JP7140964B2 - Fluorine-containing monomer, fluorine-containing polymer, pattern-forming composition using the same, and pattern-forming method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fluorine-containing monomer, a fluorine-containing polymer, a pattern-forming composition using the same, and a pattern-forming method thereof. In particular, resist materials used for lithography in the manufacture of semiconductors, or electronic circuits in the manufacture of electronic devices, for example, by printing with conductive ink on a glass or resin substrate with conductive film ink. The present invention relates to a fluorine-containing polymer that can be used for printed electronics forming a pattern circuit, a fluorine-containing monomer as a precursor thereof, a pattern-forming composition using the same, and a pattern-forming method thereof.

Fluorine-containing polymers are known to have excellent properties due to having fluorine atoms in their chemical structures. Fluorine-containing polymers having water repellency, heat resistance, transparency, low refractive index, and photosensitivity are used as resist materials in semiconductor manufacturing and pattern forming materials in printed electronics.

A fluorine-containing polymer having an acid-decomposable group, which is used as a resist material in semiconductor manufacturing, is made into a resist film by adding a photo-acid generator, and the acid-decomposable group is converted into a fluorine-containing polymer by the acid generated from the photo-acid generator by light irradiation. By dissociating from the coalescence, the property of being soluble or insoluble in the developer is changed, enabling pattern formation in the resist film. In printed electronics, fluoropolymers are used as materials for pattern-forming films provided with patterns that repel or do not repel ink.

Common to photolithography and printed electronics, when a fluoropolymer having an acid-decomposable group containing fluorine is used as a pattern forming material, the formed fluoropolymer film exhibits high water repellency before light irradiation. After light irradiation, the irradiated area changes from water-repellent to hydrophilic due to the dissociation of the fluorine-containing acid-decomposable group.

In printed electronics, when a film made of a pattern forming material is irradiated with light through a patterned mask, a parent/repellent pattern consisting of unirradiated water-repellent areas to which the mask pattern has been transferred and hydrophilic areas after irradiation is formed. After that, when ink is applied, the water-repellent portion repels the ink to form a pattern of the ink.

For example, Patent Literature 1 and Patent Literature 2 disclose a pattern forming material for printed electronics that provides a hydrophilic and repellent pattern. Resins having long-chain perfluoroalkyl groups are disclosed, and a pattern of lyophilic portions and liquid-repellent portions with respect to ink is formed by dissociation of the perfluoroalkyl groups contained in these resins upon irradiation with light.

However, resins having long-chain perfluoroalkyl groups are difficult to burn and decompose, and there is a concern that they may accumulate in the environment. For example, perfluorooctanoic acid is pointed out by the US Environmental Protection Agency to accumulate in the environment, and its use should be reduced. Thus, it is preferable to avoid using fluorine compounds having a perfluoroalkyl group having 6 or more carbon atoms from the viewpoint of accumulation in the environment.

As a polymer having an acid-decomposable group used as a resist material in the manufacture of semiconductors, a polymer having a cyclic acetal skeleton in the acid-dissociable portion is known. Polymers having a cyclic acetal skeleton in the acid-dissociable portion exhibit excellent acid-dissociable properties, and are therefore being developed in the field of electronic materials, particularly as radiation-sensitive patterning compositions.

For example, Patent Document 3 discloses a radiation-sensitive resin composition containing a polymer containing a fluorine-free cyclic acetal monomer such as 2-tetrahydrofuranyl methacrylate as an acid-dissociable monomer and a photoacid generator. A pattern forming method using an object is disclosed. Further, Patent Document 4 describes a monomer having a fluorine-free cyclic acetal group and a monomer having an acid-decomposable group as a pattern forming material having high sensitivity and high resolution and having a large residual film rate during development. , a polymer obtained by copolymerizing a monomer having a crosslinkable group, and a positive photosensitive composition comprising a radiation-sensitive acid generator.

Patent Document 5 discloses a fluoropolymer having a cyclic hemiacetal structure and a fluoromonomer as a precursor. Further, in Patent Document 6, by modifying the cyclic hemiacetal structure in a fluorine-containing monomer having a cyclic hemiacetal structure with a substituent and selecting a substituent, water repellency, oil solubility, and acidity when a fluorine-containing polymer is formed. It is disclosed that the degradability can be adjusted.

Pamphlet of International Publication WO2014/178279 JP 2016-87602 A JP-A-4-26850 JP 2012-42837 A JP 2006-152255 A Japanese Unexamined Patent Application Publication No. 2010-106138

In the present invention, when a film containing a photoacid generator is formed in a photoresist or printed electronics, it exhibits water repellency after film formation and before light irradiation, and after light irradiation, by the action of the acid generated from the photoacid generator. By becoming hydrophilic, it has a high contact angle with water before light irradiation, a low contact angle after light irradiation, and is used in a pattern-forming composition that gives a highly sensitive and high-resolution pattern. An object of the present invention is to provide a fluoropolymer containing no fluoroalkyl group.

Another object of the present invention is to provide a pattern-forming composition containing the fluorine-containing polymer as a pattern-forming material, and a pattern-forming method using the pattern-forming composition.

A further object of the present invention is to provide a fluorine-containing monomer and a fluorine-containing compound as their precursors, and a method for producing the same.

As shown in the examples of the present specification, the present inventors have found that the following repeating unit (1) having an acid-decomposable group having a fluorine-containing cyclic acetal skeleton to which a trifluoromethyl group is attached at a specific position , a fluoropolymer (hereinafter sometimes referred to as fluoropolymer (1)) was newly synthesized. Next, a pattern-forming composition containing the fluoropolymer (1) of the present invention was spread on a substrate to form a film.

(In the formula, R ¹ is a hydrogen atom, a fluorine atom or a linear alkyl group having 1 to 10 carbon atoms; R ² to R ⁵ are a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms; an alkyl group, X is a single bond or a divalent group, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and R is 1 carbon atom is a fluorine-containing alkyl group of ∼3.)

