic portion and a lyophilic portion, and coating ink on the obtained pattern forming film.
[ invention 9]
A fluorine-containing monomer represented by formula (4).
Figure GDA0003005189880000071
(in the formula, R1The alkyl group is a straight-chain or branched alkyl group having 1 to 10 carbon atoms or a hydrogen atom, fluorine atom or a branched alkyl group having 3 to 10 carbon atoms, and 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted by fluorine atoms. R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. X is a single bond or a 2-valent group, and 7 or less hydrogen atoms included in the 2-valent group are optionally substituted by fluorine atoms. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. )
[ invention 10]
According toThe fluoromonomer according to claim 9, wherein R in the above formula (4)2、R4、R5Is a hydrogen atom.
[ invention 11]
The fluorine-containing monomer according to the invention 10, wherein Y in the formula (4) is a trifluoromethyl group.
[ invention 12]
The method for producing a fluorine-containing monomer represented by formula (4) according to invention 9 comprises the steps of: a cyclic hemiacetal compound represented by formula (7) is obtained by cyclizing a hydroxycarbonyl compound represented by formula (10) below, a hydroxyvinyl ether or a hydroxyvinyl ester represented by formula (11) below.
Figure GDA0003005189880000072
(in the formula, R1The alkyl group is a straight-chain or branched alkyl group having 1 to 10 carbon atoms or a hydrogen atom, fluorine atom or a branched alkyl group having 3 to 10 carbon atoms, and 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted by fluorine atoms. R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. X is a single bond or a 2-valent group, and 7 or less hydrogen atoms included in the 2-valent group are optionally substituted by fluorine atoms. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. Z is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein part or all of the hydrogen atoms in Z are optionally substituted with a halogen atom, and wherein Z optionally contains an ether bond, a siloxane bond, a thioether bond or a carbonyl bond. )
[ invention 13]
A fluorine-containing cyclic hemiacetal represented by formula (7).
Figure GDA0003005189880000081
(in the formula, R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. )
[ invention 14]
The fluorine-containing cyclic hemiacetal according to the invention 13, wherein R in the above formula (7)2、R4、R5Is a hydrogen atom.
[ invention 15]
The fluorine-containing cyclic hemiacetal according to the invention 14, wherein Y in the formula (7) is a trifluoromethyl group.
[ invention 16]
A process for producing a fluorine-containing cyclic hemiacetal, which comprises cyclizing a hydroxycarbonyl compound represented by the following formula (10), a hydroxyvinyl ether or a hydroxyvinyl ester represented by the following formula (11), to obtain a fluorine-containing cyclic hemiacetal represented by the formula (7) according to any one of the inventions 13 to 15.
Figure GDA0003005189880000091
(in the formula, R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. Z is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein part or all of the hydrogen atoms in Z are optionally substituted with a halogen atom, and wherein Z optionally contains an ether bond, a siloxane bond, a thioether bond or a carbonyl bond. )
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there is obtained a fluorine-containing polymer containing no perfluoroalkyl group having 4 or more carbon atoms, which exhibits water repellency before light irradiation after film formation and which is hydrophilic after light irradiation due to dissociation of an acid-decomposable group containing fluorine by the action of an acid generated from a photoacid generator after light irradiation, when used for producing a film containing a photoacid generator in photoresists or printed electronics, and which has a high contact angle with water before light irradiation and a low contact angle after light irradiation, and which is a pattern-forming composition for imparting a highly sensitive and high-resolution pattern. Further, a pattern-forming composition containing the fluoropolymer as a pattern-forming material and a pattern-forming method using the pattern-forming composition were obtained. Further, a fluorine-containing monomer and a fluorine-containing compound which are precursors of the above-mentioned fluorine-containing polymer, and a process for producing the same are obtained.
The polymer having a fluorine-containing cyclic acetal skeleton of the present invention contains a C1-3 perfluoroalkyl group and does not contain a C4 or more perfluoroalkyl group, and therefore, there is no concern about accumulation in the environment.
Detailed Description
The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiments, and it should be understood that appropriate modifications and improvements to the following embodiments based on common general knowledge of those skilled in the art are also within the scope of the present invention.
1. Fluorine-containing polymer
[ fluoropolymer (1) ]
The fluorine-containing polymer of the present invention is a polymer having a cyclic acetal structure containing fluorine and containing a repeating unit represented by formula (1). Hereinafter, the fluoropolymer (1) may be referred to as "fluoropolymer".
Figure GDA0003005189880000101
(in the formula, R1Is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms. R2～R5Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X isA single bond or a 2-valent group. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR) (R is a C1-3 fluoroalkyl group.)
For R in formula (1)1、R2、R3、R4、R5X, Y.
[R1]
In the formula, R1The alkyl group is a straight-chain or branched alkyl group having 1 to 10 carbon atoms or a hydrogen atom, fluorine atom or a branched alkyl group having 3 to 10 carbon atoms, and 7 or less hydrogen atoms among hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted by fluorine atoms.
R1Examples may be given of: hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, fluorine atom, trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, 1,1,1,3,3, 3-hexafluoroisopropyl group (-C (CF)3)2H) Heptafluoroisopropyl. In terms of ease of polymerization, R1Preferably a hydrogen atom, a fluorine atom or a methyl group.
[R2～R5]
R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms.
To R2～R5From the viewpoint of ease of synthesis, an electron donating alkyl group is preferable to an electron withdrawing substituent, and a sterically-unhindered hydrogen atom or methyl group is preferable.
[X]
X is a single bond or a 2-valent group, and 7 or less hydrogen atoms included in the 2-valent group are optionally substituted by fluorine atoms.
X is preferably a 2-valent group having 2 to 10 carbon atoms, and includes: methylene, alkylene having 2 to 10 carbon atoms, alkenylene having 2 to 10 carbon atoms, aryl having 2 valence having 6 to 10 carbon atoms, or alicyclic hydrocarbon having 2 valence having 4 to 10 carbon atoms. The alkylene group or alkenylene group may contain an ether bond (-O-), a carbonyl group (- (C ═ O-), a carboxyl group (- (C ═ O) O-or-O (C ═ O) -, and since the lyophobicity decreases if the 2-valent group is long, it is preferably a single bond, and an oxyethylene group (-O-CH) —2-CH2-) or oxygenAcetyl (-O-CH)2-CO-)。
[Y]
Y is a C1-3 fluoroalkyl group or a C1-3 carboxylate group (-COOR) (R is a C1-3 fluoroalkyl group). The fluorine-containing alkyl group or the carboxylate group contains 7 or less hydrogen atoms optionally substituted with fluorine atoms.
Y may be exemplified by: trifluoromethyl, trifluoroethyl, pentafluoroethyl, trifluoropropyl, 1,1,1,3,3, 3-hexafluoroisopropyl or heptafluoroisopropyl. From the viewpoint of ease of synthesis, trifluoromethyl, trifluoroethyl, and 1,1,1,3,3, 3-hexafluoroisopropyl are preferable.
In the fluorine-containing monomer (1) of the present invention, depending on the kind and combination of the substituents shown above, there may be asymmetric carbon-hydrogen atoms in the molecule, and enantiomers (enatiomers) and diastereomers (isomers having 2 or more asymmetric carbon atoms, which are stereoisomers having no enantiomeric relationship) may be present. However, formula (1) represents all of these stereoisomers representatively. The stereoisomers may be used alone or in the form of a mixture.
[ fluoropolymer (2) ]
The fluoropolymer (1) of the present invention preferably contains R in the above formula (1)2、R4、R5A fluorine-containing polymer having the following repeating unit (2) which is a hydrogen atom. In view of the solubility in a solvent when the fluoropolymer (1) is formed into a composition for forming a pattern on a substrate, R in the above formula (1) is preferred2、R4、R5The polymer which is suitably used in the present invention is preferably a polymer having a fluorine-containing cyclic acetal structure and containing a repeating unit represented by the formula (2) as a hydrogen atom. Hereinafter, the fluoropolymer (2) may be referred to as "fluoropolymer".
Figure GDA0003005189880000121
(R in the formula1、R3X, Y has the same meaning as in formula (1). )
[ fluoropolymer (3) ]
The fluoropolymer (1) of the present invention is more preferably a fluoropolymer (3) containing a repeating unit (3) wherein Y in the formula (1) is trifluoromethyl or less. Further, in view of solubility in a solvent, Y in the formula (1) is preferably a trifluoromethyl group, and a polymer having a fluorine-containing cyclic acetal structure and containing a repeating unit represented by the formula (3) is preferable. Hereinafter, the fluoropolymer (3) may be referred to as "fluoropolymer".
Figure GDA0003005189880000122
(R in the formula1、R3X is the same as formula (1). )
1-1. decomposition of fluoropolymer (1) by acid
It is known that the cyclic acetal structure is decomposed by an acid generated from an acid generator, as in the case of an ordinary acetal. It is presumed that the following reaction proceeds similarly in the fluorinated cyclic acetal structure of the fluoropolymer (1) of the present invention.
It is presumed that the contact angle of ink to a film is decreased and a function of forming a pattern by ink is exhibited by two reaction paths shown by the following formula, that is, the acid-decomposable group (1B) is dissociated from the fluorine-containing polymer (1) and the repeating unit shown in formula (1A) remains, or the repeating unit shown in formula (1C) is generated by ring opening of the fluorine-containing cyclic acetal structure, and the water-repellent fluorine-containing polymer (1) generates a fluorine-containing polymer containing the hydrophilic repeating unit shown in formula (1A) or the repeating unit shown in formula (1C).
Figure GDA0003005189880000131
1-2 monomers imparting other repeating units
The fluoropolymer (1) of the present invention may contain other repeating units than the repeating unit (1). The repeating units other than the repeating unit (1) are added to the structure of the fluoropolymer (1) for the purpose of adjusting the solvent solubility of the fluoropolymer (1) when a film is formed from the composition for pattern formation containing the fluoropolymer (1) as a component, the hardness of the film when the film is formed, and the like.
The fluorine-containing polymer (1) comprising the repeating unit (1) and other repeating units is obtained by copolymerizing a fluorine-containing monomer (4) imparting the repeating unit (1) with a monomer imparting other repeating units.
The monomer to which the other repeating unit is added may be copolymerized with the fluorine-containing monomer (4) to which the repeating unit (1) is added, as long as it has a polymerizable unsaturated bond, and examples of the monomer to which the other repeating unit is added include: adhesion group-imparting monomer, acrylate, fluorine-containing acrylate, methacrylate, fluorine-containing methacrylate, and fluorine-containing methacrylate having hexafluoroisopropanol group (-C (CF)3)2OH, hereinafter sometimes referred to as HFIP group), styrenes, fluorine-containing styrenes, vinyl ethers, allyl ethers, fluorine-containing vinyl ethers, fluorine-containing allyl ethers, olefins, fluorine-containing olefins, norbornenes, fluorine-containing norbornenes, or other monomers having a polymerizable unsaturated bond.
[ monomer having an adhesive group ]
When the fluoropolymer (1) is used as a resist component, adhesion suitable for a substrate can be obtained in photolithography by introducing an adhesive group into the chemical structure. Examples of the adhesive group include a group having a lactone structure.
When an adhesive group is introduced into the fluoropolymer (1) of the present invention, a monomer containing a group having a monocyclic or polycyclic lactone structure, which is copolymerizable with the fluorine-containing monomer (4), may be used.
As the monocyclic lactone structure, there can be exemplified: examples of the lactone structure having a polycyclic structure, which is a group obtained by removing 1 hydrogen atom from γ -butyrolactone or mevalonolactone (Mevalonic lactone), include: a group in which 1 hydrogen atom is removed from norbornane lactone to form an atomic bond. The lactone structure is introduced into the fluoropolymer (1) of the present invention by copolymerizing an acrylate or methacrylate ester containing a lactone structure. Thus, when the fluoropolymer (1) is used as a resist component for photolithography, not only the adhesion to the substrate but also the affinity with the developer can be expected to be improved.
As the repeating unit that imparts adhesion to the substrate when a resist film is formed, the following repeating unit can be exemplified.
Figure GDA0003005189880000141
From the viewpoint of ease of obtaining, 5-methacryloyloxy-2, 6-norbornanecarbonolide (hereinafter, may be referred to as MNLA) is particularly preferable. The upper diagram is shown as MNLA.
[ acrylates ]
As the acrylic esters, there can be exemplified: methyl acrylate, ethyl acrylate, N-propyl acrylate, isopropyl acrylate, N-butyl acrylate, isobutyl acrylate, N-hexyl acrylate, N-octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate, or an acrylate having an ethylene glycol, propylene glycol or 1, 4-butanediol group, or acrylamide, N-methylolacrylamide or diacetone acrylamide as an unsaturated amide, or tert-butyl acrylate, 3-oxocyclohexyl acrylate, adamantyl acrylate, methyladamantyl acrylate, ethyladamantyl acrylate, hydroxyadamantyl acrylate, cyclohexyl acrylate or tricyclodecyl acrylate, or an acrylate having a ring structure such as a lactone ring or a norbornene ring, or a salt thereof, Or those acrylates having a cyano group in the alpha position.
[ fluorine-containing acrylates ]
Examples of the fluorine-containing acrylates include: a fluorine-containing acrylate having a fluorine-containing organic group at the alpha-position or ester position of the acrylic acid position. The fluorine-containing organic group may be present in both the α -position and the ester position, and the fluorine-containing organic group may further have a cyano group in the α -position and a fluorine-containing alkyl group in the ester position.
Examples of the fluorine-containing organic group of the fluorine-containing acrylate at the α -position include: trifluoromethyl, trifluoroethyl or nonafluoro-n-butyl.
Examples of the fluorine-containing organic group at the ester site of the fluorine-containing acrylate include: perfluoro or a fluorine-containing alkyl group containing a hydrogen atom, or a group containing a fluorine-containing benzene ring, a fluorine-containing cyclopentane ring, a fluorine-containing cyclohexane ring or a fluorine-containing cycloheptane ring in which a hydrogen atom having a cyclic structure is substituted with a fluorine atom, a trifluoromethyl group or an HFIP group.
As the fluorine-containing acrylates, there can be exemplified: 2,2, 2-trifluoroethyl acrylate, 2,2,3, 3-tetrafluoropropyl acrylate, 1,1,1,3,3, 3-hexafluoroisopropyl acrylate, heptafluoroisopropyl acrylate, 1, 1-dihydroheptafluoro-n-butyl acrylate, 1,1, 5-trihydrooctafluoro-n-pentyl acrylate, 1,1,2, 2-tetrahydrotridecafluoro-n-octyl acrylate, 1,1,2, 2-tetrahydroheptadecafluoro-n-decyl acrylate, 6- [3,3, 3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl ] bicyclo [2.2.1] hept-2-yl-2- (trifluoromethyl) acrylate, 1, 4-bis (1,1,1,3,3, 3-hexafluoro-2-hydroxyisopropyl) cyclohexyl acrylate, or 1, 4-bis (1,1,1,3,3, 3-hexafluoro-2-hydroxyisopropyl) cyclohexyl-2-trifluoromethyl acrylate.
[ methacrylic acid esters ]
As the methacrylic acid esters, there can be exemplified: methyl methacrylate, ethyl methacrylate, N-propyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, N-hexyl methacrylate, N-octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, or methacrylates having ethylene glycol, propylene glycol or 1, 4-butanediol groups, or methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide or diacetoneacrylamide as unsaturated amides, or tert-butyl methacrylate, 3-oxocyclohexyl methacrylate, adamantyl methacrylate, methyladamantyl methacrylate, ethyladamantyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, N-hexyl methacrylate, N-octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, or tert-butyl methacrylate, 3-oxocyclohexyl methacrylate, adamantyl methacrylate, methyladamantyl methacrylate, ethyl adamantyl methacrylate, or mixtures thereof, Hydroxyadamantyl methacrylate, cyclohexyl methacrylate, tricyclodecanyl methacrylate, or a methacrylate having a ring structure such as a lactone ring or a norbornene ring.
[ fluorinated methacrylates ]
Examples of the fluorine-containing methacrylic esters include fluorine-containing methacrylic esters having a fluorine-containing organic group at an ester portion.
As such fluorine-containing organic group, there can be exemplified: perfluoro or a fluorine-containing alkyl group containing a hydrogen atom, or a fluorine-containing benzene ring, a fluorine-containing cyclopentane ring, a fluorine-containing cyclohexane ring or a fluorine-containing cycloheptane ring in which a hydrogen atom of a cyclic structure is substituted with a fluorine atom, a trifluoromethyl group, an HFIP group or the like.
As the fluorine-containing acrylates, there can be exemplified: 2,2, 2-trifluoroethyl methacrylate, 2,2,3, 3-tetrafluoropropyl methacrylate, 1,1,1,3,3, 3-hexafluoroisopropyl methacrylate, heptafluoroisopropyl methacrylate, 1, 1-dihydroheptafluoro-n-butyl methacrylate, 1,1, 5-trihydrooctafluoro-n-pentyl methacrylate, 1,1,2, 2-tetrahydrotridecafluoro-n-octyl methacrylate, 1,1,2, 2-tetrahydroheptadecafluoro-n-decyl methacrylate, perfluorocyclohexylmethyl acrylate, perfluorocyclohexylmethyl methacrylate, 6- [3,3, 3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl ] bicyclo [2.2.1] hept-2-yl methacrylate or 1, 4-bis (1,1,1,3,3, 3-hexafluoro-2-hydroxyisopropyl) cyclohexyl.
[ monomer having HFIP group ]
As the monomer having an HFIP group, the monomers shown below can be exemplified.
Figure GDA0003005189880000171
(R9Represents a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group; further, as the HFIP group, part or all of which is optionally protected with a protecting group)
[ styrenes and fluorinated styrenes ]
As the styrene, styrene and hydroxystyrene may be exemplified.
Examples of the fluorine-containing styrenes include: pentafluorostyrene, trifluoromethylstyrene, bis (trifluoromethyl) styrene, styrene in which a hydrogen atom of an aromatic ring structure is substituted with a fluorine atom or a trifluoromethyl group, styrene in which a hydrogen atom of an aromatic ring structure is substituted with an HFIP group or an HFIP group in which a hydroxyl group thereof is protected with a protecting group, styrene in which a halogen atom, an alkyl group or a fluoroalkyl group is bonded to an α -position, or styrene containing a perfluorovinyl group.
[ vinyl ethers, allyl ethers, fluorine-containing vinyl ethers, fluorine-containing allyl ethers ]
The vinyl ethers or allyl ethers may comprise methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hydroxyethyl or hydroxybutyl, and may be alkyl vinyl ethers or alkyl allyl ethers. In the case of vinyl ethers containing a hydroxyethyl group or a hydroxybutyl group, the alcohol moiety can form an ester bond through an acetyl group, a butyryl group, or a propionyl group. The aromatic ring may be a cyclopentyl group, a cyclohexyl group, a norbornenyl group, a cyclic vinyl ether or a cyclic allyl ether having a hydrogen atom or a carbonyl bond in the cyclic structure. Examples of the fluorine-containing vinyl ether and fluorine-containing allyl ether include: these vinyl ethers or allyl ethers are fluorine-containing vinyl ethers or fluorine-containing allyl ethers in which a part or all of the hydrogen atoms of the vinyl ethers or allyl ethers are substituted with fluorine atoms.
[ olefins and fluoroolefins ]
As olefins, there can be exemplified: ethylene, propylene, isobutylene, cyclopentene or cyclohexene. Examples of the fluorine-containing olefins include: vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene or hexafluoroisobutylene, 1-chloro-2, 3,3,4,4,5, 5-heptafluorocyclopentene, octafluorocyclopentene or decafluorocyclopentene.
[ norbornenes and fluorine-containing norbornenes ]
The norbornene and the fluorine-containing norbornene may have only one norbornene skeleton but a plurality of norbornene skeletons as long as they have a polymerizable group. The norbornene or fluorine-containing norbornene is produced by Diels-Alder (Diels-Alder) addition reaction of an unsaturated compound and a diene compound.
As such unsaturated compounds, there can be exemplified: fluorine-containing olefin, allyl alcohol, fluorine-containing allyl alcohol, homoallyl alcohol, fluorine-containing homoallyl alcohol, acrylic acid, α -fluoroacrylic acid, α -trifluoromethylacrylic acid, methacrylic acid, the above-mentioned acrylate, methacrylate, fluorine-containing acrylate or fluorine-containing methacrylate, 2- (benzoyloxy) pentafluoropropane, 2- (methoxyethoxymethyloxy) pentafluoropropene, 2- (tetrahydroxypyranyloxy) pentafluoropropene, 2- (benzoyloxy) trifluoroethylene, or 2- (methoxymethyloxy) trifluoroethylene. As the diene compound, there can be exemplified: cyclopentadiene or cyclohexadiene.
As the fluorine-containing norbornene compound, there can be exemplified: 3- (5-bicyclo [2.2.1] hepten-2-yl) -1,1, 1-trifluoro-2- (trifluoromethyl) -2-propanol.
[ other monomers having polymerizable unsaturated bond ]
As other monomers having a polymerizable unsaturated bond, there can be exemplified: acrylic acid, methacrylic acid, acrylonitrile, maleic acid, fumaric acid, maleic anhydride.
When the length of the organic group at the self-polymerization site is long or the monomer contains many hetero atoms, the following may occur: the influence of the organic group derived from another repeating unit becomes strong, the effect of the fluorine-containing alkyl group at the terminal on the lyophobicity is reduced, and the solubility of the polymer is lowered. Therefore, as the other monomer, an acrylic acid ester or a methacrylic acid ester having a carbon number of less than 10 is preferable, and methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, or isobutyl methacrylate is particularly preferable.
1-3. content ratio of each repeating unit in the fluoropolymer (1)
The content ratio of the repeating unit represented by the formula (1) to the total amount of the fluoropolymer (1) is 10 mol% or more and 100 mol% or less, and more preferably 10 mol% or more and 90 mol% or less. If the content of the repeating unit (1) in the fluoropolymer (1) is less than 10 mol%, water repellency cannot be obtained in an unexposed portion of a pattern forming film formed by exposing a film containing the fluoropolymer (1).
The content ratio of the repeating unit derived from another monomer to the total amount of the fluoropolymer (1) is preferably 0 mol% or more and 90 mol% or less, and more preferably 10 mol% or more and 90 mol% or less.
The repeating units derived from other monomers are used for improving the solubility of the fluoropolymer (1) in an organic solvent, the adhesion to a substrate when formed into a film, the hardness, and the like. If not necessary, it may not be used, but if less than 10 mol%, adhesion to the substrate or hardness during film formation does not increase, and if more than 90 mol%, the content of the repeating unit (1) decreases, making it difficult to obtain the effect of obtaining water repellency in the unexposed portion and the effect of obtaining hydrophilicity in the exposed portion of a pattern forming film formed by exposing a film comprising the fluoropolymer (1).
1-4 molecular weight of fluoropolymer (1)
The fluoropolymer (1) of the present invention has a number average molecular weight of 1000 or more and 100000 or less, preferably 3000 or more and 50000 or less. The molecular weight dispersion is 1 to 4 inclusive, preferably 1 to 2.5 inclusive. If the number average molecular weight is less than 1000, a film containing the pattern-forming composition containing the fluoropolymer (1) as a component becomes soft, and it becomes difficult to form a film of a desired thickness. In addition, in the pattern forming film after exposure, it is difficult to form a fine pattern including a lyophobic part and a lyophilic part, and there is a fear that the pattern lacks durability. When the number average molecular weight is more than 100000, the fluoropolymer (1) is difficult to dissolve in a solvent, cracks occur after film formation, and it is difficult to form a film containing a pattern-forming composition containing the fluoropolymer (1) as a component as a coating film.
2. Synthesis of fluoropolymers
[ Synthesis of fluoropolymer (1) ]
The synthesis of the fluoropolymer (1) of the present invention can be selected from commonly used polymerization methods. Radical polymerization and ionic polymerization are preferable, and coordination anionic polymerization, living anionic polymerization and cationic polymerization may be selected according to the case. The reactor used in the polymerization reaction is not particularly limited. In addition, in the polymerization, a polymerization solvent may be used. The radical polymerization will be described below.
The radical polymerization can be carried out by: the polymerization may be carried out by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization in the presence of a radical polymerization initiator or a radical initiator, in any of a batch type, a semi-continuous type or a continuous type.
< free radical polymerization initiator >
Examples of the radical polymerization initiator include: azo compounds, peroxide compounds, and redox compounds.
As the azo-based compound, azobisisobutyronitrile can be exemplified. Examples of the peroxide-based compound include: t-butyl peroxypivalate, di-t-butyl peroxide, isobutyryl peroxide, lauroyl peroxide, succinic peroxide, dicumyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxyallylmonocarbonate, benzoyl peroxide, hydrogen peroxide, or ammonium persulfate.
< polymerization solvent >
The polymerization solvent is preferably a solvent which does not inhibit radical polymerization, and examples thereof include: an ester-based solvent, a ketone-based solvent, a hydrocarbon-based solvent, or an alcohol-based solvent. Other solvents may be used, such as water, ether-based solvents, cyclic ether-based solvents, freon-based solvents, or aromatic-based solvents.
As the polymerization solvent, there can be exemplified: ethyl acetate or n-butyl acetate as an ester solvent, acetone or methyl isobutyl ketone as a ketone solvent, toluene or cyclohexane as a hydrocarbon solvent, and methanol, isopropyl alcohol or ethylene glycol monomethyl ether as an alcohol solvent.
These polymerization solvents may be used alone or in combination of two or more. In addition, a molecular weight modifier such as thiol may be used in combination.
< polymerization conditions >
The polymerization temperature may be appropriately selected depending on the kind of the radical polymerization initiator or the radical polymerization initiator. The type of the radical polymerization initiator or the radical polymerization initiator is preferably selected as appropriate so that the polymerization temperature is 20 ℃ or more and 200 ℃ or less, preferably 30 ℃ or more and 140 ℃ or less. The molecular weight of the fluoropolymer (1) can be controlled by adjusting the selection of the radical polymerization initiator or the radical polymerization initiator and the polymerization conditions.
In addition, as a method for removing the above-mentioned polymerization solvent such as an organic solvent or water from the solution or dispersion containing the fluoropolymer (1) after polymerization, a known method can be used, and examples thereof include: reprecipitating, filtering or distilling under reduced pressure by heating.
When the fluoropolymer (1) of the present invention is used as a resist component, the solubility of the developer of the fluoropolymer (1) varies depending on the molecular weight of the fluoropolymer (1), and the patterning conditions for photolithography vary. When the molecular weight of the fluoropolymer (1) is high, the dissolution rate in the developer tends to be low, and when the molecular weight is low, the dissolution rate tends to be high. The molecular weight of the fluoropolymer (1) can be controlled by adjusting the polymerization conditions.
3. Composition for forming resist pattern
The resist pattern-forming composition of the present invention is obtained by adding an acid generator, a basic compound and a solvent to any one of the fluoropolymers (1) to (3), and can be used for lithography. Hereinafter, the composition for forming a resist pattern may be simply referred to as a resist.
The fluoropolymers (1) to (3) of the present invention are particularly suitable as components of photosensitive positive resists. The resist of the present invention is useful for providing a resist, particularly a photosensitive positive resist material, containing the fluoropolymers (1) to (3).
The resist of the present invention preferably contains (a) any one of the fluoropolymers (1) to (3) of the present invention, (B) a photoacid generator, (C) a basic compound, and (D) a solvent as resist components. Further, (E) a surfactant may be added as required.
3-1.(B) photoacid generators
The photoacid generator used in the resist of the present invention is not particularly limited, and any one selected from those used as an acid generator for a chemically amplified resist can be used, and examples thereof include onium sulfonates and sulfonic acid esters. Examples may include: iodonium sulfonate, sulfonium sulfonate, N-imide sulfonate, N-oxime sulfonate, o-nitrobenzyl sulfonate, or pyrogallol trimethosulfonate.
The acid generated from these photoacid generators by exposure in photolithography is an alkanesulfonic acid, an aromatic sulfonic acid, or an aromatic sulfonic acid or alkanesulfonic acid which is partially or completely fluorinated, or the like. Among these photoacid generators, preferred is one that generates an alkanesulfonic acid that is partially or completely fluorinated. Examples may include: triphenylsulfur triflate or triphenylsulfur perfluoro-n-butane sulfonate.
3-2.(C) basic compound
The resist containing any of the fluoropolymers (1) to (3) of the present invention may be blended with a basic compound. The basic compound has an effect of reducing the diffusion rate of the acid generated from the photoacid generator when the acid diffuses in the resist film. The following effects can be expected by the compounding of the basic compound: the shape of the resist pattern is improved by adjusting the acid diffusion distance, and the stability of the resist pattern to be provided with desired accuracy is improved even if the storage time until exposure after formation of the resist film is prolonged.
As such a basic compound, there can be exemplified: aliphatic amines, aromatic amines, heterocyclic amines or aliphatic polycyclic amines. Among these amines, aliphatic amines or alkanolamines of secondary or tertiary amines are preferable. Examples may include: trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonyl amine, tridecylamine, tridodecyl amine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicyclohexylamine, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, dioctanolamine, trioctalamine, aniline, pyridine, picoline, lutidine, bipyridine, pyrrole, piperidine, piperazine, indole, or hexamethylenetetramine. These basic compounds may be used alone, or two or more of them may be used in combination.
The amount of the basic compound to be added to the resist of the present invention is 0.001 to 2 parts by mass per 100 parts by mass of the fluoropolymer (1), and preferably 0.01 to 1 part by mass per 100 parts by mass of the fluoropolymer (1). If the amount is less than 0.001 part by mass, the effect as an additive cannot be sufficiently obtained, and if it exceeds 2 parts by mass, the resolution and sensitivity may be lowered.
3-3.(D) solvent
The resist of the present invention contains (D) a solvent in addition to (A) any one of the fluoropolymers (1) to (3) of the present invention, (B) a photoacid generator and (C) a basic compound. The solvent may be selected from the conventional resist solvents as long as it can dissolve the resist components containing (a) any one of the fluoropolymers (1) to (3) of the present invention, (B) the photoacid generator, and (C) the basic compound to form a uniform solution. In addition, two or more solvents may be mixed and used.
Examples of such solvents include: ketones, alcohols, polyols, esters, aromatic solvents, ethers, fluorine solvents, or high boiling point solvents such as turpentine naphtha solvents and paraffin solvents for improving coatability.
For example, one may exemplify: acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone or 2-heptanone as ketones, isopropanol, butanol, isobutanol, n-pentanol, isopentyl alcohol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2, 3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, sec-pentanol, tert-pentanol, isopentyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol or oleyl alcohol as alcohols, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether as polyols, and the like, Propylene glycol monobutyl ether, Propylene Glycol Monomethyl Ether Acetate (PGMEA) or Propylene Glycol Monomethyl Ether (PGME), and derivatives of these polyols, methyl lactate, Ethyl Lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate or ethyl ethoxypropionate as esters, toluene or xylene as aromatic solvents, diethyl ether, dioxane, anisole or diisopropyl ether as ethers, or hexafluoroisopropanol as a fluorine-based solvent.
Among these solvents, Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monomethyl Ether (PGME), cyclohexanone, and Ethyl Lactate (EL) are particularly preferable as the resist of the present invention.
The amount of the solvent to be blended in the resist of the present invention is not particularly limited, and the solid content concentration when the resist is produced is preferably 3 mass% or more and 25 mass% or less, and more preferably 5 mass% or more and 15 mass% or less. By adjusting the solid content concentration of the resist, the film thickness of the resin film to be formed can be adjusted.
The fluoropolymers (1) to (3) of the present invention are excellent in solubility in a wide range of solvents, and among the above alcohol solvents, it is important to propose a fluoropolymer that is soluble in an alcohol solvent having 5 to 20 carbon atoms. As such alcohols, there can be exemplified: n-pentanol, isopentyl alcohol, tert-amyl alcohol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2, 3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, sec-pentanol, tert-amyl alcohol, isopentyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, or oleyl alcohol.
(E) a surfactant
In the resist of the present invention, a surfactant may be added as necessary. Examples of the surfactant include: the fluorine-based surfactant, the silicon-based surfactant, or the surfactant having both a fluorine atom and a silicon atom may contain two or more kinds.
3-5 resist
The resist of the present invention can be solubilized by an alcohol solvent having 5 to 20 carbon atoms, which is not soluble in general resist materials. Thus, the photoresist can be used as an upper layer resist for a double patterning process. The resist of the present invention has high water resistance, appropriate water repellency, and developer affinity.
The resist of the present invention has appropriate water repellency to water before exposure and exhibits rapid solubility to a developer after exposure, and therefore it is presumed that: in immersion exposure, which is performed by filling a medium having a refractive index larger than that of air, such as water, between a resist and a lens, and performing exposure, a pattern having excellent resolution without roughness can be formed, not only in dry exposure. In the photolithography by the immersion exposure, there are a case where a top coat film (topcoat film) as a protective film of a resist is used and a case where the top coat film is not used, and it is presumed that the resist of the present invention can be applied also to the immersion exposure by adjusting the composition and blending.
Examples of the immersion exposure medium include, in addition to water, a fluorine-based solvent, a silicon-based solvent, a hydrocarbon-based solvent, a sulfur-containing solvent, and the like, and the resist containing the fluoropolymer (1) of the present invention may be applied to these media.
4. Method for forming resist pattern
The method for forming a resist pattern of the present invention comprises: a film formation step of coating the resist of the present invention on a substrate to form a film; an exposure step of irradiating electromagnetic waves or high-energy rays having an exposure wavelength of 300nm or less through a mask to transfer a pattern of the mask onto the film; and a developing step of developing the film with a developer to obtain a pattern. In the present invention, the high-energy radiation refers to electron beams or soft X-rays.
The method for forming a resist pattern of the present invention is a pattern forming method using photolithography using a resist containing any one of the fluoropolymers (1) to (3), and includes: (A) a film formation step of forming a resist film by coating a resist on a substrate; (B) an exposure step of heating the resist film and then irradiating the resist film with an electromagnetic wave or a high-energy ray having an exposure wavelength of 300nm or less through a patterned mask; (C) and a developing step of developing the exposed resist film with an alkaline developer to obtain a resist pattern on the substrate, to which the mask pattern is transferred.
For example, in the film formation step (a), a resist containing any one of the fluoropolymers (1) to (3) of the present invention is applied to a silicon wafer as a substrate by spin coating, and the silicon wafer is prebaked on a hot plate at 60 to 200 ℃ for 10 seconds to 10 minutes, preferably at a temperature of 80 ℃ to 150 ℃ for 30 seconds to 2 minutes, thereby forming a film on the substrateAnd a resist film. Next, in the (B) exposure step, the patterned mask was set on an exposure apparatus so that the exposure amount became 1mJ/cm2Above and 200mJ/cm2Preferably 10mJ/cm or less2Above and 100mJ/cm2After the resist film is irradiated with high-energy radiation such as ultraviolet rays, excimer laser light, and X-rays or with electrons through a mask, the resist film is subjected to post-exposure baking (PEB) for 10 seconds to 5 minutes, preferably 30 seconds to 3 minutes, at a temperature of 60 ℃ to 150 ℃, preferably 80 ℃ to 130 ℃, on a hot plate, as necessary. Next, in the developing step (C), a developing solution based on a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 0.1% by mass or more and 5% by mass or less, preferably 2% by mass or more and 3% by mass or less is used, and the resist film is brought into contact with the developing solution by a conventional method such as a dipping method, a grooving method, a spraying method for developing for 10 seconds or more and 3 minutes or less, preferably 30 seconds or more and 2 minutes or less, thereby obtaining a target resist pattern.