Next, the fluorine-containing polymer (1) of the present invention, a fluorine-containing polymer containing the repeating unit (A) described in Patent Document 6 shown below, and a fluorine-containing polymer containing the repeating unit (B) described in Patent Document 3 After preparing each pattern-forming composition by adding a photoacid generator, a solvent, etc. to a polymer or a fluorine-containing polymer containing a repeating unit (C) known as a general-purpose resist material, it is spread on a substrate and manufactured. It was coated and heat-cured. Then, the film containing the fluoropolymer (1) showed a contact angle higher by about 10° to water than the films containing the fluoropolymer (A) and the fluoropolymer (B) ( See Examples 1 to 7 and Comparative Examples 1 and 2 in [Table 3] of Examples). In addition, when the resist sensitivity was measured, the resist film containing the fluoropolymer (1) was found to be more sensitive than the resist film containing the fluoropolymer containing the repeating unit (A) or the resist film containing the repeating unit (B). , showed high sensitivity. The resist film containing the fluoropolymer (1) is a resist film containing a copolymer having the repeating unit (A), a copolymer having the repeating unit (B) and a copolymer having the repeating unit (C). In comparison, high sensitivity was exhibited (see resists 1 to 3 and comparative resists 1 to 3 in [Table 4] of Examples). Since the resist film containing the fluoropolymer (1) showed higher sensitivity than the resist film containing the fluoropolymer having the repeating unit (A), the fluoropolymer having the repeating unit (A) In comparison, the acid decomposability of the fluorinated cyclic acetal structure of the fluoropolymer (1) of the present invention is presumed to be higher than that of the fluoropolymer (A).

Next, a photomask having a 30 nm line-and-space pattern was prepared, and each film was irradiated with ultraviolet light through the mask. It was found that the resist pattern made of the pattern-forming composition has high sensitivity and high resolution compared to resist patterns made of other pattern-forming compositions outside the scope of the present invention. (Refer to resists 1 to 3 and comparative resists 1 to 3 in [Table 4] of Examples)

In this way, the present inventors have found that when a film containing a photoacid generator is formed in lithography and printed electronics, it exhibits high water repellency after film formation and before light irradiation, and after light irradiation, the photoacid generator is separated from the film. The pattern-forming composition becomes hydrophilic due to the action of the generated acid, so that the contact angle with respect to water before light irradiation is high before light irradiation, the contact angle after light irradiation is low, and the pattern is highly sensitive and highly accurate. It was confirmed that a fluorine-containing polymer containing no perfluoroalkyl group having 4 or more carbon atoms was obtained.

（式中、Ｒ^１は、水素原子、フッ素原子または炭素数１～１０の直鎖状のまたは炭素数３～１０の分枝状のアルキル基であり、アルキル基中の炭素原子に結合する水素原子のうち、７個以下がフッ素原子と置換されていてもよい。Ｒ^２～Ｒ^５は、水素原子、炭素数１～１０の直鎖状または炭素数３～１０の分枝状のアルキル基であり、アルキル基中の炭素原子に結合する水素原子のうち、７個以下がフッ素原子と置換されていてもよい。Ｘは、単結合または２価の基であり、２価の基が含む７個以下の水素原子がフッ素原子で置換されていてもよい。Ｙは、炭素数１～３の含フッ素アルキル基、またはカルボン酸エステル基(－ＣＯＯＲ)であり、含フッ素アルキル基、またはカルボン酸エステル基が含む７個以下の水素原子がフッ素原子で置換されていてもよい。Ｒは、炭素数１～３の含フッ素アルキル基である。） That is, the present invention includes Inventions 1 to 16 below.
[Invention 1]
A fluoropolymer comprising a repeating unit represented by formula (1).

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Of the atoms, 7 or less may be substituted with fluorine atoms, and R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or 3 to 10 carbon atoms. Of the hydrogen atoms bonded to carbon atoms in the alkyl group, 7 or less may be substituted with fluorine atoms X is a single bond or a divalent group, including a divalent group 7 or less hydrogen atoms may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms.R is a fluorine-containing alkyl group having 1 to 3 carbon atoms.)

[Invention 2]
The fluoropolymer according to invention 1, wherein R ² , R ⁴ and R ⁵ in the formula (1) are hydrogen atoms.

[Invention 3]
Furthermore, the fluoropolymer of invention 2, wherein Y in the formula (1) is a trifluoromethyl group.
[Invention 4]
A resist pattern-forming composition comprising the fluorine-containing polymer of Inventions 1 to 3, an acid generator, a basic compound and a solvent.

[Invention 5]
A film-forming step of applying the composition for forming a resist pattern of Invention 4 onto a substrate to form a film;
A resist comprising an exposure step in which an electromagnetic wave having a wavelength of 300 nm or less or a high-energy beam is irradiated through a photomask to transfer the pattern of the photomask onto the film, and a development step in which the film is developed using a developer to obtain a pattern. How the pattern is formed.

[Invention 6]
An ink pattern-forming composition comprising the fluorine-containing polymer of Inventions 1 to 3, an acid generator and a solvent.

[Invention 7]
a film-forming step of applying the composition for forming an ink pattern of invention 6 onto a substrate to form a film;
an exposure step of irradiating and exposing the film to light having a wavelength of 150 nm or more and 500 nm or less through a photomask to transfer the pattern of the mask onto the film to obtain a patterned film having a lyophobic portion and a lyophilic portion;
A method of forming an ink pattern, including a pattern forming step of applying ink to the obtained pattern forming film.

[Invention 8]
a film-forming step, which is a step of heating (pre-baking) a coating film obtained by applying the composition for forming an ink pattern of invention 6 onto a substrate;
Next, the film is scanned with light having a wavelength of 150 nm or more and 500 nm or less by a drawing device to draw a pattern on the film to obtain a patterned film having a lyophobic portion and a lyophilic portion,
A method for forming an ink pattern, comprising a pattern forming step of applying ink to the obtained pattern forming film.