The substrate may be a metal or glass substrate other than a silicon wafer. In addition, an organic or inorganic film may be provided on the substrate. For example, an antireflection film, a lower layer of a multilayer resist, or a resist pattern may be present.
In the lithography of a resist according to the present invention, the wavelength of the electromagnetic wave used for exposure is not limited, and the wavelength can be selected from: UV (ultraviolet) light (wavelength 248nm) using a KrF excimer laser, UV light (wavelength 193nm) using an ArF excimer laser, Extreme ultraviolet lithography (EUV), and X-rays, and particularly UV light using an ArF excimer laser can be suitably used.
The resist of the present invention has appropriate water repellency to water before exposure, exhibits rapid solubility in a developer after exposure, and can form a pattern having excellent resolution without roughness.
By using the pattern forming method of photolithography using the resist of the present invention, a semiconductor device can be manufactured. The apparatus is not particularly limited, and examples thereof include: a semiconductor device manufactured by microfabrication, such as a CPU (Central Processing Unit), an SRAM (Static Random Access Memory), or a DRAM (Dynamic Random Access Memory), which is formed on a silicon wafer, a compound semiconductor substrate, an insulating substrate, or the like.
5. Composition for forming ink pattern
The ink pattern forming composition of the present invention is obtained by adding an acid generator and a solvent to any one of the fluoropolymers (1) to (3), and is useful for ink pattern formation in printed electronics. Hereinafter, the pattern formed by the ink is sometimes referred to as an ink pattern.
The ink pattern-forming composition of the present invention contains any of the fluoropolymers (1) to (3), an acid generator (a), and a solvent (B) as its components. It is preferable to contain other (C) quencher (quencher), (D) sensitizer, (E) polymerizable compound, and if necessary, a surfactant, storage stabilizer, adhesion promoter or heat resistance improver.
(A) The acid generator is a compound that generates an acid by light irradiation at the time of exposure in a film formed from the composition for ink pattern formation. (B) The solvent is a substance for dissolving or dispersing the components of the ink pattern-forming composition. (C) The quencher is a substance for preventing diffusion of an acid from an acid generator at the time of exposure to make the obtained pattern highly fine. (D) The sensitizer is a substance for improving exposure sensitivity. (E) The polymerizable compound is a substance for making the pattern forming film obtained after exposure harder. The following discloses the respective components.
5-1.(A) acid generator
As the acid generator (a) used as a component of the ink pattern forming composition of the present invention, a photoacid generator which is a compound that generates an acid by light irradiation can be used.
The acid generator (a) used as a component in the ink pattern forming composition of the present invention may be a compound that generates an acid by light irradiation, and examples thereof include: oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds, or the like.
[ Oxime sulfonic acid ester Compound ]
Examples of the oxime sulfonate compound include: an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Some or all of the hydrogen atoms possessed by these groups are optionally substituted with halogen atoms or substituents. Preferably a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms. Examples of the substituent include: an alkoxy group having 1 to 10 carbon atoms, an alicyclic group containing a bridged cyclic alicyclic group such as a 7, 7-dimethyl-2-oxonorbornenyl group, and the like.
Examples of the fluoroalkyl group having 1 to 12 carbon atoms include: trifluoromethyl, pentafluoroethyl or heptylfluoropropyl. Examples of the substituent that the alicyclic hydrocarbon having 4 to 12 carbon atoms may have include: an alkyl group or an alkoxy group having 1 to 5 carbon atoms.
Examples of the aryl group having 6 to 20 carbon atoms include: phenyl, naphthyl, tolyl, or xylyl. Examples of the substituent that the aryl group having 6 to 20 carbon atoms may have include: an alkyl group or an alkoxy group having 1 to 5 carbon atoms or a halogen atom.
As the oxime sulfonate compound, there can be exemplified: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile or (5-octylsulfonyloxyimino) - (4-methoxyphenyl) acetonitrile.
[ onium salt ]
Examples of onium salts include: diphenyliodonium salts, triphenylsulfonium salts, alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, benzothiazolium salts, or tetrahydrothiophenium salts.
< Diphenyliodonium salt >
As diphenyliodonium salts, there can be exemplified: diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium p-toluenesulfonate, diphenyliodonium butyl tris (2, 6-difluorophenyl) borate, 4-methoxyphenyliodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate or bis (4-tert-butylphenyl) iodonium camphorsulfonate.
< triphenylsulfonium salt >
As the triphenylsulfonium salt, there can be exemplified: triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate or triphenylsulfonium butyltris (2, 6-difluorophenyl) borate.
< alkyl sulfonium salt >
As the alkyl sulfonium salt, there can be exemplified: 4-acetoxyphenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenyl sulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenyl sulfonium hexafluoroarsenate, or dimethyl-3-chloro-4-acetoxyphenyl sulfonium hexafluoroantimonate.
< benzylsulfonium salt >
As the benzylsulfonium salt, there can be exemplified: benzyl-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl benzyl methyl sulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl methyl sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenyl methyl sulfonium hexafluoroarsenate or 4-methoxybenzyl-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate.
< dibenzylsulfonium salt >
As the dibenzylsulfonium salt, there can be exemplified: dibenzyl-4-hydroxyphenyl sulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenyl sulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzyl sulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenyl sulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenyl sulfonium hexafluoroantimonate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenyl sulfonium hexafluoroantimonate or benzyl-4-methoxybenzyl-4-hydroxyphenyl sulfonium hexafluorophosphate.
< substituted benzylsulfonium salt >
As the substituted benzylsulfonium salt, there can be exemplified: p-chlorobenzyl-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenyl methyl sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate, 3, 5-dichlorobenzyl-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate or o-chlorobenzyl-3-chloro-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate.
< benzothiazolium salts >
As the benzothiazolium salt, there can be exemplified: 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, 3- (p-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate or 3-benzyl-5-chlorobenzthiazolium hexafluoroantimonate.
< tetrahydrothiophenium salt >
As tetrahydrothiophenium salts, there can be exemplified: 4, 7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butylsulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1, 1,2, 2-tetrafluoro-2- (norbornane-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-tert-butoxycarbonyloxybenzoxybicyclo [2.2.1] heptan-2-yl) -1,1,2, 2-tetrafluoroethanesulfonate or 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium- 2- (6-tert-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2, 2-tetrafluoroethanesulfonate.
< sulfonimide Compound >
As the sulfonimide compound, there can be exemplified: n- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, N-methyl-phenylsulfonyloxy-N-phenylsulfonyloxy-phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (nonafluorobutylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxo-2, 3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxo-2, 3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxo-2, 3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxo-2, 3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxo-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboximide, N- (camphorsulfonyloxy) naphthyl dicarboximide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboximide, N- (phenylsulfonyloxy) naphthyl dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboximide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboximide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboximide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboximide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboximide, N- (ethylsulfonyloxy) naphthyl dicarboximide, N- (propylsulfonyloxy) naphthyl dicarboximide, N- (butylsulfonyloxy) naphthyl dicarboximide, N- (pentylsulfonyloxy) naphthyl dicarboximide, N- (hexylsulfonyloxy) naphthyl dicarboximide, N- (heptylsulfonyloxy) naphthyl dicarboximide, N- (octylsulfonyloxy) naphthyl dicarboximide or N- (nonylsulfonyloxy) naphthyl dicarboximide.
< halogen-containing Compound >
Examples of the halogen-containing compound include: a halogenated alkyl group-containing hydrocarbon compound, a halogenated alkyl group-containing heterocyclic compound.
< diazomethane Compound >
As the diazomethane compound, there can be exemplified: bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2, 4-xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyl diazomethane, cyclohexylsulfonyl (1, 1-dimethylethylsulfonyl) diazomethane, bis (1, 1-dimethylethylsulfonyl) diazomethane or phenylsulfonyl (benzoyl) diazomethane.
< sulfone Compound >
Examples of the sulfone compound include: beta-ketone sulfone compounds, beta-sulfonyl sulfone compounds, diaryl disulfone compounds.
< sulfonic acid ester Compound >
As the sulfonic acid ester compound, there can be mentioned: alkyl sulfonates, haloalkyl sulfonates, aryl sulfonates, or imide sulfonates.
< carboxylic ester Compound >
As the carboxylate compound, there may be mentioned: carboxylic acid o-nitrobenzyl ester.
< acid generator (A) contained in the ink pattern-forming composition of the present invention >
These acid generators (a) may be used alone or in combination of two or more. The oxime sulfonate compound, the onium salt, or the sulfonate compound is preferable, and the oxime sulfonate compound is particularly preferable, in terms of a large effect of improving the exposure sensitivity of a film containing the ink pattern forming composition.
[ Containment of acid Generator (A) in composition for Forming ink Pattern ]
The acid generator (a) in the ink pattern forming composition of the present invention is preferably contained in an amount of 0.1% to 10% by mass, more preferably 1% to 5% by mass, based on the fluoropolymer (1) of the present invention. By setting the content of the (a) acid generator to the above range, a higher exposure sensitivity of the ink pattern-forming composition can be obtained, and a higher-definition pattern-forming film formed by the lyophobic part and the lyophilic part can be obtained.
5-2.(B) solvent
As the solvent (B) used as a component of the ink pattern forming composition of the present invention, as long as each component of the ink pattern forming composition can be dissolved or dispersed, there may be mentioned: organic solvents such as alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, or esters. Hereinafter, each (B) solvent is disclosed.
[ alcohols ]
Examples of alcohols include: long-chain alkyl alcohols, aromatic alcohols, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ethers.
< Long chain alkyl alcohols >
As long-chain alkyl alcohols, there may be exemplified: 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1, 6-hexanediol or 1, 8-octanediol.
< aromatic alcohols >
As the aromatic alcohol, there can be exemplified: benzyl alcohol. As ethylene glycol monoalkyl ethers, there can be exemplified: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether or ethylene glycol monobutyl ether.
< propylene glycol monoalkyl ethers >
As propylene glycol monoalkyl ethers, there can be exemplified: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether.
< dipropylene glycol monoalkyl ethers >
As the dipropylene glycol monoalkyl ethers, there can be exemplified: dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, or dipropylene glycol monobutyl ether.
Among these alcohols, benzyl alcohol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, or propylene glycol monoethyl ether is preferable in terms of ease of dissolving the ink pattern forming composition of the present invention and ease of film formation.
[ ethers ]
As ethers, there can be exemplified: tetrahydrofuran, hexyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether or 1, 4-dioxane.
[ diethylene glycol alkyl ethers ]
As the diethylene glycol alkyl ethers, there can be exemplified: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, or diethylene glycol ethyl methyl ether.
[ glycol alkyl ether acetates ]
As the ethylene glycol alkyl ether acetates, there can be exemplified: methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate or ethylene glycol monoethyl ether acetate.
[ propylene glycol alkyl ether acetates ]
As propylene glycol monoalkyl ether acetates, there can be exemplified: propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate or propylene glycol monobutyl ether acetate.
[ propylene glycol monoalkyl ether propionates ]
As propylene glycol monoalkyl ether propionic acid esters, there can be exemplified: propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate or propylene glycol monobutyl ether propionate.
[ aliphatic hydrocarbons ]
As the aliphatic hydrocarbon, there can be exemplified; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane or decalin.
[ aromatic hydrocarbons ]
As aromatic hydrocarbons, there can be exemplified: benzene, toluene, xylene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, mesitylene, chlorobenzene, or dichlorobenzene.
[ ketones ]
As ketones, there can be exemplified: methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone or 4-hydroxy-4-methyl-2-pentanone.
[ esters ]
As the esters, there can be exemplified: methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxylacetate, ethyl propoxyethyl acetate, ethyl 2-hydroxy-2-methylpropionate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl methoxyacetate, butyl methoxyacetate, Propyloxypropyl acetate, propyloxy-butyl acetate, butoxymethyl acetate, butoxyethyl acetate, butoxypropyl acetate, butoxybutyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate or ethyl 2-ethoxypropionate.
These (B) solvents may be used alone or in combination of two or more.
[ content of solvent (B) in ink Pattern Forming composition ]
The content of the solvent (B) in the ink pattern forming composition is preferably 200 to 1600 parts by mass, and more preferably 400 to 1000 parts by mass, based on 100 parts by mass of the ink pattern forming composition other than the solvent (B). By using the solvent (B) in the above range, the wettability of the ink pattern-forming composition to a glass substrate or the like can be improved, and the occurrence of coating unevenness can be suppressed, thereby obtaining a uniform film.
5-3.(C) quenching agent
The quencher (C) used in the ink pattern forming composition of the present invention functions as an acid diffusion suppressing material for preventing diffusion of an acid derived from the acid generator (a) at the time of exposure in forming a film, and includes a photodegradable base which generates a weak acid by being exposed to light. As the photodegradable base, an onium salt compound is preferable.
The photodegradable base generates an acid in the exposed portion, and on the other hand, exhibits a high acid-capturing function by an anion in the unexposed portion, captures an acid from the acid generator (a), and inactivates an acid diffused from the exposed portion to the unexposed portion. The acid is deactivated only in the unexposed portions. In the pattern forming film obtained by exposing the composition for forming a pattern of the present invention, the boundary between the lyophobic region and the lyophilic region becomes clear, the contrast of the pattern after ink application is improved, and a fine pattern is obtained. (C) The quencher may be used alone or in combination of two or more.
[ Containment of quencher (C) in composition for ink Pattern formation ]
The content of the quencher (C) in the ink pattern-forming composition is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 3 parts by mass, based on 100 parts by mass of the fluoropolymer (1). When the content of the quencher (C) is in the above range, in a pattern forming film obtained by exposing the ink pattern forming composition of the present invention, the boundary between the lyophobic part and the lyophilic part becomes clear, the contrast of the pattern after ink application is improved, and a fine pattern is obtained.
(D) sensitizers
The (D) sensitizer used in the ink pattern-forming composition of the present invention is added when the exposure sensitivity of the ink pattern-forming composition is to be further improved. (D) The sensitizer is preferably a compound that absorbs light or radiation to become an excited state. When the sensitizer (D) is in an excited state, electron transfer, energy transfer, heat generation, or the like occurs when the sensitizer (D) comes into contact with the acid generator (a), whereby the acid generator (a) is easily decomposed to generate an acid. (D) The sensitizer may have an absorption wavelength in the range of 350nm to 450nm, and examples thereof include: polynuclear aromatics, xanthenes, heteroanthrenes, cyanines, merocyanines, rhodanines, oxonols, thiazines, acridines, acridones, anthraquinones, squaryliums, styrenes, benzostyryls or coumarins.
Hereinafter, each (D) sensitizer is disclosed.
[ polynuclear aromatic Compounds ]
As the polynuclear aromatic species, there can be exemplified: pyrene, perylene, triphenylene, anthracene, 9, 10-dibutoxyanthracene, 9, 10-diethoxyanthracene, 3, 7-dimethoxyanthracene or 9, 10-dipropoxyanthracene.
[ xanthenes ]
Examples of xanthenes are: fluorescein, tetrabromo fluorescein, erythrosine, rhodamine B and rose bengal.
[ Heteroanthrones ]
As the heteroanthrone, there can be exemplified: xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone or isopropylthioxanthone.
[ Cyanines ]
Examples of the cyanine group include: thiacarbocyanines, oxacarbocyanines (oxacarbocyanines).
[ merocyanines ]
Examples of merocyanines include: merocyanine, carbocyanine (carbocyanine).
[ thiazines ]
As thiazines, there may be exemplified: thionine, methylene blue, toluidine blue.
[ acridines ]
As acridine, there can be exemplified: acridine orange, chloroflavin, acridine yellow.
[ acridones ]
As acridones, there can be exemplified: acridone and 10-butyl-2-chloroacridone.
[ anthraquinones ]
As anthraquinones, there can be exemplified: anthraquinone.
[ squarylium cyanine compounds ]
As squarylium, mention may be made of: squaraine.
[ styryl group ]
As the styryl group, there can be exemplified: 2- [2- [4- (dimethylamino) phenyl ] ethenyl ] benzoxazole.
[ coumarins ]
As coumarins, there can be exemplified: 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin or 2,3,6, 7-tetrahydro-9-methyl-1H, 5H,11 Hl benzopyrano [6,7,8-ij ] quinolizin-11-one.
These (D) sensitizers may be used singly or in combination of two or more.
[ sensitizer (D) contained in the ink pattern-forming composition of the present invention ]
As the (D) sensitizer used in the ink pattern forming composition of the present invention, polynuclear aromatic compounds, acridones, styryl compounds, coumarins, or heteroanthrone compounds are preferable, and heteroanthrone compounds are particularly preferable, in view of the great effect of improving the exposure sensitivity. Among the heteroanthrone compounds, diethyl thioxanthone and isopropyl thioxanthone are preferable.
[ content of sensitizer (D) in ink Pattern Forming composition ]
The content of the sensitizer (D) is preferably 0.1 to 8 parts by mass, more preferably 1 to 4 parts by mass, per 100 parts by mass of the fluoropolymer (1). When the content of the sensitizer (D) is in the above range, the exposure sensitivity of the ink pattern-forming composition can be improved, and in a pattern-forming film obtained by exposing the pattern-forming composition of the present invention, the boundary between the lyophobic part and the lyophilic part becomes clear, and the contrast of the ink pattern after ink application is improved, thereby obtaining a fine pattern.