（式中、Ｒ^１は、水素原子、フッ素原子または炭素数１～１０の直鎖状のまたは炭素数３～１０の分枝状のアルキル基であり、アルキル基中の炭素原子に結合する水素原子のうち、７個以下がフッ素原子と置換されていてもよい。Ｒ^２～Ｒ^５は、水素原子、炭素数１～１０の直鎖状または炭素数３～１０の分枝状のアルキル基であり、アルキル基中の炭素原子に結合する水素原子のうち、７個以下がフッ素原子と置換されていてもよい。Ｘは、単結合または２価の基であり、２価の基が含む７個以下の水素原子がフッ素原子で置換されていてもよい。Ｙは、炭素数１～３の含フッ素アルキル基、またはカルボン酸エステル基(－ＣＯＯＲ)であり、含フッ素アルキル基、またはカルボン酸エステル基が含む７個以下の水素原子がフッ素原子で置換されていてもよい。Ｒは、炭素数１～３の含フッ素アルキル基である。） [Invention 9]
A fluorine-containing monomer represented by formula (4).

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Of the atoms, 7 or less may be substituted with fluorine atoms, and R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or 3 to 10 carbon atoms. Of the hydrogen atoms bonded to carbon atoms in the alkyl group, 7 or less may be substituted with fluorine atoms X is a single bond or a divalent group, including a divalent group 7 or less hydrogen atoms may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms.R is a fluorine-containing alkyl group having 1 to 3 carbon atoms.)

[Invention 10]
The fluorine-containing monomer according to invention 9, wherein R ² , R ⁴ and R ⁵ in the formula (4) are hydrogen atoms.

[Invention 11]
Furthermore, the fluorine-containing monomer of invention 10, wherein Y in the formula (4) is a trifluoromethyl group.

（式中、Ｒ^１は、水素原子、フッ素原子または炭素数１～１０の直鎖状のまたは炭素数３～１０の分枝状のアルキル基であり、アルキル基中の炭素原子に結合する水素原子のうち、７個以下がフッ素原子と置換されていてもよい。Ｒ^２～Ｒ^５は、水素原子、炭素数１～１０の直鎖状または炭素数３～１０の分枝状のアルキル基であり、アルキル基中の炭素原子に結合する水素原子のうち、７個以下がフッ素原子と置換されていてもよい。Ｘは、単結合または２価の基であり、２価の基が含む７個以下の水素原子がフッ素原子で置換されていてもよい。Ｙは、炭素数１～３の含フッ素アルキル基、またはカルボン酸エステル基(－ＣＯＯＲ)であり、含フッ素アルキル基、またはカルボン酸エステル基が含む７個以下の水素原子がフッ素原子で置換されていてもよい。Ｒは、炭素数１～３の含フッ素アルキル基である。Ｚは、炭素数１－２０の直鎖状、炭素数３－２０分岐鎖状または環状のアルキル基であり、Ｚ中の水素原子の一部または全部がハロゲン原子で置換されていてもよく、エーテル結合、シロキサン結合、チオエーテル結合、カルボニル結合を含んでいてもよい。）
[Invention 12]
A step 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) ,
A method for producing a fluorine-containing monomer represented by Formula (4) of Invention 9.

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Of the atoms, 7 or less may be substituted with fluorine atoms, and R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or 3 to 10 carbon atoms. Of the hydrogen atoms bonded to carbon atoms in the alkyl group, 7 or less may be substituted with fluorine atoms X is a single bond or a divalent group, including a divalent group 7 or less hydrogen atoms may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms, R is a fluorine-containing alkyl group having 1 to 3 carbon atoms, and Z is a straight chain having 1 to 20 carbon atoms. , a branched or cyclic alkyl group with 3 to 20 carbon atoms, some or all of the hydrogen atoms in Z may be substituted with halogen atoms, and ether bonds, siloxane bonds, thioether bonds, carbonyl bonds may contain.)

（式中、Ｒ^２～Ｒ^５は、水素原子、炭素数１～１０の直鎖状または炭素数３～１０の分枝状のアルキル基であり、アルキル基中の炭素原子に結合する水素原子のうち、７個以下がフッ素原子と置換されていてもよい。Ｙは、炭素数１～３の含フッ素アルキル基、またはカルボン酸エステル基(－ＣＯＯＲ)であり、含フッ素アルキル基、またはカルボン酸エステル基が含む７個以下の水素原子がフッ素原子で置換されていてもよい。Ｒは、炭素数１～３の含フッ素アルキル基である。） [Invention 13]
A fluorine-containing cyclic hemiacetal represented by formula (7).

(Wherein, R ² to R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Among them, 7 or less may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (—COOR), and a fluorine-containing alkyl group or carboxylic 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms.R is a fluorine-containing alkyl group having 1 to 3 carbon atoms.)

[Invention 14]
The fluorine-containing cyclic hemiacetal of invention 13, wherein R ² , R ⁴ and R ⁵ in the formula (7) are hydrogen atoms.

[Invention 15]
Furthermore, the fluorine-containing cyclic hemiacetal of Invention 14, wherein Y in the formula (7) is a trifluoromethyl group.

（式中、Ｒ^２～Ｒ^５は、水素原子、炭素数１～１０の直鎖状または炭素数３～１０の分枝状のアルキル基であり、アルキル基中の炭素原子に結合する水素原子のうち、７個以下がフッ素原子と置換されていてもよい。Ｙは、炭素数１～３の含フッ素アルキル基、またはカルボン酸エステル基(－ＣＯＯＲ)であり、含フッ素アルキル基、またはカルボン酸エステル基が含む７個以下の水素原子がフッ素原子で置換されていてもよい。Ｒは、炭素数１～３の含フッ素アルキル基である。Ｚは、炭素数１－２０の直鎖状、炭素数３－２０分岐鎖状または環状のアルキル基であり、Ｚ中の水素原子の一部または全部がハロゲン原子で置換されていてもよく、エーテル結合、シロキサン結合、チオエーテル結合、カルボニル結合を含んでいてもよい。） [Invention 16]
A hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or a hydroxyvinyl ester represented by the formula (11) is cyclized to obtain a fluorine-containing cyclic hemi compound represented by the formula (7) of Inventions 13 to 15. get acetal,
A method for producing a fluorine-containing cyclic hemiacetal.

(Wherein, R ² to R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Among them, 7 or less may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (—COOR), and a fluorine-containing alkyl group or carboxylic 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms, R is a fluorine-containing alkyl group having 1 to 3 carbon atoms, and Z is a straight chain having 1 to 20 carbon atoms. , a branched or cyclic alkyl group with 3 to 20 carbon atoms, some or all of the hydrogen atoms in Z may be substituted with halogen atoms, and ether bonds, siloxane bonds, thioether bonds, carbonyl bonds may contain.)

According to the present invention, when a film containing a photoacid generator is formed in a photoresist or printed electronics, the film exhibits water repellency after film formation and before light irradiation, and after light irradiation, the acid generated from the photoacid generator is repelled. The acid-decomposable group containing fluorine is dissociated by the action and the film becomes hydrophilic, so that the contact angle to water before light irradiation is high, the contact angle after light irradiation is low, and a pattern with high sensitivity and high resolution is provided. A fluorine-containing polymer containing no perfluoroalkyl group having 4 or more carbon atoms, which is used in the pattern-forming composition, was obtained.

Moreover, a pattern-forming composition containing the fluoropolymer as a pattern-forming material and a pattern-forming method using the pattern-forming composition were obtained.

Furthermore, a fluorine-containing monomer and a fluorine-containing compound as their precursors and a method for producing the same were obtained.

Since the polymer having a fluorine-containing cyclic acetal skeleton of the present invention contains a perfluoroalkyl group having 1 to 3 carbon atoms and does not contain a perfluoroalkyl group having 4 or more carbon atoms, there is no concern that it will accumulate in the environment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention will be described. It should be understood that the scope of the present invention also includes modifications, improvements, etc., to the following embodiments.

1. Fluoropolymer The fluoropolymer of the present invention is a polymer having a fluorinated cyclic acetal structure containing a repeating unit represented by formula (1). Hereinafter, it may be referred to as fluoropolymer (1).

[Fluorine-containing polymer (1)]

(wherein R ¹ is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms; R ² to R ⁵ are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; X is a single bond; or a divalent group, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a carboxylic acid ester group (--COOR) (R is a fluorine-containing alkyl group having 1 to 3 carbon atoms.)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X and Y in formula (1) will be explained.
[R ¹ ]
In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a linear or branched alkyl group having 1 to 10 carbon atoms or 3 to 10 carbon atoms, and Among them, 7 or less hydrogen atoms may be substituted with fluorine atoms.

R ¹ is hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, fluorine atom, trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, 1,1,1,3,3,3-hexa Examples include a fluoroisopropyl group (--C(CF ₃ ) ₂ H) and a heptafluoroisopropyl group. For ease of polymerization, R ¹ is preferably a hydrogen atom, a fluorine atom, or a methyl group.

[R ² to R ⁵ ]
R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 3 to 10 carbon atoms and having 1 to 10 primes, and 7 of the hydrogen atoms bonded to the carbon atoms in the alkyl group The following may be substituted with a fluorine atom.

For ease of synthesis, R ² to R ⁵ are preferably donating alkyl groups rather than electron-withdrawing substituents, and are preferably hydrogen atoms or methyl groups free of steric hindrance.

[X]
X is a single bond or a divalent group, and 7 or less hydrogen atoms in the divalent group may be substituted with fluorine atoms.

X is preferably a divalent group having 2 to 10 carbon atoms, such as a methylene group, an alkylene group having 2 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, and a divalent aryl group having 6 to 10 carbon atoms. , or a divalent alicyclic hydrocarbon group having 4 to 10 carbon atoms.
The alkylene group or alkenylene group includes an ether bond (-O-), a carbonyl group (-(C=O-), a carboxyl group (-(C=O)O-, or -O(C=O)- A single bond, an oxyethylene group (—O—CH ₂ —CH ₂ —), or an oxyacetyl group (—O —CH ₂ —CO—).

[Y]
Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (--COOR) having 1 to 3 carbon atoms (R is a fluorine-containing alkyl group having 1 to 3 carbon atoms). Seven or less hydrogen atoms contained in the fluorine-containing alkyl group or carboxylic acid ester group may be substituted with fluorine atoms.

Y can be exemplified by a trifluoromethyl group, a trifluoroethyl group, a pentafluoroethyl group, a trifluoropropyl group, a 1,1,1,3,3,3-hexafluoroisopropyl group, or a heptafluoroisopropyl group. can. For ease of synthesis, trifluoromethyl group, trifluoroethyl group and 1,1,1,3,3,3-hexafluoroisopropyl group are preferred.

Further, in the fluorine-containing monomer (1) of the present invention, depending on the type and combination of substituents shown above, the molecule may have asymmetric carbon hydrogen, enantiomers, diastereoisomers, Mers (stereoisomers with two or more asymmetric carbon atoms, which are not mirror images) can exist. Formula (1), however, represents all of these stereoisomers. Stereoisomers may be used singly or as a mixture.

[Fluorine-containing polymer (2)]
The fluoropolymer (1) of the present invention is a fluoropolymer containing the following repeating unit (2), wherein R ² , R ⁴ and R ⁵ in the formula (1) are hydrogen atoms. is preferred. When the fluorine-containing polymer (1) is used as a pattern-forming composition to form a film on a substrate, R ² , R ⁴ and R ⁵ in the formula (1) are hydrogen atoms due to solubility in solvents. It is preferably a polymer having a fluorine-containing cyclic acetal structure containing a repeating unit represented by formula (2). Hereinafter, it may be referred to as fluoropolymer (2).

(R ¹ , R ³ , X and Y in the formula have the same meanings as in formula (1).)

[Fluorine-containing polymer (3)]
The fluoropolymer (1) of the present invention is further a fluoropolymer (3) containing the following repeating unit (3), wherein Y in the formula (1) is a trifluoromethyl group. preferable.

Furthermore, for solubility in solvents, Y in formula (1) is preferably a trifluoromethyl group, and has a fluorine-containing cyclic acetal structure containing a repeating unit represented by formula (3). Polymers are preferred. Hereinafter, it may be referred to as fluoropolymer (3).

(R ¹ , R ³ and X in the formula have the same meanings as in formula (1).)

1-1. Decomposition of Fluorine-Containing Polymer (1) by Acid It is known that the cyclic acetal structure is decomposed by an acid from an acid generator in the same manner as common acetals. The fluorine-containing cyclic acetal structure of the fluorine-containing polymer (1) of the present invention is also presumed to undergo the following reaction.