5-5 (E) polymerizable compound
The polymerizable compound (E) used as a component of the ink pattern-forming composition of the present invention is contained in the ink pattern-forming composition in order to make the resulting pattern-forming film harder. (E) The polymerizable compound is a compound having an ethylenically unsaturated bond other than the fluoropolymer (1). As the polymerizable compound (E), a polymerizable compound having good polymerizability and capable of hardening a pattern-forming film obtained from the ink pattern-forming composition includes: monofunctional or more than bifunctional acrylates and methacrylates.
Hereinafter, each (E) polymerizable compound is disclosed.
[ monofunctional acrylates and methacrylates ]
< monofunctional acrylate >)
As monofunctional acrylates, there may be exemplified: 2-hydroxyethyl acrylate, diethylene glycol monoethyl ether acrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate or (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate.
< monofunctional methacrylate >)
As monofunctional methacrylates, there can be exemplified: 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether methacrylate or omega-carboxy polycaprolactone monoacrylate.
Monofunctional acrylates and methacrylates are commercially available, for example: trade names ARONIX (registered trademark) from Toyo Synthesis K.K., product numbers M-101, M-111, M-114 and M-5300, trade name KAYARAD from Nippon Kagaku, product number TC-110S, TC-120S, and trade names Viscoat 158 and 2311Viscoat from Osaka organic chemical industries, Ltd.
[ bifunctional acrylic acid esters and methacrylic acid esters ]
As the bifunctional acrylate, there can be exemplified: ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, 1, 6-hexanediol diacrylate or 1, 9-nonanediol diacrylate.
As the bifunctional methacrylate, there can be exemplified: propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate or 1, 9-nonanediol dimethacrylate.
Difunctional acrylates and methacrylates are commercially available, for example: trade names ARONIX (registered trade name) from Toyo Synthesis K.K., product numbers M-210, M-240, and M-6200, trade name KAYARAD from Kazak chemical Co., Ltd., product numbers HDDA, HX-220, and R-604, trade name Viscoat from Osaka organic chemical industry K.K., product numbers 260, 312, and 335HP, and trade name Light Acrylate1,9-NDA from Kyowa chemical Co., Ltd.
[ trifunctional or higher acrylate and methacrylate ]
Examples of the trifunctional or higher acrylate and methacrylate include: trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, tris (2-acryloyloxyethyl) phosphate, tris (2-methacryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, tris (acryloyloxyethyl) isocyanurate, or a mixture of a compound having a linear alkylene group and an alicyclic structure and having 2 or more isocyanate groups in the molecule and a compound having 1 or more hydroxyl groups in the molecule And a compound having 3,4 or 5 (meth) acryloyloxy groups, and a polyfunctional urethane acrylate compound obtained by reacting the compound.
Trifunctional or higher acrylates and methacrylates are commercially available, for example: trade names ARONIX (registered trademark) from Toyo Synthesis K.K., product numbers M-309, M-315, M-400, M-405, M-450, M-7100, M-8030, M-8060, TO-1450, trade names KAYARAD from Kayaki chemical Co., Ltd, product numbers TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12, trade names Viscoat from Osaka organic chemical industries, product numbers 295, 300, 360, GPT, 3PA, 400, trade names Light Acrylate1,9-NDA from Kyowa chemical Co., Ltd, and the like. Polyfunctional urethane acrylate compounds are commercially available as: a trade name New Frontier (registered trademark) from first Industrial pharmaceutical Co., Ltd., product number R-1150, a trade name KAYARAD from Nippon chemical Co., Ltd., product number DPHA-40H, and the like.
The polymerizable compound (E) used in the ink pattern-forming composition of the present invention is preferably ω -carboxy polycaprolactone monoacrylate, 1, 9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, or a polyfunctional urethane acrylate-based compound, in view of the effect of making the resulting pattern-forming film harder. Particularly preferred are mixtures of trifunctional or higher (meth) acrylates, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.
[ content of polymerizable Compound (E) in the composition for Forming an ink Pattern ]
These (E) polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound (E) is preferably 1 to 300 parts by mass, more preferably 3 to 200 parts by mass, and particularly preferably 5 to 100 parts by mass, based on 100 parts by mass of the fluoropolymer (1). By making the amount of the (E) polymerizable compound in the above range, the pattern forming film obtained from the ink pattern forming composition can be made harder.
6. Method for forming ink pattern
The ink pattern forming method of the present invention includes the following two pattern forming methods (a) and (B). The ink pattern forming method (a) is a method using a mask, and the ink pattern forming method (B) is a method using a drawing device.
[ method (A) for Forming ink Pattern ]
The ink pattern forming method (a) of the present invention includes the steps of: a film forming step of coating the ink pattern forming composition on a substrate to form a film; an exposure step of exposing the film by irradiating the film with light having a wavelength of 150nm to 500nm through a mask, and transferring a pattern of the mask onto the film to obtain a pattern forming film having a lyophobic portion and a lyophilic portion; and an ink pattern forming step of coating ink on the resultant pattern forming film, thereby obtaining a pattern formed using the ink.
[ Pattern Forming method (B) ]
The ink pattern forming method (B) of the present invention includes the steps of: a film forming step of applying the ink pattern-forming composition to a substrate and heating the resultant coating film; a drawing step of drawing a pattern on the film by exposing the film to light having a scanning wavelength of 150nm to 500nm by a drawing device, thereby obtaining a pattern-formed film having a lyophobic part and a lyophilic part; and an ink pattern forming step of coating an ink on the resultant pattern forming film.
6-1. film-forming step, exposure or drawing step, and ink pattern-forming step of ink pattern-forming method
The following discloses a film formation step common to the ink pattern forming methods (a) and (B), an exposure fixing step in the ink pattern forming method (a) and a drawing step in (B), and an ink pattern forming step common to the ink pattern forming methods (a) and (B).
6-2. film preparation step
The film forming step is a step of applying the ink pattern-forming composition of the present invention described above on a substrate and heating (prebaking) the resulting coating film.
[ base plate ]
Examples of the substrate used in the film formation step include a resin substrate, a glass substrate, and a semiconductor substrate such as quartz or silicon, which are used in an electronic circuit. As the resin, there can be exemplified: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethersulfone, polycarbonate, or polyimide.
Before applying the composition for forming an ink pattern on a substrate, the substrate surface may be pretreated, if necessary, by cleaning, roughening, or providing a fine uneven surface.
[ coating method ]
The method of applying the ink pattern-forming composition to the substrate is not particularly limited, and examples thereof include: coating using a brush or a brush, a dipping method, a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, flexographic printing, offset printing, inkjet printing, or a dispensing (discrete) method. In the pattern forming method of the present invention, a spin coating method is preferable.
[ film thickness ]
The thickness of the coating film formed in the above step can be appropriately adjusted depending on the intended use. In the ink pattern forming method of the present invention, it is preferably 0.1 μm to 20 μm.
[ Pre-baking ]
The conditions for the prebaking common to the ink pattern forming methods (a) and (B) of the present invention are preferably 60 to 120 ℃ for 1 to 10 minutes, but may be different depending on the composition of the ink pattern forming composition used.
6-3. Exposure step and drawing step
[ Exposure step ]
The exposure step in the ink pattern formation method (a) is the following step: the film obtained in the film-forming step is exposed to light having a wavelength of 150nm to 500nm through a mask, and the pattern of the mask is transferred onto the film, thereby obtaining a pattern-formed film having a lyophobic portion and a lyophilic portion. The exposure is performed through a mask having a specific pattern so as to form an exposure portion having the same pattern as a desired pattern.
[ drawing step ]
The drawing step in the ink pattern forming method (B) is the following step: the film obtained in the film-forming step is exposed to light having a scanning wavelength of 150nm to 500nm by a drawing device, and a pattern is drawn on the film, thereby obtaining a pattern-formed film having a lyophobic part and a lyophilic part. For example, by scanning a specific pattern using a direct writing exposure apparatus.
[ use of light ]
Radiation as visible light, ultraviolet light, X-rays, or charged particle flux can be used for exposure and drawing. Ultraviolet rays having a wavelength of 150nm to 500nm are preferable, and ultraviolet rays having a wavelength of 365nm generated by an ultraviolet light emitting diode are particularly preferable.
By exposure and drawing, the acid-dissociable group of the fluoropolymer (1) is detached and volatilized by the effect of the acid generated from the acid generator (a) in the film. As a result, the film thickness of the exposed portion becomes thinner than that of the unexposed portion, and a concave pattern is formed. In this case, since the acid-dissociable group has a fluorine atom, the unexposed portion exhibits lyophobicity, and the exposed portion exhibits lyophilic properties. Therefore, the film formed on the substrate becomes a pattern forming film having unexposed portions having liquid-repellent properties and exposed portions having liquid-affinity properties as concave patterns.
[ heating ]
The pattern forming film after exposure is preferably heated. By heating the exposed pattern forming film, a component generated by the acid-dissociable group dissociated from the fluoropolymer (1) in the exposed portion can be further volatilized, and a more refined pattern including exposed recesses and unexposed protrusions can be obtained.
Examples of the method of heating the pattern forming film include: a method of heating the film-forming substrate using a hot plate, a batch oven, or a conveyor oven, a method of hot air drying using a dryer, or the like, or a method of vacuum baking. The heating conditions vary depending on the composition of the composition, the thickness of the obtained coating film, and the like, and are preferably 60 ℃ to 150 ℃ and 3 minutes to 30 minutes.
6-4 ink Pattern Forming step
The formation of the ink pattern is performed by the following method: an ink is applied to the resulting pattern forming film to obtain a pattern formed using the ink.
The difference in contact angle between the lyophilic and lyophobic sections before and after exposure of the pattern forming film to water and hexadecane as ink solvents is preferably 30 ° or more, and more preferably 50 ° or more. By setting the contact angle difference to the above range, even when ink is applied to the convex liquid-repellent portion, the ink is repelled and easily moves to the concave portion which is the lyophilic portion, and a more delicate ink pattern including exposed concave portions and unexposed convex portions can be obtained.
[ formation of conductive ink Pattern ]
In the ink pattern forming method of the present invention, a conductive ink pattern can be formed on a substrate by using a conductive ink as an ink.
6-5 application in electronic circuit and electronic device
In the ink pattern forming method of the present invention, a motor circuit including a conductive ink pattern is formed on a substrate, so that an electronic device can be manufactured. The electronic circuit is a wiring formed of a conductive ink pattern formed on a substrate. The electronic device is a device having an electronic circuit, and examples thereof include: a portable information device such as a liquid crystal display or a mobile phone, a digital camera, an organic display, an organic EL (Electroluminescence) lighting, various sensors, or a wearable device.
7. Fluorine-containing monomer
The fluoropolymers (1) to (3) of the present invention are synthesized by homopolymerizing or copolymerizing the following fluorinated monomer (4) of the present invention.
[ fluoromonomer (4) ]
The fluorine-containing monomer of the present invention is a fluorine-containing monomer represented by the following formula (4) and has a fluorine-containing cyclic acetal structure, and the fluorine-containing polymer (1) is obtained by homopolymerizing or copolymerizing the fluorine-containing monomer (4). Hereinafter, the monomer may be referred to as a fluoromonomer (4).
Figure GDA0003005189880000421
(in the formula, R1The alkyl group is a straight-chain or branched alkyl group having 1 to 10 carbon atoms or a hydrogen atom, fluorine atom or a branched alkyl group having 3 to 10 carbon atoms, and 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted by fluorine atoms. R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. X is a single bond or a 2-valent group, and 7 or less hydrogen atoms included in the 2-valent group are optionally substituted by fluorine atoms. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. The same applies hereinafter)
[ fluoromonomer (5) ]
The fluorine-containing monomer (4) of the present invention is preferably R in the above formula (4)2、R4、R5A fluorine-containing monomer (5) which is a hydrogen atom.
When the fluorine-containing polymer (1) obtained by polymerizing the fluorine-containing monomer (4) is used as a component of the resist or ink pattern-forming composition of the present invention for film formation on a substrate, R in the above formula (4) is considered to be soluble in a solvent2、R4、R5Preferably a hydrogen atom, and preferably a fluorine-containing monomer having a fluorine-containing cyclic acetal structure represented by the following formula (5). Hereinafter, the monomer may be referred to as a fluoromonomer (5).
Figure GDA0003005189880000431
R in (formula (5))1、R3X, Y has the same meaning as in formula (4). )
[ fluoromonomer (6) ]
The fluorine-containing monomer (5) of the present invention is a fluorine-containing monomer (6) wherein Y in the formula (5) is a trifluoromethyl group or less. When the above-mentioned fluoropolymer (2) obtained by homopolymerizing or copolymerizing the fluorine-containing monomer (5) is used as a resist or ink pattern-forming composition for film formation on a substrate, Y in the above-mentioned formula (4) is preferably a trifluoromethyl group, and more preferably a fluorine-containing monomer having a fluorine-containing cyclic acetal structure represented by the following formula (6), in view of solubility in a solvent. Hereinafter, the monomer may be referred to as a fluoromonomer (6).
Figure GDA0003005189880000432
R in (formula (6)1、R3X is the same as formula (4). )
Specific examples of the fluoromonomer (4) of the present invention are given below, but the fluoromonomer is not limited to these.
Figure GDA0003005189880000441
8. Method for producing fluorine-containing monomer (4)
A method for producing the fluoromonomer (4) of the present invention is shown. The method for producing a fluorine-containing monomer of the present invention comprises the steps of: a cyclic hemiacetal compound represented by formula (7) is obtained by cyclizing a hydroxycarbonyl compound represented by formula (10) below, or a hydroxyvinyl ether or hydroxyvinyl ester represented by formula (11).
Figure GDA0003005189880000451
(in the formula, R1The alkyl group is a straight-chain or branched alkyl group having 1 to 10 carbon atoms or a hydrogen atom, fluorine atom or a branched alkyl group having 3 to 10 carbon atoms, and 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted by fluorine atoms. R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. X is a single bond or a 2-valent group, and less than 7 hydrogen atoms contained in the 2-valent group are optionally fluorine atomsAnd (4) atom substitution. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. Z is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein some or all of the hydrogen atoms in Z are optionally substituted with a halogen atom, and wherein Z optionally contains an ether bond, a siloxane bond, a thioether bond or a carbonyl bond. The same applies hereinafter)
8-1 acylation or alkylation of fluorine-containing cyclic hemiacetal compound
The fluorine-containing monomer (4) of the present invention can be synthesized by: the fluorinated monomer (4) is obtained by introducing a polymerizable group into a fluorinated cyclic hemiacetal compound represented by the formula (7) (hereinafter, may be referred to as a fluorinated cyclic hemiacetal compound (7)). The reaction is shown below.
Figure GDA0003005189880000452
(R1、R2～R5X, Y is the same as the above formula, A is a hydrogen atom, a halogen atom, an acryloyl group or a methacryloyl group. )
This reaction is a reaction which can be carried out by acylation or alkylation of the hydroxyl group of the fluorine-containing cyclic hemiacetal compound (7) having a hydroxyl group, as follows: the fluorine-containing monomer (4) is synthesized by reacting an acryloyl compound represented by the above reaction formula with an acylating agent in which X is a single bond or an alkylating agent in which X is an organic group having a valence of 2 in the presence or absence of a base in a solvent.
Acylation of fluorine-containing cyclic hemiacetal compounds
[ acylating agent ]
Examples of the acylating agent include: carboxylic acid chlorides or carboxylic acid anhydrides. As the acylating agent, there can be exemplified: acryloyl chloride, methacryloyl chloride, acrylic anhydride, methacrylic anhydride, 2-fluoroacryloyl chloride or 2-methacryloxyacetyl chloride.
The amount of the acylating agent to be used is preferably 0.5 mol or more and 10mol or less based on 1mol of the fluorine-containing cyclic hemiacetal compound (7), and particularly preferably 1mol or more and 3mol or less in terms of improving the acylation yield. The reaction with the acylating agent can be carried out in the presence of a base, and the reaction can be carried out in the absence of a solvent or in a solvent.
[ alkali ]
Examples of the base include: inorganic bases, organic bases. The amount of the base used in the reaction is preferably 0.05mol or more and 10mol or less based on 1mol of the fluorine-containing cyclic hemiacetal compound (7), and particularly preferably 1mol or more and 3mol or less in terms of improving the yield.
< inorganic base >
As the inorganic base, there can be exemplified: lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate.
< organic base >
As the organic base, there can be exemplified: triethylamine, diisopropylethylamine, pyridine, imidazole, triethylenediamine, dimethylaminopyridine, and the like.
[ solvent ]
Examples of the solvent include: a hydrocarbon solvent, an ether solvent or a chlorine solvent. Can be used together with water according to the requirement.
< Hydrocarbon-based solvent >
Examples of the hydrocarbon solvent include: hexane, heptane, cyclohexane, methylcyclohexane, toluene or xylene.
< Ether-based solvent >
Examples of the ether solvent include: diethyl ether, dibutyl ether, tetrahydrofuran, 1, 4-dioxane, or ethylene glycol dimethyl ether.
< chlorine-based solvent >
As the chlorine-based solvent, there can be exemplified: dichloromethane, chloroform or 1, 2-dichloroethylene.
8-1-2. alkylation of fluorine-containing cyclic hemiacetal compounds
The polymerizable group may be introduced by alkylation of the hydroxyl group of the fluorine-containing cyclic hemiacetal compound (7). In the reaction, a catalyst may be used to accelerate the reaction rate.
[ alkylating agent ]
Examples of alkylating agents include: halogenated alkyl groups, and sulfonic acid esters.
The reaction with the alkylating agent may be in the presence of a base, and the reaction may be carried out in the absence of a solvent or in a solvent. The amount of the alkylating agent to be used is preferably 0.5 mol or more and 10mol or less based on 1mol of the fluorine-containing cyclic hemiacetal compound (7), and particularly preferably 1mol or more and 3mol or less in terms of improvement in yield.
< halogenated alkyl >)
As the halogenated alkyl group, there can be exemplified: chloroethyl acrylate, chloroethyl methacrylate, bromoethyl acrylate and bromoethyl methacrylate.
< sulfonic acid ester >
As the sulfonic acid ester, there can be exemplified; 2-methylsulfonyloxyethyl acrylate, 2-methylsulfonyloxyethyl methacrylate, 2-p-toluenesulfonyloxyethyl acrylate and 2-p-toluenesulfonyloxyethyl methacrylate.
[ alkali ]
Examples of the base include: inorganic bases, organic bases. As the organic base, an organic metal salt is exemplified. The amount of the base used in the reaction is preferably 0.05mol or more and 10mol or less, and particularly preferably 1mol or more and 3mol or less in terms of improving the yield.
< inorganic base >
As the inorganic base, there can be exemplified: lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium hydride, sodium hydride, potassium hydride, and ammonia.
< organic base >
As the organic metal salt, there can be exemplified: organic lithium salts, grignard reagents or alkali metal salts.
As the organic lithium salt, there may be exemplified: triethylamine, diisopropylethylamine, pyridine, imidazole, triethylenediamine, dimethylaminopyridine, methyllithium or n-butyllithium.
As the grignard reagent, there can be exemplified: methyl magnesium bromide.
As the alkali metal salt, there can be exemplified: sodium methoxide, sodium ethoxide or potassium tert-butoxide.
[ solvent ]
As the solvent, a solvent which is generally considered to be favorable for the nucleophilic substitution reaction is preferable, and there may be mentioned: aprotic polar solvents and protic polar solvents. Two-phase systems of these solvents with water are also possible.
Examples of the aprotic polar solvent include: n, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide or N-methylpyrrolidinone.
As the protic polar solvent, there can be exemplified: acetone, methyl ethyl ketone, acetonitrile, propionitrile, diethyl ether, dibutyl ether, tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, or ethylene dichloride.
[ catalyst ]
To accelerate the reaction rate of the alkylation reaction, an iodide or bromide may be added as a catalyst. The amount of the catalyst to be added is preferably 0.001 to 1mol, and particularly preferably 0.005 to 0.5 mol, based on 1mol of the hemiacetal compound (7).
< iodide >)
As the iodide, there can be exemplified: sodium iodide, lithium iodide or tetrabutylammonium iodide.
< bromide >
As the bromide, there can be exemplified: sodium bromide, lithium bromide or tetrabutylammonium bromide.
9. Fluorine-containing cyclic hemiacetal
[ fluorinated cyclic hemiacetal (7) ]
The fluoropolymer (1) of the present invention is obtained by polymerizing a fluoromonomer (4). The fluorine-containing monomer is a fluorine-containing monomer and has a fluorine-containing cyclic acetal structure. The fluorine-containing cyclic hemiacetal (7) is a compound which is a precursor of the fluorine-containing monomer (4).
Figure GDA0003005189880000491
(in the formula, R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. )
[ fluorinated cyclic hemiacetal (8) ]
The fluorine-containing hemiacetal (7) of the present invention is preferably R in the above formula (7)2、R4、R5The following fluorine-containing hemiacetal (8) which is a hydrogen atom.
The fluoropolymer (2) of the present invention is obtained by polymerizing a fluoromonomer (5). The fluorine-containing monomer is a fluorine-containing monomer and has a fluorine-containing cyclic acetal structure. The following fluorinated cyclic hemiacetal (8) is a compound which is a precursor of the fluorinated monomer (5).
Figure GDA0003005189880000492
(R in the formula (8))3X is the same as formula (7). )
[ fluorinated cyclic hemiacetal (9) ]
The fluorine-containing hemiacetal (7) of the present invention is preferably a fluorine-containing hemiacetal (9) in which Y in the formula (8) is a trifluoromethyl group.
The fluoropolymer (3) of the present invention is obtained by polymerizing a fluoromonomer (6). The fluorine-containing monomer is a monomer having a fluorine-containing cyclic acetal structure. The following fluorinated cyclic hemiacetal (9) is a compound which is a precursor of the fluorinated monomer (6).
Figure GDA0003005189880000501
(R in the formula (9))3The meaning of the formula (7) is the same. )
10. Synthesis of fluorinated cyclic hemiacetal (7)
A process for producing the fluorinated cyclic hemiacetal (7) of the present invention will be described.
The method for producing the cyclic hemiacetal compound is as follows: the cyclic hemiacetal compound of invention 12 represented by formula (7) is obtained by cyclizing a hydroxycarbonyl compound represented by formula (10) below or a hydroxyvinyl ether or hydroxyvinyl ester represented by formula (11).
Figure GDA0003005189880000502
(in the formula, R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. Z is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein some or all of the hydrogen atoms in Z are optionally substituted with a halogen atom, and wherein Z optionally contains an ether bond, a siloxane bond, a thioether bond or a carbonyl bond. )
The fluorinated cyclic hemiacetal (7) of the present invention can be synthesized mainly through two steps shown below.
10-1. step 1
The step 1 is as follows: the hydroxy vinyl ester represented by formula (10) or the hydroxy vinyl ether represented by formula (11) is obtained by reacting allyl alcohols, allyl ethers or allyl esters with hexafluoroacetone (hereinafter, sometimes referred to as HFA) or carbonyl-ene of trifluoroacetate.
The following discloses a reaction for obtaining a hydroxyvinylcarbonyl compound represented by formula (10) or a hydroxyvinyl ether or a hydroxyester represented by formula (11) by reacting an allyl alcohol, an allyl ether or an allyl ester represented by formula (12) with a carbonyl-ene of a trifluorocarbonyl compound represented by formula (13). Hereinafter, they may be referred to as hydroxycarbonyl compound (10), hydroxyvinyl ether (11), allyl alcohol (12), allyl ether (12), allyl ester (12), and trifluorocarbonyl compound (13).
Figure GDA0003005189880000511
(in the formula, R1The alkyl group is a straight-chain or branched alkyl group having 1 to 10 carbon atoms or a hydrogen atom, fluorine atom or a branched alkyl group having 3 to 10 carbon atoms, and 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted by fluorine atoms. R2～R5Is a hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted by fluorine atoms. Y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms. R is a C1-3 fluoroalkyl group. Z is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein some or all of the hydrogen atoms in Z are optionally substituted with a halogen atom, and wherein Z optionally contains an ether bond, a siloxane bond, a thioether bond or a carbonyl bond. )
An allyl alcohol (12) wherein Z is a hydrogen atom, an allyl ether (12) wherein Z is an alkyl group and the hydroxyl group is protected, or an allyl ester (12) is mixed with HFA wherein Y is a trifluoromethyl group, and the mixture is heated as necessary under a pressure sealed by an autoclave or the like, thereby selectively synthesizing a hydroxyvinyl ester (10) or a hydroxyvinyl ether (11). Further, when trifluoroacetonate is used instead of HFA, the reaction proceeds efficiently.
This reaction is a reaction of an allyl site of an allyl alcohol (12), an allyl ether (12) or an allyl ester (12) with an alkene of a fluorine-containing carbonyl compound (13), and the higher the electron density of the alkene moiety on the side of the allyl alcohol (12), the allyl ether (12) or the allyl ester (12), the more easily the reaction proceeds, and the fewer side reactions, the more selectively the reaction can proceed. With allyl alcohols (12), allyl ethers (12) or R of allyl esters (12)2～R5It is preferable that all of (a) are hydrogen atoms, and some of the groups are substituted with electron-donating groups, and the electron-donating groups are preferably methyl groups.
The amount of HFA or trifluoroacetonate used is preferably 0.5 mol or more and 10mol or less, and particularly preferably 1mol or more and 3mol or less, based on 1mol of allyl alcohol (12), allyl ether (12), or allyl ester (12).
[ allyl alcohols ]
Examples of the allyl alcohol (12) in which Z is a hydrogen atom include: allyl alcohol, beta-methallyl alcohol, 1-buten-3-ol, crotyl alcohol or 3-methyl-2-buten-1-ol.
[ allyl ethers ]
The allyl ether (12) or allyl ester (12) in which Z is other than a hydrogen atom is preferably an allyl ether obtained by introducing a protecting group to the hydroxyl group of the allyl alcohol (12), and examples of the kind of the protecting group include: silyl, acetal, acyl, benzyl or carbamate. In order to increase the electron density of the olefin portion and promote the reaction, the protective group is preferably an acetal, silyl, carbamate, or benzyl group.
< silyl groups >
Examples of the silyl group include: trimethylsilyl, triethylsilyl, tributylsilyl, tert-butyldimethylsilyl or tert-butyldiphenylsilyl.
< acetals >
As acetals, there can be exemplified: tetrahydropyranyl, ethoxyethyl, butoxyethyl, methoxymethyl, methylthiomethyl, benzyloxymethyl or methoxyethoxymethyl.
< acyl group >
As the acyl group, there can be exemplified: formyl, acetyl, trifluoroacetyl, propionyl, benzoyl, pivaloyl, acryloyl or methacryloyl.
< benzyl group >
As benzyl groups, there can be exemplified: benzyl, p-methoxybenzyl.
< urethanes >
As the carbamates, there can be exemplified: tert-butoxycarbonyl, benzyloxycarbonyl.
10-2, step 1
The reaction in the above step 1 may be carried out in the absence of a catalyst or a solvent, but an acid catalyst may be used in a solvent to promote the reaction. For the production at a lower cost, it is preferable to separate a hydroxycarbonyl compound represented by the following formula (10), a hydroxyvinyl ether represented by the following formula (11), or a hydroxyvinyl ester from the reaction product by a purification operation such as distillation without a solvent or a catalyst.
Figure GDA0003005189880000531
The use of the catalyst is not particularly limited, and when used, any of an inorganic acid, an organic acid, and a lewis acid may be used.
As the inorganic acid, there can be exemplified: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, or zeolite. Examples of the organic acid include: carboxylic acid, sulfonic acid, cation exchange resin, lewis acid. Specifically, as the carboxylic acid, there can be exemplified: formic acid, acetic acid or trifluoroacetic acid, as sulfonic acids, there may be exemplified: methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid, as lewis acids, mention may be made of: aluminum chloride, titanium tetrachloride or tin chloride.
The reaction can be carried out without using a solvent, and when a solvent is used, it is only necessary to use a solvent inert to the allyl alcohol (12), the allyl ether (12) or the allyl ester (12), and the HFA or the trifluoroacetate (13) as the raw materials, and the target fluorine-containing compound represented by the formula (10) or the formula (11). Examples are: aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons or ethers.
[ aliphatic hydrocarbons ]
As the aliphatic hydrocarbon, there can be exemplified: hexane, heptane, cyclohexane, methylcyclohexane as a cyclic aliphatic hydrocarbon.
[ aromatic hydrocarbons ]
As the aromatic hydrocarbon, there can be exemplified: benzene, toluene or xylene.
[ halogenated hydrocarbons ]
As the halogenated hydrocarbon, there can be exemplified: dichloromethane.
[ ethers ]
As ethers, there can be exemplified: diethyl ether, dibutyl ether, tetrahydrofuran or ethylene glycol dimethyl ether.
10-3. step 2
The 2 nd step is as follows: the hydroxycarbonyl compound (10), a hydroxyvinyl ether or a hydroxyvinyl ester (11) is subjected to intramolecular cyclization to obtain a cyclic hemiacetal compound (7).
The three methods (methods 1 to 3) described above can be mainly used, but they are different depending on the kind and substituents of the product in the step 1.
10-3-1. method-1
Method-1 is a method represented by the following reaction formula, in which a hydroxycarbonyl compound (10) is selectively cyclized intramolecularly in a solvent by the action of an acid or a base to obtain a fluorine-containing cyclic hemiacetal (7).
Method-1
Figure GDA0003005189880000541
The process is preferably carried out in a solvent under acidic or basic conditions.
As the acid, any of an inorganic acid, an organic acid, and a lewis acid can be used. The amount of the acid used in the reaction is preferably 0.01mol or more and 1mol or less, and particularly preferably 0.05mol or more and 0.2mol or less, based on 1mol of the hydroxycarbonyl compound (10).
Examples of the base include: inorganic bases, organic bases. In the case of a two-phase system in which unreacted raw materials and a water-organic solvent containing a fluorine-containing alcohol contained in a small amount can be removed, it is particularly preferable to use sodium hydroxide or potassium hydroxide under alkaline conditions. The amount of the base used in the reaction is preferably 0.5 mol or more and 10mol or less based on 1mol of the hydroxycarbonyl compound (10), and particularly preferably 1mol or more and 3mol or less in terms of improving the yield.
[ inorganic acid ]
As the inorganic acid, there can be exemplified: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, or zeolite.
[ organic acid ]
Examples of the organic acid include: carboxylic acid, sulfonic acid, cation exchange resin, lewis acid. As the carboxylic acid, there can be exemplified: formic acid, acetic acid or trifluoroacetic acid, as sulfonic acids, there may be exemplified: methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid, as lewis acids, mention may be made of: aluminum chloride, titanium tetrachloride or tin chloride.
[ inorganic base ]
As the inorganic base, there can be exemplified: lithium chlorohydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium hydride, sodium hydride, potassium hydride, and ammonia.
[ organic base ]
As the organic base, there may be mentioned: organic lithium salt, Grignard reagent and organic alkali metal salt.
As the organic lithium salt, there may be exemplified: triethylamine, diisopropylethylamine, pyridine, imidazole, triethylenediamine, dimethylaminopyridine, methyllithium or n-butyllithium. As the grignard reagent, there can be exemplified; methyl magnesium bromide. As the organic alkali metal salt, there can be exemplified: sodium methoxide, sodium ethoxide, and potassium tert-butoxide.
[ solvent ]
The reaction can be carried out without using a solvent, and when a solvent is used, it is only necessary to use a solvent which is inert to the hydroxycarbonyl compound (10) as the raw material and the fluorine-containing cyclic hemiacetal (7) as the product. Examples thereof include: water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers.
As the aliphatic hydrocarbon, there can be exemplified: hexane, heptane, cyclohexane, methylcyclohexane as a cyclic aliphatic hydrocarbon. As the aromatic hydrocarbon, there can be exemplified: benzene, toluene or xylene. As the halogenated hydrocarbon, there can be exemplified: dichloromethane, as ethers, can be exemplified: diethyl ether, dibutyl ether, tetrahydrofuran or ethylene glycol dimethyl ether.
10-3-2. method-2
Method-2 is a method represented by the following reaction formula, in which a hydroxyl vinyl ether (11) or a hydroxyl vinyl ester (11) is deprotected, and then hydrogen atoms of the hydroxyl groups are abstracted by the action of an acid or a base in a solvent, thereby selectively causing intramolecular cyclization to obtain a fluorine-containing cyclic hemiacetal (7). The reaction is shown below.
Method-2
Figure GDA0003005189880000561
The hydroxy vinyl ether (11) or the hydroxy vinyl ester (11) is a compound in which a hydroxyl group is protected, the protecting group of the hydroxy vinyl ether (11) or the hydroxy vinyl ester (11) is deprotected, and after conversion of the hydroxy vinyl ether (11) or the hydroxy vinyl ester (11) into a hydroxycarbonyl compound (10), intramolecular cyclization is carried out in the same manner as in the process-1, whereby a fluorine-containing cyclic hemiacetal (7) can be obtained. The deprotection can be carried out by a common deprotection method. The acid, base or solvent used is the same as in method-1.
10-3-3. method-3
Method-3 is a method represented by the following reaction formula, in which a hydrogen atom of a hydroxyl group is abstracted from a hydroxyvinyl ether (11) or a hydroxyvinyl ester (11) in a solvent by the action of an acid or a base to selectively perform intramolecular cyclization to obtain a fluorine-containing cyclic acetal intermediate (14), and then deprotection is performed to obtain a fluorine-containing cyclic hemiacetal (7). The reaction is shown below.
Method-3
Figure GDA0003005189880000562
[ intramolecular cyclization ]
The fluorine-containing cyclic acetal intermediate represented by the formula (14) can be obtained by adding an acid catalyst to a hydroxyvinyl ether (11) or a hydroxyvinyl ester (11) in the absence of a solvent or a solvent and heating the mixture to about the boiling point of the solvent.
Trifluoroacetic acid, methanesulfonic acid, or sulfuric acid is particularly preferable in terms of obtaining the fluorine-containing cyclic acetal intermediate (14) in a higher yield. The amount of the acid used in the reaction is preferably 0.01mol or more and 1mol or less, and particularly preferably 0.05mol or more and 0.2mol or less, based on 1mol of the hydroxyvinyl ether (11) or the hydroxyvinyl ester (11).
[ acid ]
As the acid used in the method-3, any of an inorganic acid, an organic acid and a Lewis acid can be used.
< inorganic acid >
As the inorganic acid, there can be exemplified: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, or zeolite.
< organic acid >
Examples of the organic acid include: carboxylic acid, sulfonic acid, cation exchange resin, lewis acid.
As the carboxylic acid, there can be exemplified: formic acid, acetic acid or trifluoroacetic acid, as sulfonic acids, there may be exemplified: methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid. As lewis acids, there can be exemplified: aluminum chloride, titanium tetrachloride or tin chloride.
[ deprotection ]
The fluorinated cyclic acetal intermediate (14) is in a form in which a hydroxyl group of the fluorinated cyclic hemiacetal (7) is protected with another substituent, and the fluorinated cyclic hemiacetal (7) can be obtained by removing the protecting group. The deprotection can be carried out by a common deprotection method.
On the other hand, in the case of the fluorine-containing compound (15) in which Z of the hydroxyvinyl ether (11) has a polymerizable group, the fluorine-containing monomer (4) can be synthesized by cyclizing the first half portion of the molecule according to Process-3. The reaction is shown below.