The reaction with an acid is represented by the following formula. From the fluorine-containing polymer (1), the acid-decomposable group (1B) is dissociated to leave the repeating unit represented by the formula (1A), or the fluorine-containing cyclic acetal structure is opened. It is presumed that there are two reaction pathways through which the repeating unit represented by the formula (1C) is generated by the ring. It is presumed that the formation of the fluorine-containing polymer containing the unit or the repeating unit represented by formula (1C) reduces the contact angle of the ink with respect to the film, and the function of pattern formation by the ink is exhibited.

1-2. Monomers Providing Other Repeating Units The fluoropolymer (1) of the present invention may contain repeating units other than the repeating units (1). Repeating units other than the repeating unit (1) are determined by the solvent solubility of the fluoropolymer (1) when forming a film from the pattern forming composition containing the fluoropolymer (1) as a component, or the solubility of the fluoropolymer (1) with the film. It is added to the structure of the fluoropolymer (1) for the purpose of adjusting the hardness of the film when it is coated.

A fluorine-containing polymer (1) containing repeating units (1) and other repeating units is obtained by copolymerizing a fluorine-containing monomer (1) that gives repeating units (1) and a monomer that gives other repeating units. obtained by

A monomer that provides another repeating unit has a polymerizable unsaturated bond and is copolymerizable with the fluorine-containing monomer (1) that provides the repeating unit (1). Examples of the monomers include monomers that provide an adhesive group, acrylic acid esters, fluorine-containing acrylic acid esters, methacrylic acid esters, fluorine-containing methacrylic acid esters, hexafluoroisopropanol group (—C(CF ₃ ) ₂ OH (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 adhesion group]
When the fluorine-containing polymer (1) is used as a resist component, by introducing an adhesion group into the chemical structure, favorable adhesion to a substrate can be obtained in lithography. Examples of adhesive groups include groups containing a lactone structure.

When introducing an adhesive group into the fluoropolymer (1) of the present invention, a monomer containing a group having a monocyclic or polycyclic lactone structure copolymerizable with the fluoromonomer (1) body can be used.

A monocyclic lactone structure is a group in which one hydrogen atom is removed from γ-butyrolactone or mevalonic lactone to form a bond. can be exemplified. A lactone structure is introduced into the fluoropolymer (1) of the present invention by copolymerizing an acrylic acid ester or a methacrylic acid ester containing a lactone structure. By doing so, when the fluorine-containing polymer (1) is used as a resist component for lithography, it is expected that not only the adhesiveness to the substrate is improved but also the compatibility with the developing solution is enhanced.

The following repeating units can be exemplified as repeating units that provide adhesion to the substrate when formed into a resist film.

5-methacryloyloxy-2,6-norbornanecarboractone (hereinafter sometimes referred to as MNLA) is particularly preferred because of its easy availability. It is indicated by MNLA in the above figure.

[Acrylic esters]
Acrylic esters include 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-hydroxy Ethyl acrylate or 2-hydroxypropyl acrylate, or acrylates with ethylene glycol, propylene glycol or tetramethylene glycol groups, or acrylamide, N-methylolacrylamide or diacetone acrylamide as unsaturated amides, or tert-butyl acrylate, 3-oxo Cyclohexyl acrylate, adamantyl acrylate, methyladamantyl acrylate, ethyladamantyl acrylate, hydroxyadamantyl acrylate, cyclohexyl acrylate or tricyclodecanyl acrylate, or acrylates having a ring structure such as a lactone ring or norbornene ring, or those having a cyano group at the α-position Acrylic acid esters can be exemplified.

[Fluorine-containing acrylic esters]
Examples of fluorine-containing acrylic acid esters include fluorine-containing acrylic acid esters having a fluorine-containing organic group at the α-position of the acrylic moiety or at the ester moiety. Both the α-position and the ester moiety may have a fluorine-containing organic group, or the α-position may have a cyano group and an ester moiety-containing fluorine-containing alkyl group.

Examples of the fluorine-containing organic group that the fluorine-containing acrylates have at the α-position include a trifluoromethyl group, a trifluoroethyl group and a nonafluoro-n-butyl group.

The fluorine-containing organic group in the ester moiety of the fluorine-containing acrylates includes perfluoro or fluorine-containing alkyl groups containing hydrogen atoms, or groups containing fluorine atoms, trifluoromethyl groups, and HFIP groups substituted for hydrogen atoms in a cyclic structure. Groups containing a fluorine-containing benzene ring, a fluorine-containing cyclopentane ring, a fluorine-containing cyclohexane ring, or a fluorine-containing cycloheptane ring can be exemplified.

Fluorine-containing acrylic acid esters include 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, Heptafluoroisopropyl acrylate, 1,1-diphydroheptafluoro-n-butyl acrylate, 1,1,5-trifidrooctafluoro-n-pentyl acrylate, 1,1,2,2-tetraphydrotridecafluoro- 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]heptyl-2-yl acrylate, 6-[3,3,3-trifluoro-2-hydroxy 2-(trifluoromethyl)propyl]bicyclo[2.2.1]heptyl-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 can be exemplified.

[Methacrylic acid esters]
Methacrylate esters include 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-hydroxy Ethyl methacrylate, 2-hydroxypropyl methacrylate or methacrylates with ethylene glycol, propylene glycol or tetramethylene glycol groups, or methacrylamide, N-methylol acrylamide, N-methylol methacrylamide or diacetone acrylamide as unsaturated amides, or tert -Butyl methacrylate, 3-oxocyclohexyl methacrylate, adamantyl methacrylate, methyladamantyl methacrylate, ethyladamantyl methacrylate, hydroxyadamantyl methacrylate, cyclohexyl methacrylate or tricyclodecanyl methacrylate, or methacrylates having a ring structure such as a lactone ring or a norbornene ring be able to.

[Fluorine-containing methacrylic acid esters]
Examples of fluorine-containing methacrylic acid esters include fluorine-containing methacrylic acid esters having a fluorine-containing organic group in the ester moiety.

Such a fluorine-containing organic group includes perfluorofluoro or a fluorine-containing alkyl group containing a hydrogen atom, or a fluorine-containing benzene 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, A fluorine-containing cyclopentane ring, a fluorine-containing cyclohexane ring, or a fluorine-containing cycloheptane ring can be exemplified.