Figure GDA0003005189880000571
[ examples ]
The present invention will be described in detail below with reference to examples. The present invention is not limited to the following examples.
1. Synthesis of fluorine-containing cyclic hemiacetal
Fluorinated cyclic hemiacetals-1 to 7, which are precursors for obtaining a fluorinated monomer (4), are synthesized from the fluorinated monomer represented by the above formula (7) by the following method.
1-1-1 Synthesis of fluorinated Cyclic hemiacetal-1
Allyl alcohol (11.6 g (0.2mol) produced by tokyo chemical corporation) was charged into a reactor equipped with a stirrer, the reactor was sealed, then, the inside of the reactor was degassed by a vacuum pump, 66.4g (0.40mol) of HFA was introduced while stirring the contents with the stirrer, then, the inside of the reactor was heated to 150 ℃.
Figure GDA0003005189880000581
< result of nuclear magnetic resonance analysis >
The results of nuclear magnetic resonance analysis (hereinafter, may be referred to as NMR) are shown below.
1H-NMR (solvent: deuterated chloroform, standard substance: TMS (tetramethylsilane)): delta (ppm)2.32-2.59(2H, m),2.65-2.78(2H, m),4.11(1H, br),6.20(1H, d)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-77.5(3F,s),-79.5(3F,s)
1-1-2 Synthesis of fluorinated Cyclic hemiacetal-1 (its second)
A reaction vessel equipped with a stirrer was charged with 11.6g (0.2mol) of allyl alcohol and 0.2g (0.0002mol) of methanesulfonic acid, the reaction vessel was sealed, then the inside of the reaction vessel was degassed by a vacuum pump, 66.4g (0.40mol) of HFA was introduced while stirring the contents with the stirrer, the inside of the reaction vessel was heated to 120 ℃ and then stirred for 20 hours, after the reaction was completed, the contents were taken out and transferred to a separatory funnel, 50ml of a 4 mass% aqueous sodium hydroxide solution was added, after stirring for 1 hour, the organic layer was separated, and distillation was carried out under reduced pressure at a pressure of 3.0kPa and a temperature of 60 to 62 ℃ to obtain a fluorine-containing cyclic hemiacetal represented by the following formula in a yield of 63% to 128 g or less.
Figure GDA0003005189880000591
1-2. Synthesis of fluorine-containing cyclic hemiacetal-2
The reaction was performed by charging beta-methallyl alcohol (14.4 g (0.2mol) manufactured by tokyo chemical corporation) into a reactor equipped with a stirrer, sealing the reactor, degassing the inside of the reactor by a vacuum pump, introducing 66.4g (0.40mol) of HFA while stirring the contents by the stirrer, heating the inside of the reactor to 40 ℃, then continuing to stir for 2 hours, after the reaction was completed, taking out the contents and transferring the contents to a separatory funnel, adding 50ml of hydrochloric acid having a concentration of 3.5 mass%, stirring for 2 hours, separating an organic layer and a water layer, adding 50ml of a sodium hydroxide aqueous solution having a concentration of 4 mass% to the organic layer, stirring for 1 hour, separating the organic layer, and distilling under reduced pressure under a pressure of 3.0kPa and a temperature of 68 to 69 ℃, whereby a cyclic hemiacetal having a fluorine content represented by the following formula was obtained at a yield of 92%, 243 to 7.7 g or less.
Figure GDA0003005189880000592
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): delta (ppm)
Isomer 1: 1.14(3H, d),1.93-2.05(1H, m),2.40(2H, dd),3.80(1H, d),5.19(1H, d)
Isomer 2: 1.10(3H, d),2.18(1H, dd),2.2-2.5(1H, m),2.55(1H, dd),3.25(1H, d),5.55(1H, d)
19F-NMR (solvent: deuterated chloroform,standard substance: c6D6)：δ(ppm)-77.5(3F,m),-79.5(3F,m)
1-3 Synthesis of fluorinated Cyclic hemiacetal-3
The reaction shown by the following formula was carried out in the same manner as in the synthesis of the fluorinated cyclic hemiacetal-2 except that 2-methyl-3-buten-2-ol (manufactured by Tokyo chemical Co., Ltd.) was used instead of the β -methallyl alcohol used in the synthesis of the fluorinated cyclic hemiacetal-2, whereby the fluorinated cyclic hemiacetal-3 was obtained in a yield of 87%.
The reaction is shown below.
Figure GDA0003005189880000601
1-4. Synthesis of fluorine-containing cyclic hemiacetal-4
The reaction shown by the following formula was carried out in the same manner as in the synthesis of the fluorinated cyclic hemiacetal-2 except that crotyl alcohol (manufactured by Tokyo chemical Co., Ltd.) was used instead of the β -methallyl alcohol used in the synthesis of the fluorinated cyclic hemiacetal-2, and the fluorinated cyclic hemiacetal-4 was obtained in a yield of 75%. The reaction is shown below.
Figure GDA0003005189880000602
1-5 Synthesis of fluorine-containing cyclic hemiacetal-5
The reaction shown by the following formula was carried out in the same manner as in the synthesis of the fluorinated cyclic hemiacetal-2 except that 3-methyl-2-buten-1-ol (manufactured by Tokyo chemical Co., Ltd.) was used instead of the β -methallyl alcohol used in the synthesis of the fluorinated cyclic hemiacetal-2, whereby fluorinated cyclic hemiacetal-5 was obtained in a yield of 65%.
The reaction is shown below.
Figure GDA0003005189880000603
1-6 synthesis of fluorine-containing cyclic hemiacetal-6
In a 100ml glass flask equipped with a stirrer, 1.86g (0.01mol) of β -methylallyl-t-butyldimethylsilyl ether obtained by protecting β -methylallyl alcohol with t-butyldimethylsilyl group according to a conventional method in advance and 2.92g (0.01mol) of separately synthesized 1,1,1,3,3, 3-hexafluoroisopropyl trifluoroacetate were mixed. Subsequently, the temperature in the reactor was raised to 50 ℃ and the stirring was continued for 18 hours. After completion of the reaction, the contents were taken out and transferred to a separatory funnel, 10ml of hydrochloric acid having a concentration of 3.5% by mass was added, and after stirring for 2 hours, the organic layer and the aqueous layer were separated. To the organic layer was added 10ml of a 4 mass% aqueous sodium hydroxide solution, and after stirring for 1 hour, the organic layer was separated and separated by silica gel column chromatography. The cyclic hemiacetal having fluorine-containing structure represented by the following formula-619.0 g was obtained in a yield of 52%. The reaction is shown below.
Figure GDA0003005189880000611
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): delta (ppm)
Isomer 1: 1.17(3H, d),1.97-2.11(1H, m),2.45(2H, dd),3.81(1H, d),5.25(1H, d),5.68(1H, m)
Isomer 2: 1.11(3H, d),2.22(1H, dd),2.25-2.53(1H, m),2.65(1H, dd),3.30(1H, d),5.60(1H, d),5.68(1H, m)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-77.1(6F,m),-78.5(3F,m)
[ Synthesis of 1,1,1,3,3, 3-hexafluoroisopropyl trifluoroacetate ]
The procedure for synthesizing 1,1,1,3,3, 3-hexafluoroisopropyl trifluoroacetate used for the synthesis of the fluorinated cyclic hemiacetal-6 is shown below.
To a 100ml Glass flask equipped with a stirrer, 17.0g (0.1mol) of ethyl trifluoropyruvate (Central Glass Co., Ltd., trade name: E-TFPA) was added, and 50ml of a 10 mass% aqueous solution of sodium hydroxide was added and stirred for 2 hours. After ethanol was distilled off by concentration under reduced pressure, 55ml of 10 mass% hydrochloric acid was added for neutralization, 30ml of dichloromethane was added, and the resulting trifluoropyruvic acid was extracted from the dichloromethane layer. The dichloromethane layer was separated, water was removed by a drying agent, 16.2g (0.1mol) of CDI (carbonyldiimidazole) (Wako pure chemical industries, Ltd.) was added thereto, and the mixture was stirred at room temperature for 1 hour, and 16.8g (0.1mol) of HFIP (Central Glass Co., Ltd.) was added thereto, and further stirred for 2 hours. 30ml of hydrochloric acid having a concentration of 3.5% by mass was added to the reaction solution, and the mixture was washed 2 times with 30ml of pure water. The organic layer was separated and distilled under reduced pressure at a pressure of 40kPa and a temperature of 65 ℃ to obtain 16g of 1,1,1,3,3, 3-hexafluoroisopropyl trifluoroacetate in a yield of 55%. The reaction is shown below.
Figure GDA0003005189880000621
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): delta (ppm)5.65(1H, m)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-76.6(6F,s),-83.1(3F,s)
1-7 Synthesis of fluorine-containing cyclic hemiacetal-7
The reaction represented by the following formula was carried out in the same manner as in the synthesis of the fluorinated cyclic hemiacetal-6 except that 2,2, 2-trifluoroethyl trifluoroacetate separately synthesized was used instead of 1,1,1,3,3, 3-hexafluoroisopropyl trifluoroacetate used in the synthesis of the fluorinated cyclic hemiacetal-6, and fluorinated cyclic hemiacetal-7 was obtained in a yield of 61%. The reaction is shown below.
Figure GDA0003005189880000622
[ Synthesis of 2,2, 2-trifluoroethyl trifluoroacetate ]
The procedure for synthesizing 2,2, 2-trifluoroethyl trifluoropyruvate used for the synthesis of the fluorinated cyclic hemiacetal-7 will be described below.
In a 100ml glass flask equipped with a stirrer, 16.2g (0.1mol) of CDI (carbonyldiimidazole) was added to a dichloromethane solution of trifluoropyruvic acid shown in the above synthesis example, and stirred at room temperature for 1 hour, 10.0g (0.1mol) of 2,2, 2-trifluoroethanol (Wako pure chemical industries, Ltd.) was added, and further stirred for 2 hours. 30ml of hydrochloric acid having a concentration of 3.5% by mass was added to the reaction solution, and the mixture was washed 2 times with 30ml of pure water. The organic layer was separated and distilled under reduced pressure at a pressure of 30kPa and a temperature of 65 ℃ to obtain 11g of 2,2, 2-trifluoroethyl trifluoroacetate in a yield of 50%. The reaction is shown below.
Figure GDA0003005189880000631
2. Synthesis of fluorine-containing monomer
The fluorinated monomer (4) is synthesized using the fluorinated cyclic hemiacetal-1, 2,6, 7 represented by the above formula (7).
2-1. Synthesis of fluoromonomer-1
A300 ml glass flask equipped with a stirrer was charged with 122.4g (0.1mol) of fluorinated cyclic hemiacetal, 15.1g (0.15mol) of triethylamine, and methoxyphenol (1000ppm) as a polymerization inhibitor, and 16.9g (0.11mol) of methacrylic anhydride was added dropwise at an internal temperature of 30 ℃ or lower. After stirring for 2 hours, 40ml of diisopropyl ether and 30ml of pure water were added and stirred, and after separating, 20ml of a 1 wt% aqueous sodium hydroxide solution was added and stirred for 1 hour, and then separating was performed. The organic layer was washed 2 times with 30ml of pure water, and then distilled under reduced pressure at a temperature of 70 to 72 ℃ under 1.1kPa to obtain fluoromonomer-1 in a yield of 85%. The reaction is shown below.
Figure GDA0003005189880000632
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): δ (ppm)1.92(3H, s),2.32-2.59(2H, m),2.72-2.89(2H, m),5.65(1H, q),6.12(1H, q),6.68(1H, d)
19F-NMRPreparation: deuterated chloroform, standard substance: c6D6)：δ(ppm)-77.5(3F,s),-79.5(3F,s)
2-2. Synthesis of fluoromonomer-2
The reaction shown by the following formula was carried out in the same manner as in the synthesis of the fluorinated monomer-1 except that the fluorinated cyclic hemiacetal-2 was used instead of the fluorinated cyclic hemiacetal-1 used in the synthesis of the fluorinated monomer-1, whereby the fluorinated monomer-2 was obtained in a yield of 93%. The reaction is shown below.
Figure GDA0003005189880000641
< result of NMR analysis >
The results of the nmr analysis are shown below.
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): δ (ppm)1.19(3H, s) (isomer a),1.23(3H, s) (isomer B), after which no peak separation of the isomers occurred, which was assigned to the mixture. 1.92(3H, s),2.32-2.59(2H, m),2.72-2.89(2H, m),5.65(1H, q),6.14(1H, q),6.17(1H, dd)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-77.3(3F,s),-79.0(3F,s)
2-3. Synthesis of fluoromonomer-3
The reaction represented by the following formula was carried out in the same manner as in the synthesis of the fluoromonomer-2 except that 2-fluoroacryloyl chloride was used instead of methacrylic anhydride used in the synthesis of the fluoromonomer-2, whereby fluoromonomer-3 was obtained in a yield of 70%. The reaction is shown below.
Figure GDA0003005189880000642
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): δ (ppm)1.17(3H, s) (isomer a),1.22(3H, s) (isomer B), after which no peak separation of the isomers occurred, which was assigned to the mixture. 1.92(3H,s),2.32-2.59(2H,m),2.72-2.89(2H,m),6.12(1H,q),6.45(1H,q),6.68(1H,d)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-10.3(1F,S),-77.3(3F,s),-79.0(3F,s)
2-4. Synthesis of fluoromonomer-4
The reaction represented by the following formula was carried out in the same manner as in the synthesis of the fluoromonomer-2 except that 2-methacryloyloxyacetyl chloride was used instead of methacrylic anhydride used in the synthesis of the fluoromonomer-2, to obtain fluoromonomer-4 in a yield of 80%. The reaction is shown below.
Figure GDA0003005189880000651
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): δ (ppm)1.21(3H, s),1.90(3H, s),2.30-2.55(2H, m),2.74-2.86(2H, m),4.43(2H, s),5.60(1H, q),6.09(1H, q),6.15(1H, dd)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-77.7(3F,s),-79.6(3F,s)
2-5. Synthesis of fluoromonomer-5
A300 ml glass flask equipped with a stirrer was charged with 222.4g (0.1mol) of fluorinated cyclic hemiacetal, 15.1g (0.15mol) of triethylamine, 0.8g (0.05mol) of potassium iodide, 20ml of dimethylformamide, and methoxyphenol (1000ppm) as a polymerization inhibitor, and 16.3g (0.11mol) of chloroethyl methacrylate was added dropwise at an internal temperature of 30 ℃ or lower. After stirring for 2 hours, 40ml of diisopropyl ether and 30ml of pure water were added and stirred, and after liquid separation, 50ml of 5 wt% hydrochloric acid water was added and stirred for 30 minutes, liquid separation was performed. The organic layer was washed 2 times with 50ml of pure water, and then distilled under reduced pressure at 1.0kPa and a temperature of 89 to 91 ℃ to obtain fluoromonomer-5 in a yield of 45%. The reaction is shown below.
Figure GDA0003005189880000661
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): δ (ppm)1.23(3H, s),1.92(3H, s),2.22-2.50(2H, m),2.70-2.81(2H, m),3.85(2H, m),4.03(2H, m),5.63(1H, q),6.15(1H, q),6.22(1H, dd)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-77.0(3F,s),-79.3(3F,s)
2-6. Synthesis of fluoromonomer-6
The reaction represented by the following formula was carried out in the same manner as in the synthesis of the fluorinated monomer-2 except that the fluorinated cyclic hemiacetal-6 was used in place of the fluorinated cyclic hemiacetal-2 used in the synthesis of the fluorinated cyclic monomer-2, whereby the fluorinated monomer-6 was obtained in a yield of 78%. The reaction is shown below.
Figure GDA0003005189880000662
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): δ (ppm)1.16(3H, s),1.95(3H, s),2.27-2.54(2H, m),2.65-2.80(2H, m),5.61(1H, q),5.83(1H, m),6.12(1H, q),6.18(1H, dd)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-77.5(6F,m),-79.5(3F,m)
2-7. Synthesis of fluoromonomer-7
The reaction shown by the following formula was carried out in the same manner as in the synthesis of the fluorinated monomer-7 except that the fluorinated cyclic hemiacetal-7 was used in place of the fluorinated cyclic hemiacetal-2 used in the synthesis of the fluorinated monomer-2, whereby the fluorinated monomer-7 was obtained in a yield of 74%. The reaction is shown below.
Figure GDA0003005189880000671
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): δ (ppm)1.22(3H, s),1.89(3H, s),2.24-2.50(2H, m),2.68-2.87(2H, m),4.86(2H, m),5.65(1H, q),6.13(1H, q),6.18(1H, dd)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-77.9(3F,m),-78.5(3F,m)
2-8. Synthesis of fluoromonomer-8
The reaction shown by the following formula was carried out in the same manner as in the synthesis of the fluoromonomer-6 except that 2-fluoroacryloyl chloride was used instead of methacrylic anhydride used in the synthesis of the fluoromonomer-6, whereby fluoromonomer-8 was obtained in a yield of 68%. The reaction is shown below.
Figure GDA0003005189880000672
< result of NMR analysis >
1H-NMR (solvent: deuterated chloroform, standard substance: TMS): δ (ppm)1.17(3H, s),2.27-2.52(2H, m),2.62-2.82(2H, m),5.64(1H, q),5.93(1H, m),6.42(1H, q),6.68(1H, dd)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-10.1(1F,S),-77.9(6F,m),-79.0(3F,m)
2-9 Synthesis of fluoromonomer-9
The reaction represented by the following formula was carried out in the same manner as in the synthesis of the fluoromonomer-7 except that 2-fluoroacryloyl chloride was used instead of methacrylic anhydride used in the synthesis of the fluoromonomer-7, whereby fluoromonomer-9 was obtained in a yield of 65%. The reaction is shown below.
Figure GDA0003005189880000681
< result of NMR analysis >
1H-NMR (solvent: deuterated chlorine)Imitation, standard substance: TMS): δ (ppm)1.17(3H, s),2.27-2.52(2H, m),2.62-2.82(2H, m),4.93(2H, m),5.64(1H, q),6.42(1H, q),6.68(1H, dd)
19F-NMR (solvent: deuterated chloroform, standard substance: C)6D6)：δ(ppm)-10.4(1F,S),-77.1(6F,m),-79.3(3F,m)
3. Synthesis of comparative monomers
In order to compare with the fluorine-containing monomers 1 to 7 of the present invention, comparative monomers 1 to 3 which do not belong to the fluorine-containing monomer represented by the formula (6) were synthesized.
3-1 Synthesis of comparative monomer-1
Comparative monomer-1 was synthesized using the method described in patent document 3.
In a 1000ml glass flask equipped with a stirrer, 30.0g of methacrylic acid and 58.6g of dihydroxypyran were dissolved in 450ml of dichloroethane, and 0.1g of p-toluenesulfonic acid was added thereto and stirred for 1 hour. The reaction was stopped by adding 3ml of triethylamine. The resulting reaction mixture was washed with 50ml of water, dried over anhydrous magnesium sulfate, and distilled to remove the solvent, and then distilled under reduced pressure at a temperature of 66 ℃ to 67 ℃ under 0.4kPa to obtain-150 g of a comparative monomer. The reaction is shown below. The reaction is shown below.
Figure GDA0003005189880000682
3-2 Synthesis of comparative monomer-2
Comparative monomer-2 was synthesized using the method described in patent document 5.
To a mixture of 16.8g of HFIP and 120g of tetrahydrofuran, 129ml of butyllithium (1.6M hexane solution) was added at 5 ℃ under a nitrogen atmosphere, and the mixture was stirred at 5 ℃ for 1 hour. Next, 14.2g of 2-oxopropyl methacrylate was added at 5 ℃. After stirring for 10 hours, the reaction was stopped by addition of dilute hydrochloric acid and neutralization was carried out. After ordinary aqueous post-treatment, the product was purified by silica gel column chromatography to obtain 25.3g of triol as a synthetic intermediate. A mixture of 24g of triol compound, 15.6g of triethylamine and 15g of toluene was stirred at 70 ℃ for 4 hours. After cooling to room temperature, the mixture was neutralized with dilute hydrochloric acid, and the organic layer was separated. The crude product obtained in the usual workup of washing, drying and concentration was distilled under reduced pressure to obtain 20g of hemiacetal.
A mixture of 3.2g of the hemiacetal obtained above, 2.8g of methyl iodide, 2.8g of silver (I) oxide and 150g of ethyl acetate was stirred at 40 ℃ for 24 hours. Insoluble matter was separated by filtration, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 23 g of comparative monomer. The reaction is shown below.
Figure GDA0003005189880000691
(Mel stands for methyl iodide)
3-3 Synthesis of comparative monomer-3
A300 ml glass flask equipped with a stirrer was charged with 33.6g (0.3mol) of vinyl methacrylate (manufactured by Tokyo Kasei Co., Ltd., the same shall apply hereinafter) and 52.9g (0.315mol) of HFIP, 0.74g (7.5mmol) of sulfuric acid was slowly added thereto, and the mixture was stirred at a reaction temperature of 40 ℃ for 6 hours to carry out a reaction represented by the following formula.
The reaction is shown below.
Figure GDA0003005189880000692
After the reaction mixture was cooled to room temperature, 50ml of a 6% by mass aqueous sodium bicarbonate solution was added thereto and stirred. Subsequently, the reaction solution was transferred to a separatory funnel, and the organic layer was collected by standing and separating. The collected organic layer was distilled under reduced pressure to obtain comparative monomer-339 g in a yield of 47%. The boiling point of the comparative monomer-3 obtained was 62 ℃ under a pressure of 4.0 kPa.
4. Synthesis of polymers
Fluoropolymers 1 to 12 and comparative polymers 1 to 7 were synthesized using fluoromonomers 1 to 9, comparative monomers 1 to 3, and hexafluoroisopropyl methacrylate (trade name HFIP-M, manufactured by Central Glass corporation) as comparative monomer 4. The fluorine-containing polymers 1 to 12 belong to the fluorine-containing polymer (1). The comparative monomers-1 to 7 are used for comparison with the fluoropolymers-1 to 12 of the present invention, and do not belong to the fluoropolymer (1).
In addition, for the fluorine-containing polymers-1 to 9 and the comparative polymers-1 to 4, in order to clearly show the effect of the monomer and the difference in the performance, the self-polymerization was synthesized and the performance was compared. For fluoropolymers 10 to 12 and comparative polymers 5 to 7, a comonomer was fixed to 5-methacryloxy-2, 6-norbornanecarbonolactone (MNLA) to compare the performance of the fluoromonomer of the present invention and the comparative monomer as a resist material.
[ analysis of Polymer ]
＜NMR＞
Composition of the repeating composition of the polymer by NMR1H-NMR and19F-NMR measurement value.
< molecular weight >
The number average molecular weight Mn and the molecular weight dispersion (ratio of the number average molecular weight Mn to the mass average molecular weight Mw: Mw/Mn) of the polymer were measured by connecting an ALPHA-M column and an ALPHA-2500 column, each in series, using a high-speed gel permeation chromatograph (hereinafter sometimes referred to as GPC; manufactured by Tosoh corporation, model HLC-8320GPC), and using tetrahydrofuran as a developing solvent. The detector uses a refractive index difference to determine the detector.
4-1. Synthesis of fluoropolymer-1
A300 ml glass flask equipped with a stirrer was charged with 129.2g (0.1mol) of a fluoromonomer and 60g of 2-butanone as a solvent at room temperature to prepare a butanone solution having a concentration of 33 mass%. 0.8g (0.005mol) of 2,2' -azobis (isobutyronitrile) (hereinafter, sometimes referred to as AIBN, manufactured by Wako pure chemical industries, Ltd.) was added as a polymerization initiator, and the mixture was degassed while stirring, then the inside of the flask was replaced with nitrogen gas, and the temperature was raised to 80 ℃ to conduct a reaction for 6 hours. The content after the completion of the reaction was added dropwise to 500g of n-heptane, to obtain a white precipitate. The precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 ℃ to obtain 125.6 g of a fluoropolymer containing repeating units based on fluoromonomer-1 as a white solid in a yield of 88%.
Figure GDA0003005189880000711
< result of GPC measurement >
Mw＝22000，Mw/Mn＝2.0
4-2 Synthesis of fluoropolymer-2
Fluoropolymer-2 containing the following repeating units was synthesized in the same manner as in the synthesis of fluoropolymer-1, except that fluoromonomer-2 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1, and fluoropolymer-2 was obtained in a yield of 87%.
Figure GDA0003005189880000712
< result of GPC measurement >
Mw＝23100，Mw/Mn＝2.1
4-3 Synthesis of fluoropolymer-3
Fluoropolymer-3 containing the following repeating units was synthesized in the same manner as in the synthesis of fluoropolymer-1, except that fluoromonomer-3 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1, and fluoropolymer-3 was obtained in a yield of 93%.
Figure GDA0003005189880000721
< result of GPC measurement >
Mw＝21200，Mw/Mn＝2.3
4-4 Synthesis of fluoropolymer-4
Fluoropolymer-4 having the following repeating units was synthesized in the same manner as in the synthesis of fluoropolymer-1, except that fluoromonomer-4 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1, and fluoropolymer-4 was obtained in a yield of 92%.
Figure GDA0003005189880000722
< result of GPC measurement >
Mw＝22500，Mw/Mn＝2.1
4-5 Synthesis of fluoropolymer-5
Fluoropolymer-5 containing the following repeating units was synthesized in the same manner as in the synthesis of fluoropolymer-1, except that fluoromonomer-5 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1, and fluoropolymer-5 was obtained in a yield of 90%.
Figure GDA0003005189880000731
< result of GPC measurement >
Mw＝24200，Mw/Mn＝2.3
4-6 Synthesis of fluoropolymer-6
Fluoropolymer-6 having the following repeating units was synthesized in the same manner as in the synthesis of fluoropolymer-1, except that fluoromonomer-6 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1, and fluoropolymer-6 was obtained in a yield of 72%.
Figure GDA0003005189880000732
< result of GPC measurement >
Mw＝20700，Mw/Mn＝2.5
4-7 Synthesis of fluoropolymer-7
Fluoropolymer-7 containing the following repeating units was synthesized in the same manner as in the synthesis of fluoropolymer-1, except that fluoromonomer-7 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1, and fluoropolymer-7 was obtained in a yield of 78%.
Figure GDA0003005189880000741
< result of GPC measurement >
Mw＝20100，Mw/Mn＝2.2
4-8 Synthesis of fluoropolymer-8
Fluoropolymer 8 having the following repeating units was synthesized in the same manner as in the synthesis of fluoropolymer 1, except that fluoromonomer 8 was used instead of fluoromonomer 1 used in the synthesis of fluoropolymer 1, and fluoropolymer 8 was obtained in a yield of 90%.
Figure GDA0003005189880000742
< result of GPC measurement >
Mw＝19700，Mw/Mn＝2.3
4-9 Synthesis of fluoropolymer-9
Fluoropolymer-9 having the following repeating units was synthesized in the same manner as in the synthesis of fluoropolymer-1, except that fluoromonomer-9 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1, and fluoropolymer-9 was obtained in a yield of 89%.
Figure GDA0003005189880000751
< result of GPC measurement >
Mw＝20900，Mw/Mn＝2.1
4-10 Synthesis of fluoropolymer-10
A glass flask was charged with 129.2g (0.1mol) of a fluorine-containing monomer, 11.1g (0.05mol) of 5-methacryloyloxy-2, 6-norbornanecarbonolide (MNLA) which is a repeating unit for imparting adhesion when a resist was produced, and 0.67g of n-dodecylmercaptan (manufactured by Tokyo chemical Co., Ltd.) at room temperature (about 20 ℃ C.), and then dissolved by adding 82.8g of 2-butanone. 1.7g of 2,2' -azobis (isobutyronitrile) (hereinafter, sometimes referred to as AIBN, manufactured by Wako pure chemical industries, Ltd.) was added as a polymerization initiator, and the mixture was degassed while stirring, then the inside of the flask was replaced with nitrogen gas, and the temperature was raised to 75 ℃ to conduct a reaction for 16 hours. The content after the completion of the reaction was added dropwise to 620.0g of n-heptane, whereby a white precipitate was obtained. The precipitate was separated by filtration and dried under reduced pressure at a temperature of 60 ℃ to obtain 1034 g of a fluoropolymer containing recurring units derived from fluoromonomer-1 and recurring units derived from MNLA shown below as a white solid in a yield of 85%.
Figure GDA0003005189880000752
< result of NMR measurement >
The composition ratio of each repeating unit in the fluoropolymer-10 was determined by NMR. The results of the measurement are expressed in mol% as repeating units derived from fluoromonomer-1: repeat units derived from MNLA 67: 33.
< result of GPC measurement >
Mw＝8500，Mw/Mn＝1.7
4-11 Synthesis of fluoropolymer-11
Fluoropolymer 11 was synthesized in the same manner as in the synthesis of fluoropolymer 10, except that fluoromonomer-2 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer 10, and fluoropolymer 11 containing the following repeating units was obtained in a yield of 86%.
Figure GDA0003005189880000761
< result of NMR measurement >
The composition ratio of each repeating unit in the fluoropolymer-11 was determined by NMR. The results of the measurement are expressed in mol% as repeating units derived from fluoromonomer-2: repeat units derived from MNLA 65: 35.
< result of GPC measurement >
Mw＝8700，Mw/Mn＝1.6
4-12 Synthesis of fluoropolymer-12
Fluoropolymer 12 was synthesized in the same manner as in the synthesis of fluoropolymer 10, except that fluoromonomer-6 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer 10, and fluoropolymer 12 containing the following repeating units was obtained in a yield of 73%.
Figure GDA0003005189880000762
< result of NMR measurement >
The composition ratio of each repeating unit in the fluoropolymer-12 was determined by NMR. The results of the determination are expressed in mol% as repeating units derived from fluoromonomer-6: repeat units derived from MNLA 64: 36.
< result of GPC measurement >
Mw＝7700，Mw/Mn＝1.7
5. Synthesis of comparative polymers
For comparison of the fluoropolymers 1 to 10 of the present invention, comparative polymers 1 to 7, which are not the fluoropolymer (1), were synthesized.
5-1 Synthesis of comparative Polymer-1
A comparative polymer-1 having the following repeating units was synthesized in the same manner as in the synthesis of the fluoropolymer-1, except that the comparative monomer-1 was used in place of the fluoromonomer-1 used in the synthesis of the fluoropolymer-1.
Figure GDA0003005189880000771
< result of GPC measurement >
Mw＝20100，Mw/Mn＝2.2
5-2 Synthesis of comparative Polymer-2
Comparative polymer-2, which contained the following repeating units, was synthesized in the same procedure as in the synthesis of fluoropolymer-1, except that comparative monomer-2 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1.
Figure GDA0003005189880000772
< result of GPC measurement >
Mw＝23400，Mw/Mn＝2.1
5-3 Synthesis of comparative Polymer-3
A comparative polymer-3 having the following repeating units was synthesized in the same manner as in the synthesis of the fluoropolymer-1, except that the comparative monomer-3 was used in place of the fluoromonomer-1 used in the synthesis of the fluoropolymer-1.
Figure GDA0003005189880000781
< result of GPC measurement >
The Mw of the polymer was 22800 and the Mw/Mn was 2.1 in accordance with GPC measurement.
5-4 Synthesis of comparative Polymer-4
A comparative polymer-4 having the following repeating units was synthesized in the same manner as in the synthesis of the fluoropolymer-1, except that the comparative monomer-4 was used in place of the fluoromonomer-1 used in the synthesis of the fluoropolymer-1.
Figure GDA0003005189880000782
< result of GPC measurement >
Mw＝20100，Mw/Mn＝2.1
5-5 Synthesis of comparative Polymer-5
Comparative polymer-5, which contained the following repeating units, was synthesized in the same procedure as in the synthesis of fluoropolymer-10, except that comparative monomer-1 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-10, and comparative polymer-5 was obtained in a yield of 89%.
Figure GDA0003005189880000791
< result of NMR measurement >
The composition ratio of each repeating unit in comparative polymer-5 was determined by NMR. The results of the assay are expressed in mol% as repeating units derived from comparative monomer-1: repeat units derived from MNLA 67: 33.
< result of GPC measurement >
Mw＝8300，Mw/Mn＝1.7
5-6 Synthesis of comparative Polymer-6
Comparative polymer-6, which contained the following repeating units, was synthesized in the same procedure as in the synthesis of fluoropolymer-10, except that comparative monomer-2 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-10, and comparative polymer-6 was obtained in a yield of 83%.
Figure GDA0003005189880000792
< result of NMR measurement >
The composition ratio of each repeating unit in comparative polymer-6 was determined by NMR. The results of the assay are expressed in mol% as repeating units derived from comparative monomer-2: repeat units derived from MNLA 65: 35.
< result of GPC measurement >
Mw＝8900，Mw/Mn＝1.6
5-7 Synthesis of comparative Polymer-7
Comparative polymer-7, which contained the following repeating units, was synthesized in the same procedure as in the synthesis of fluoropolymer-10, except that comparative monomer-3 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-10, and comparative polymer-7 was obtained in a yield of 81%.
Figure GDA0003005189880000801
< result of NMR measurement >
The composition ratio of each repeating unit in comparative polymer-7 was determined by NMR. The results of the assay are expressed in mol% as repeating units derived from comparative monomer-3: repeat units derived from MNLA 66: 34.
< result of GPC measurement >
Mw＝8100，Mw/Mn＝1.6
5-8 repeating units of fluoropolymer-1 to 10 and comparative polymer-1 to 7
The following shows the repeating units contained in the fluoropolymers 1 to 10 and the comparative polymers 1 to 7.
Figure GDA0003005189880000811
5-9 composition, molecular weight and yield of fluoropolymer-1-10 and comparative polymer-1-7
Table 1 shows compositions (ratio of repeating units), weight average molecular weights, molecular weight distributions and yields of fluoropolymers 1 to 10 and comparative polymers 1 to 7.
[ Table 1]
Figure GDA0003005189880000821
"monomer" is the ratio of repeating units derived from a fluoromonomer or a comparative monomer in a polymer
"MNLA" is the content ratio of the repeating units derived from MNLA (5-methacryloyloxy-2, 6-norbornanecarbonolide) in the polymer
5-10 glass transition temperature and 5% weight loss ratio of fluoropolymer-1-9 and comparative polymer-1-4
The glass transition temperatures and 5% weight loss ratios of fluoropolymers-1 to 9 and comparative polymers-1 to 4 were measured by the following methods.
[ method for measuring glass transition temperature and 5% weight loss ]
The thermal properties of the fluoropolymers-1 to 9 and the comparative polymers-1 to 4 were measured. The glass transition temperature (hereinafter sometimes referred to as Tg) and the 5% weight loss rate under thermogravimetry (hereinafter sometimes referred to as Td5) were measured using a differential scanning calorimeter (hereinafter sometimes referred to as DSC) manufactured by Hitachi High-Tech Science Corporation and a differential thermal-thermogravimetry synchronous measuring apparatus (hereinafter sometimes referred to as DTA).
[ measurement results ]
Table 2 shows the results of the Tg and Td5 measurements of the fluoropolymers-1 to 9 and comparative polymers-1 to 4. It is known that, in a pattern forming material for lithography and printed electronics, Tg and Td5 tend to be high as follows: the mask pattern was transferred more faithfully, and the Line Edge Roughness (Line Edge Roughness) and Line Width Roughness (Line Width Roughness) of the resulting pattern were good.