Fluorine-containing acrylic acid esters include 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]heptyl-2-yl methacrylate, or 1,4-bis(1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl)cyclohexyl Methacrylates can be exemplified.

[Monomer having HFIP group]
As the monomer having an HFIP group, the monomers shown below can be exemplified.

( ^R9 represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. Further, the HFIP group may be partially or wholly protected with a protecting group.)

[Styrenes, fluorine-containing styrenes]
Examples of styrenes include styrene and hydroxystyrene.

Examples of fluorine-containing styrenes include pentafluorostyrene, trifluoromethylstyrene, bistrifluoromethylstyrene, styrene obtained by substituting a hydrogen atom of an aromatic ring structure with a fluorine atom or a trifluoromethyl group, HFIP group or its hydroxyl group as a protective group. Styrenes obtained by substituting the hydrogen atom of the aromatic ring structure with an HFIP group protected with, those styrenes in which a halogen atom, an alkyl group or a fluorine-containing alkyl group is bonded to the α-position, or a perfluorovinyl group-containing styrene are exemplified. be able to.

[Vinyl ethers, allyl ethers, fluorine-containing vinyl ethers, fluorine-containing allyl ethers]
Vinyl ethers or allyl ethers are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, hydroxyethyl or hydroxybutyl groups and may be alkyl vinyl ethers or alkyl allyl ethers. In the case of a vinyl ether containing a hydroxyethyl group or a hydroxybutyl group, the alcohol moiety may form an ester bond with an acetyl group, a butyroyl group or a propinoyl group. It may be a cyclopentyl group, a cyclohexyl group, a norbornyl group, an aromatic ring, or a cyclic vinyl ether or cyclic allyl ether having a hydrogen atom or a carbonyl bond in its cyclic structure. Examples of fluorine-containing vinyl ethers and fluorine-containing allyl ethers include fluorine-containing vinyl ethers and fluorine-containing allyl ethers in which some or all of the hydrogen atoms of these vinyl ethers or allyl ethers have been substituted with fluorine atoms.

[Olefins, fluorine-containing olefins]
Examples of olefins include ethylene, propylene, isobutene, cyclopentene and cyclohexene. Examples of fluorine-containing olefins include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene or hexafluoroisobutene, 1-chloro-2,3,3,4,4, 5,5-heptafluorocyclopentene, octafluorocyclopentene or decafluorocyclohexene may be mentioned.

[Norbornenes, fluorine-containing norbornenes]
Norbornenes and fluorine-containing norbornenes only need to have a polymerizable group, and may have not only one norbornene skeleton but also a plurality of norbornene skeletons. Norbornenes or fluorine-containing norbornenes are produced by the Diels-Alder addition reaction between an unsaturated compound and a diene compound.

Examples of such unsaturated compounds include fluorine-containing olefins, allyl alcohol, fluorine-containing allyl alcohol, homoallyl alcohol, fluorine-containing homoallyl alcohol, acrylic acid, α-fluoroacrylic acid, α-trifluoromethylacrylic acid, methacrylic acid. , the above acrylic acid ester, methacrylic acid ester, fluorine-containing acrylic acid ester or fluorine-containing methacrylic acid ester, 2-(benzoyloxy) pentafluoropropane, 2-(methoxyethoxymethyloxy) pentafluoropropene, 2-(tetrahydroxypyrani Examples include pentafluoropropene, 2-(benzoyloxy)trifluoroethylene, or 2-(methoxymethyloxy)trifluoroethylene. Examples of diene compounds include cyclopentadiene and cyclohexadiene.

Examples of fluorine-containing norbornene compounds include 3-(5-bicyclo[2.2.1]hepten-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanol. be able to.

[Monomers having other polymerizable unsaturated bonds]
Other monomers having polymerizable unsaturated bonds include acrylic acid, methacrylic acid, acrylonitrile, maleic acid, fumaric acid, and maleic anhydride.

As other monomers, if the length of the organic group from the polymerization site is long, or if it contains many heteroatoms, the effect of the organic group derived from other repeating units becomes stronger, and the terminal There is a concern that the effect of the fluorine-containing alkyl group on the liquid repellency will be reduced and the solubility of the polymer will be lowered. Therefore, other monomers are preferably acrylic acid esters and methacrylic acid esters having less than 10 carbon atoms, and particularly preferably methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Or isobutyl methacrylate.

1-3. Content ratio of each repeating unit in the fluoropolymer (1) The content ratio of the repeating unit represented by the formula (4) with respect to the total amount of the fluoropolymer (1) is 10 mol% or more and 100 mol% or less. It is preferably 10 mol % or more and 90 mol %. When the content of the repeating unit (1) in the fluoropolymer (1) is less than 10 mol %, the non-exposed areas of the pattern forming film formed by exposing the film comprising the fluoropolymer (1) are water-repellent. is not obtained.

The content of repeating units derived from other monomers is preferably 0 mol % or more and 90 mol % or less, more preferably 10 mol % or more and 90 mol % or less, relative to the total amount of the fluoropolymer (1).

The repeating units derived from other monomers are intended to improve the solubility of the fluoropolymer (1) in organic solvents, the adhesion to the substrate when formed into a film, the hardness, and the like. Although it may not be used if necessary, if it is less than 10 mol %, the adhesiveness or hardness to the substrate when formed into a film will not improve, and if it exceeds 90 mol %, the content of the repeating unit (1) will decrease. It is difficult to obtain the effect of imparting water repellency to the unexposed areas of the pattern forming film obtained by exposing the film comprising the fluoropolymer (1) and the effect of imparting hydrophilicity to the exposed areas.

1-4. Molecular Weight of Fluoropolymer (1) The number average molecular weight of the fluoropolymer (1) of the present invention is 1,000 or more and 100,000 or less, preferably 3,000 or more and 50,000 or less. The molecular weight distribution is 1 or more and 4 or less, preferably 1 or more and 2.5 or less.

If the number-average molecular weight is less than 1,000, the film formed from the pattern-forming composition containing the fluoropolymer (1) as a component becomes soft, and it becomes difficult to form a film of desired thickness. In addition, it is difficult to form a fine pattern consisting of a liquid-repellent portion and a liquid-philic portion in the pattern-formed film after exposure, and the durability of the pattern may be poor. If the number average molecular weight is more than 100,000, the fluorine-containing polymer (1) becomes difficult to dissolve in a solvent, cracks occur after film formation, and the pattern forming composition containing the fluorine-containing polymer (1) as a component. It is difficult to form a film composed of as a coating film.