[ Table 2]
Figure GDA0003005189880000831
The fluoropolymers-1 to 9 and comparative polymers-1 to 2 having a cyclic acetal structure have a Tg higher by about 25 ℃ than the chain-like comparative polymers 3 and 4. The fluoropolymers 1 to 3, 8 and 9 showed a higher Tg than the comparative polymer 1 having the same skeleton but no fluorine atom.
6. Composition for forming pattern for printed electronics
6-1 preparation of Pattern Forming composition for printed electronics
The compositions-1 to 9 for pattern formation of the present invention and comparative compositions-1 to 4 for comparison thereof were prepared using fluoropolymers-1 to 9 and comparative polymers-1 to 4 each containing a repeating unit shown below.
Figure GDA0003005189880000841
Compositions 1 to 9 for forming a pattern and comparative compositions 1 to 4 were prepared by adding N-hydroxynaphthalimide-trifluoromethanesulfonate (A) as an acid generator, 2-isopropyl-thioxanthone (D) as a sensitizer, 2-phenylbenzimidazole (C) as a quencher, and diethylene glycol monoethyl ether (B) as an organic solvent to fluoropolymers 1 to 9 and comparative polymers 1 to 4. The composition ratios of the pattern-forming compositions-1 to 9 and the comparative compositions-1 to 4 are expressed as the following polymers in parts by mass: (A) acid generators: (D) sensitizer: (C) quenching agent: (B) the organic solvent is 100: 2: 1: 0.05: 300, were compounded.
6-2. film formation of composition for pattern formation for printed electronics
The pattern-forming compositions 1 to 9 and comparative compositions 1 to 4 prepared by coating on a glass substrate with a spin coater were dried on a hot plate heated to 100 ℃ for 2 minutes to form a film having a film thickness of 0.5. mu.m. Subsequently, the film was irradiated with a high-pressure mercury lamp. Further, the pattern of the mask was transferred to the film by irradiating ultraviolet light through the mask using a high-pressure mercury lamp, and then dried by heating at a temperature of 100 ℃ for 5 minutes using a hot plate. In this manner, a glass substrate on which a pattern (hydrophilic-hydrophobic pattern) including a hydrophilic portion and a water-repellent portion was formed was obtained.
6-3 measurement of contact Angle before and after Exposure of film comprising composition for Pattern formation and Pattern formation Using aqueous ink
[ measurement of contact Angle ]
A water droplet was placed on a film on a glass substrate, and the static contact angles of the non-irradiated portion and the irradiated portion of the ultraviolet light were measured by a liquid droplet method and the dynamic receding contact angle of the non-irradiated portion of the ultraviolet light was measured by an expansion and contraction method using a contact angle meter (manufactured by kyowa interface science). In the present invention, the static contact angle is an angle formed with the film surface when a water droplet is placed on the film surface and dropped, the dynamic receding contact angle is a contact angle when the water droplet is attracted by a needle or the like and contracted, and the dynamic advancing contact angle is a contact angle when the water droplet is discharged by a needle or the like and expanded.
In a pattern forming material for lithography and printed electronics, it is preferable that the pattern forming film has a high static contact angle of an unirradiated portion, that a mask pattern be more faithfully transferred, that the line edge roughness and the line width roughness of the obtained pattern be appropriate, and that a high-resolution pattern be obtained. In addition, when the static contact angle of the irradiated portion is low and the difference in contact angle between the non-irradiated portion and the irradiated portion is large, the pattern is easily cut.
When the dynamic receding contact angle of the non-irradiated portion of the pattern formation film is high, the mask pattern is transferred more faithfully, the line edge roughness and the line width roughness of the obtained pattern are appropriate, and a high-resolution pattern is obtained. In order to obtain a high-resolution pattern, it is preferable that both the dynamic advancing contact angle and the dynamic receding contact angle are high and hysteresis (dynamic advancing contact angle — dynamic receding contact angle) is small in the non-irradiated portion.
[ ink Pattern ]
On the obtained hydrophilic and hydrophobic pattern on the glass substrate, 50pl of aqueous ink was dropped through a borosilicate glass capillary (microcapilary) using an automatic minimum contact angle meter (product number MCA-2, manufactured by synechia interfacial science corporation), and the pattern was observed under a microscope after 5 seconds. Further, the aqueous ink is good when patterned along the lyophilic and lyophobic pattern, is poor when it overflows from the pattern, and is good when it cannot be either.
[ measurement results ]
Table 3 shows the results of measuring the static contact angle and the dynamic contact angle of the above-mentioned pattern-forming compositions 1 to 9 and comparative examples 1 to 4. In Table 3, examples 1 to 9 correspond to compositions-1 to 9 for pattern formation, and comparative examples 1 to 4 correspond to the measured values of comparative compositions-1 to 4.
[ Table 3]
Figure GDA0003005189880000861
Hysteresis: dynamic advancing contact Angle-dynamic receding contact Angle
[ contact Angle ]
The pattern-forming compositions of examples 1 to 9 containing a trifluoromethyl group exhibited a large contact angle in the non-irradiated part of the ultraviolet light and good water repellency.
The contact angle of the non-irradiated portion of the film formed from the comparative composition-1 of comparative example 1 using the comparative polymer-1 containing no fluorine atom was 73 °, and the receding contact angle was 58 °. The contact angle of the non-irradiated portion of the ultraviolet ray of the film formed from comparative composition-2 using comparative polymer-2 containing a fluorine atom of comparative example 2 was 94 degrees, and the water repellency of the films formed from the pattern-forming compositions-1 to 9 of examples 1 to 9 was poor. Comparative composition 4 of comparative example 4 Using comparative polymer 4 having hexafluoroisopropyl group which has no acid dissociation property, the contact angle of the ultraviolet light irradiation part was large and hydrophilicity was not exhibited.
[ ink Pattern ]
In the lyophilic and hydrophobic patterns formed by the compositions-1 to 9 for forming patterns using the fluoropolymers-1 to 9 of examples 1 to 9, the difference between the contact angle of the non-irradiated portion and the contact angle of the irradiated portion was 40 ° or more, and the receding contact angle was high, so that the aqueous ink in the water-repellent portion rapidly flowed to the hydrophilic portion.
On the other hand, in the lyophilic and hydrophobic pattern formed using the comparative composition-2 using the comparative polymer-2, the difference between the non-irradiated portion and the irradiated portion of the lyophilic and hydrophobic pattern was about 30 °, the receding contact angle was 80 ° which was low, and the water-repellent portion was observed to remain in the aqueous ink. In comparative example 1, comparative polymer-1 contained no fluorine atom. The water-repellent portion had insufficient water repellency, and water wettability was present, and the aqueous ink remained, while comparative example 4 used comparative polymer 4 having hexafluoroisopropyl group which has no acid dissociation property, and formed a film having an aqueous ink on the surface of the film without forming a hydrophilic-hydrophobic pattern.
7. Resist and method for producing the same
7.1 preparation of resist
Resists 1 to 3 and comparative resists 1 to 3 as resist solutions were prepared using fluoropolymers 10 to 12 and comparative polymers 5 to 7 each having the following repeating unit.
Figure GDA0003005189880000871
To each of the above polymers, triphenylsulfur nonafluorobutanesulfonate as a photoacid generator, triethanolamine as a basic compound, and Propylene Glycol Monomethyl Ether Acetate (PGMEA) as a solvent were added to prepare a resist solution. The composition ratio of the corrosion inhibitor is expressed as the following polymer in parts by mass: photo-acid generator: alkaline substance: the solvent is 100: 5: 1: 900, to prepare each resist solution.
[ formation of resist film ]
After a solution for an antireflection film (product No. ARC29A, manufactured by Nissan chemical industries Co., Ltd.) was applied to a silicon wafer, the silicon wafer was dried at 200 ℃ for 60 seconds to form an antireflection film having a film thickness of 78 nm. Subsequently, each of the resist solutions was filtered through a 0.2 μm membrane filter, and then applied to an antireflection film using a spin coater at 1500rpm, and dried on a hot plate at 100 ℃ for 90 seconds to form a resist film.
7.2 evaluation of developer solubility of resist and resolution of resist Pattern
The resist films were evaluated for solubility in a developer of the resist, resolution of the resist pattern, and contact angle. The measurement method is shown below.
[ solubility in developing solution ]
The silicon wafer with the resist film formed thereon was immersed in an alkaline developer at room temperature for 60 seconds, and the solubility in the developer was tested. The alkaline developer is an aqueous tetramethylammonium hydroxide solution (hereinafter, also referred to as TMAH) having a concentration of 2.38 mass% which is used in the standard for lithography. The solubility of the resist film was determined by measuring the film thickness of the resist film after immersion using an optical interference type film thickness meter. The case where the resist film completely disappeared was rated as "soluble", and the case where no change was observed in the film thickness of the resist film was rated as "insoluble".
[ sensitivity and resolution of resist Pattern ]
A mask having a pattern of lines and gaps each having a width of a wiring and a spacing between adjacent wirings of 30nm was prepared.
After a silicon wafer having a resist film formed thereon was prebaked at 100 ℃ for 60 seconds, the resist film was exposed to ultraviolet light through a mask by irradiation with an argon fluoride excimer laser beam at an oscillation wavelength of 193nm so that the pattern of the mask was transferred through the mask. While the silicon wafer was rotated, pure water was dropped for 2 minutes. Then, post-exposure baking was performed at 120 ℃ for 60 seconds, and then development was performed using TMAH as an alkaline developer, and then, after immersion in pure water for 30 seconds, drying was performed by an air knife. Subsequently, post baking was performed for 45 seconds at 100 ℃, and thus, a silicon wafer having a resist pattern formed thereon was obtained.
< sensitivity >
In the above operation, the optimum exposure Eop (mj/cm) was obtained for forming a pattern of 30nm lines and spaces 1 time2) As a criterion for sensitivity.
< resolution >
The obtained silicon wafer having the transferred pattern was cut, and the resist pattern on the wafer having the transferred pattern of 30nm lines and spaces of the mask was observed with a microscope, and the case where the line edge roughness could not be confirmed was evaluated as "excellent" resolution, the case where the line edge roughness was slightly confirmed was evaluated as "good" resolution, and the case where the line edge roughness was remarkable was evaluated as "poor" resolution.
[ method for measuring contact Angle ]
The contact angle of a water droplet was measured with a contact angle meter (manufactured by Kyowa Kagaku K.K.) for the resist film on the obtained silicon wafer.
In a resist film having a high contact angle, a mask pattern is transferred more faithfully, and the line edge roughness and line width roughness of the obtained pattern are suitable, thereby obtaining a high-resolution pattern. In addition, in immersion exposure lithography, water does not penetrate into the film, and watermark defects occur less.
Table 4 shows the results of evaluation of the solubility of the developer in the resist, the sensitivity and resolution of the resist pattern, and the results of measurement of the contact angle.
[ Table 4]
Figure GDA0003005189880000901
[ evaluation of solubility of developing solution ]
As shown in Table 4, each of the resists-1 to 3 and the comparative resists-1 to 3 was insoluble in an alkaline developer in an unexposed state and became soluble after exposure. This shows that all the resists tested had a solubility contrast to TMAH as an alkaline developer as a photosensitive resin.
[ evaluation of sensitivity and resolution of resist Pattern ]
< sensitivity >
As for the sensitivity, the optimal exposure amount of the resists-1 to 3 is lower than the optimal exposure amount of the resists-1 to 3. The value was lower than that of the cyclic acetal structure of the resist-2 of comparative example. Further, the optimum exposure dose was lower for the cyclic acetal structure of the resist-1 having no fluorine atom, and the optimum exposure dose was the lowest for the acyclic acetal structure of the resist-3.
< resolution >
As shown in Table 4, when resists 1 to 3 and comparative resist 2 were used, a pattern having a desired pattern of lines and spaces of 30nm was formed, and the pattern was judged to be "good" because of the favorable resolution. On the other hand, when the resist-1 was compared, the line edge roughness was confirmed, and the determination was "fail". In the case of comparative resist-3, it was confirmed that the line edge roughness was very small and inferior to those of resists-1 to 3 and comparative resist-2, and thus it was judged as "pass".
[ measurement result of contact Angle ]
The water receding contact angles of the resists 1 to 3 are higher than those of the comparative resists 1 to 2. The comparative resist 2 contains a polymer having a fluorinated cyclic acetal structure, but is inferior to the resists 1 to 3.

Claims (16)

1. A fluorine-containing polymer comprising a repeating unit represented by the formula (1), wherein the content of the repeating unit represented by the formula (1) is 10 mol% or more and 100 mol% or less based on the total amount of the fluorine-containing polymer,
Figure FDA0003005189870000011
in the formula (1), R1A hydrogen atom, a fluorine atom, or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, wherein 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted with fluorine atoms; r2～R5A hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted with fluorine atoms; x is a single bond or a 2-valent group, wherein 7 or less hydrogen atoms contained in the 2-valent group are optionally substituted by fluorine atoms; y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionalSubstituted by fluorine atoms; r is a C1-3 fluoroalkyl group.
2. The fluorine-containing polymer according to claim 1, wherein R in the formula (1)2、R4、R5Is a hydrogen atom.
3. The fluorine-containing polymer according to claim 2, wherein Y in the formula (1) is a trifluoromethyl group.
4. A resist pattern-forming composition comprising the fluorine-containing polymer according to any one of claims 1 to 3, an acid generator, a basic compound and a solvent.
5. A method of forming a resist pattern, comprising the steps of:
a film formation step of applying the resist pattern-forming composition according to claim 4 to a substrate to form a film;
an exposure step of irradiating an electromagnetic wave or a high-energy ray having an exposure wavelength of 300nm or less through a mask to transfer a pattern of the mask onto the film; and
and a developing step of developing the film with a developer to obtain a pattern.
6. An ink pattern-forming composition containing the fluoropolymer according to any one of claims 1 to 3, an acid generator, and a solvent.
7. A method of forming an ink pattern, comprising the steps of:
a film forming step of coating the composition for forming an ink pattern according to claim 6 on a substrate to form a film;
an exposure step of irradiating the film with light having an exposure wavelength of 150nm to 500nm through a mask to transfer a pattern of the mask onto the film, thereby obtaining a pattern-forming film having a lyophobic portion and a lyophilic portion; and
an ink pattern forming step of coating ink on the obtained pattern forming film.
8. An ink pattern forming method, comprising the steps of:
a film forming step of applying the ink pattern-forming composition according to claim 6 on a substrate and heating the obtained coating film;
a drawing step of scanning the film with light having an exposure wavelength of 150nm to 500nm by a drawing device to draw a pattern on the film, thereby obtaining a pattern-formed film having a lyophobic portion and a lyophilic portion; and
an ink pattern forming step of coating ink on the obtained pattern forming film.
9. A fluorine-containing monomer represented by formula (4);
Figure FDA0003005189870000021
in the formula (4), R1A hydrogen atom, a fluorine atom, or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, wherein 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted with fluorine atoms; r2～R5A hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted with fluorine atoms; x is a single bond or a 2-valent group, wherein 7 or less hydrogen atoms contained in the 2-valent group are optionally substituted by fluorine atoms; y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms; r is a C1-3 fluoroalkyl group.
10. The fluorine-containing monomer according to claim 9, wherein R in the formula (4)2、R4、R5Is a hydrogen atom.
11. The fluorine-containing monomer according to claim 10, wherein Y in the formula (4) is a trifluoromethyl group.
12. A method for producing the fluorine-containing monomer represented by the formula (4) according to claim 9, comprising the steps of: cyclizing a hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or hydroxyvinyl ester represented by the formula (11) to obtain a cyclic hemiacetal compound represented by the formula (7);
Figure FDA0003005189870000031
in the formula, R1A hydrogen atom, a fluorine atom, or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, wherein 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted with fluorine atoms; r2～R5A hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted with fluorine atoms; x is a single bond or a 2-valent group, wherein 7 or less hydrogen atoms contained in the 2-valent group are optionally substituted by fluorine atoms; y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms; r is a C1-3 fluoroalkyl group; z is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein part or all of the hydrogen atoms in Z are optionally substituted with a halogen atom, and wherein Z optionally contains an ether bond, a siloxane bond, a thioether bond or a carbonyl bond.
13. A fluorine-containing cyclic hemiacetal represented by formula (7);
Figure FDA0003005189870000032
in the formula (7), R2～R5Is a hydrogen atom, a straight chain alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms, wherein the hydrogen atom is bonded to a carbon atom in the alkyl groupLess than 7 of (a) are optionally substituted by fluorine atoms; y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms; r is a C1-3 fluoroalkyl group.
14. The fluorine-containing cyclic hemiacetal according to claim 13, wherein R in the formula (7)2、R4、R5Is a hydrogen atom.
15. The fluorine-containing cyclic hemiacetal according to claim 14, wherein Y in the formula (7) is a trifluoromethyl group.
16. A process for producing a fluorine-containing cyclic hemiacetal compound, which comprises cyclizing a hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or hydroxyvinyl ester represented by the formula (11) to obtain a fluorine-containing cyclic hemiacetal compound represented by the formula (7) according to any one of claims 13 to 15;
Figure FDA0003005189870000041
in the formula, R2～R5A hydrogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched-chain alkyl group having 3 to 10 carbon atoms, wherein 7 or less of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted with fluorine atoms; y is a C1-3 fluoroalkyl group or a carboxylate group (-COOR), and 7 or less hydrogen atoms contained in the fluoroalkyl group or the carboxylate group are optionally substituted by fluorine atoms; r is a C1-3 fluoroalkyl group; z is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein part or all of the hydrogen atoms in Z are optionally substituted with a halogen atom, and wherein Z optionally contains an ether bond, a siloxane bond, a thioether bond or a carbonyl bond.
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