2. Synthesis of Fluoropolymer [Synthesis of Fluoropolymer (1)]
Synthesis of the fluoropolymer (1) of the present invention can be selected from commonly used polymerization methods. Radical polymerization and ionic polymerization are preferred, and coordinated anionic polymerization, living anionic polymerization, and cationic polymerization can be selected depending on the case. A reactor used for the polymerization reaction is not particularly limited. Moreover, in polymerization, a polymerization solvent may be used. Radical polymerization will be described below.

Radical polymerization is carried out in the presence of a radical polymerization initiator or a radical initiation source by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, either batchwise, semicontinuously or continuously. Operation can be done.

<Radical polymerization initiator>
Examples of radical polymerization initiators include azo-based compounds, peroxide-based compounds, and redox-based compounds. As an azo compound, azobisisobutyronitrile can be exemplified. Peroxide compounds include t-butyl peroxypivalate, di-t-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propylperoxy Dicarbonates, t-butyl peroxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide or ammonium persulfate may be mentioned.

<Polymerization Solvent>
The polymerization solvent is preferably one that does not inhibit radical polymerization, and examples thereof include ester solvents, ketone solvents, hydrocarbon solvents, and alcohol solvents. In addition, water, ether-based, cyclic ether-based, flon-based, or aromatic solvents may be used.

Polymerization solvents include 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, methanol, isopropyl alcohol or ethylene as an alcohol solvent. Glycol monomethyl ether can be exemplified.

These polymerization solvents may be used alone or in combination of two or more. A molecular weight modifier such as mercaptan may also be used in combination.

<Polymerization conditions>
The polymerization temperature may be appropriately selected according to the type of radical polymerization initiator or radical polymerization initiation source. It is preferable to appropriately select the type of radical polymerization initiator or radical polymerization initiation source so that the polymerization temperature is 20° C. or higher and 200° C. or lower, preferably 30° C. or higher and 140° C. or lower. The molecular weight of the fluoropolymer (1) can be controlled by selecting a radical polymerization initiator or a radical polymerization initiation source and adjusting polymerization conditions.

In addition, as a method for removing the polymerization solvent such as an organic solvent or water from the solution or dispersion containing the fluoropolymer (1) after polymerization, known methods can be used, such as reprecipitation, Filtration or hot distillation under reduced pressure may be mentioned.

When the fluoropolymer (1) of the present invention is used as a resist component, the solubility of the fluoropolymer (1) in a developer varies depending on the molecular weight of the fluoropolymer (1). Patterning conditions may vary. When the molecular weight of the fluoropolymer (1) is high, the dissolution rate in the developer tends to be slow, and when the molecular weight is low, the dissolution rate tends to be fast. The molecular weight of the fluoropolymer (1) can be controlled by adjusting the polymerization conditions.

3. Resist Pattern Forming Composition 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 is used in lithography. be able to. Hereinafter, the composition for forming a resist pattern may simply be referred to as a resist.

The fluoropolymers (1) to (3) of the present invention are particularly suitable for use as components of photosensitized positive resists. The resist of the present invention provides a resist containing fluorine-containing polymers (1) to (3), particularly a photosensitized positive resist material.

The resist of the present invention comprises, as its components, (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. preferably included. Moreover, (E) a surfactant may be added as necessary.

3-1. (B) Photo-acid generator The photo-acid generator used in the resist of the present invention is not particularly limited, and an arbitrary one may be selected and used from those used as acid generators for chemically amplified resists. and include onium sulfonates or sulfonate esters. Examples include iodonium sulfonate, sulfonium sulfonate, N-imidosulfonate, N-oxime sulfonate, o-nitrobenzylsulfonate, or trismethanesulfonate of pyrogallol.

Acids generated from these photoacid generators upon exposure in lithography include alkanesulfonic acids, arylsulfonic acids, or partially or fully fluorinated arylsulfonic or alkanesulfonic acids. Among these photoacid generators, photoacid generators that generate partially or completely fluorinated alkanesulfonic acids are preferred. Examples include triphenylsulfonium trifluoromethanesulfonate and triphenylsulfonium perfluoro-n-butanesulfonate.

3-2. (C) a basic compound
A resist containing any one of the fluoropolymers (1) to (3) of the present invention may contain a basic compound. The basic compound has the function of slowing down the diffusion speed of the acid generated from the photoacid generator when it diffuses into the resist film. In the formulation of the basic compound, the acid diffusion distance is adjusted to improve the shape of the resist pattern, and even if the leave time after the resist film formation until exposure is long, the stability of giving the resist pattern with the desired accuracy is improved. effect is expected.

Such basic compounds may include aliphatic amines, aromatic amines, heterocyclic amines, or aliphatic polycyclic amines. Among these amines, secondary or tertiary aliphatic amines or alkyl alcohol amines are preferred. For example, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecanylamine, tridodecylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecanylamine, didodecylamine, dicyclohexylamine, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine , decanylamine, dodecylamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, dioctanolamine, trioctanolamine, aniline, pyridine, picoline, lutidine, bipyridine, pyrrole, piperidine, piperazine, indole, or hexamethylenetetramine can be exemplified. These basic compounds may be used alone or in combination of two or more.

The amount of the basic compound to be blended in the resist of the present invention is 0.001 to 2 parts by mass with respect to 100 parts by mass of the fluoropolymer (1), preferably with respect to 100 parts by mass of the fluoropolymer (1). It is 0.01 to 1 part by mass. If the amount is less than 0.001 parts 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 (A) any one of the fluoropolymers (1) to (3) of the present invention, (B) a photoacid generator, and (C) a basic compound, (D) Add a solvent. The solvent should dissolve (A) any one of the fluoropolymers (1) to (3) of the present invention, (B) a photoacid generator, and (C) a resist component containing a basic compound to form a uniform solution. Often, it can be selected and used from conventional resist solvents. Moreover, you may mix and use a solvent of 2 or more types.

Examples of such solvents include ketones, alcohols, polyhydric alcohols, esters, aromatic solvents, ethers, fluorine-based solvents, and terpene-based petroleum naphtha, which is a high-boiling solvent for the purpose of improving coating properties. Solvents and paraffinic solvents can be mentioned.

For example, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isobutyl ketone methyl isopentyl ketone or 2-heptanone as ketones, isopropanol, butanol, isobutanol, n-pentanol, isopentanol, 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, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol or oleyl alcohol, ethylene glycol as polyhydric alcohol, 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, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA) or propylene Glycol monomethyl ether (PGME), derivatives of these polyhydric alcohols, methyl lactate as esters, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate or Examples include ethyl ethoxypropionate, toluene or xylene as aromatic solvents, diethyl ether, dioxane, anisole or diisopropyl ether as ethers, and hexafluoroisopropyl alcohol as fluorine solvents.

Among these solvents, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are particularly preferred 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, but the solid content concentration of the resist is preferably 3% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 15% by mass. It is below. By adjusting the solid content concentration of the resist, it is possible to adjust the film thickness of the formed resin film.

In addition, the fluoropolymers (1) to (3) of the present invention have excellent solubility in a wide range of solvents, and among the above alcohol-based solvents, they are soluble in alcohol-based solvents having 5 to 20 carbon atoms. It is worth mentioning. Such alcohols include n-pentanol, isopentanol, 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, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol or oleyl alcohol be able to.

3-4. (E) Surfactant A surfactant may be added to the resist of the present invention, if necessary. Examples of surfactants include fluorine-based surfactants, silicon-based surfactants, and surfactants having both fluorine atoms and silicon atoms, and two or more of them can be contained.

3-5. Resist The resist of the present invention can be dissolved in a C5-C20 alcoholic solvent or the like that cannot dissolve general resist materials. This allows it to be used as an upper layer resist for double patterning processes. Moreover, the resist of the present invention has high water resistance, and has an affinity for a developing solution while having moderate water repellency.

The resist of the present invention has moderate water repellency before exposure and exhibits rapid solubility in a developer after exposure. It is presumed that a high-resolution pattern without roughness can be formed by liquid immersion exposure in which a medium having a large refractive index is used for exposure. In photolithography by immersion exposure, a topcoat film, which is a resist protective film, may or may not be used, but the resist of the present invention can be applied to immersion exposure by adjusting the composition and formulation. It is presumed that

In addition to water, the medium for immersion exposure includes fluorine-based solvents, silicon-based solvents, hydrocarbon-based solvents, sulfur-containing solvents, and the like. It can also be applied to media.

4. Method for Forming a Resist Pattern The method for forming a resist pattern of the present invention comprises a film forming step of coating the resist of the present invention on a substrate to form a film, and irradiating an electromagnetic wave having a wavelength of 300 nm or less or a high-energy ray through a photomask. It includes an exposure step of exposing to light and transferring the pattern of the photomask onto the film, and a developing step of developing the film using a developer to obtain a pattern.
In the present invention, the high-energy beam refers to electron beams or soft X-rays.

The method for forming a resist pattern of the present invention is a method for forming a pattern by lithography using a resist containing any one of the fluoropolymers (1) to (3). (B) After heating the resist film, an exposure step of irradiating the resist film with an electromagnetic wave having a wavelength of 300 nm or less or a high-energy ray through a patterned photomask and exposing it, (C) Exposure The developed resist film is developed with an alkaline developer to obtain a resist pattern in which the pattern of the photomask is transferred onto the substrate.

For example, in (A) the film forming step, a silicon wafer as a substrate is coated with a resist containing any one of the fluoropolymers (1) to (3) of the present invention by spin coating, and the silicon wafer is coated. A resist film is formed on the substrate by pre-baking on a hot plate at 60 to 200° C. for 10 seconds to 10 minutes, preferably 80° C. to 150° C. for 30 seconds to 2 minutes. Next, in the exposure step (B), the patterned photomask is set in an exposure device, and high-energy rays such as ultraviolet rays, excimer lasers, X-rays, or electron beams are applied at an exposure amount of 1 mJ/ ^cm2 or more and 200 mJ/cm2. cm ² or less, preferably 10 mJ/cm ² or more and 100 mJ/cm ² or less. Post-exposure baking (PEB) is performed for 30 seconds or more and 3 minutes or less, preferably 80° C. or more and 130° C. or less, for 3 minutes or less, if necessary. Next, in the development step (C), a developer using an aqueous tetramethylammonium hydroxide (TMAH) 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, The target resist pattern is obtained by contacting the resist film with the resist film for 10 seconds or more and 3 minutes or less, preferably 30 seconds or more and 2 minutes or less, by an existing method such as a dip method, a puddle method, or a spray method.

As the substrate, a metal or glass substrate can be used in addition to the silicon wafer. Also, an organic or inorganic film may be provided on the substrate. For example, there may be an antireflection film, a lower layer of multilayer resist, and a resist pattern may be formed.

In the lithography of the resist of the present invention, the wavelength of the electromagnetic wave used for exposure is not limited. EUV), X-rays can be selected, and in particular UV light from an ArF excimer laser is preferably employed.

The resist of the present invention has moderate water repellency before exposure, exhibits rapid solubility in a developer after exposure, and enables pattern formation with excellent resolution without roughness.

A semiconductor device can be manufactured by a pattern forming method by lithography using the resist of the present invention. Devices are not particularly limited, but microfabrication such as CPU (Central Processing Unit), SRAM (Static Random Access Memory), DRAM (Dynamic Random Access Memory) formed on silicon wafers, compound semiconductor substrates, insulating substrates, etc. and a semiconductor device manufactured by

5. Ink pattern-forming composition 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 used for ink pattern formation in printed electronics. can be used. Hereinafter, a pattern made of ink may be referred to as an ink pattern.

The ink pattern-forming composition of the present invention contains, as its components, any one of the fluoropolymers (1) to (3), (A) an acid generator, and (B) a solvent. In addition, it preferably contains (C) a quencher, (D) a sensitizer, and (E) a polymerizable compound. good too.

(A) The acid generator is a compound that generates an acid in a film formed from the composition for forming an ink pattern by light irradiation at the time of exposure. (B) The solvent is a substance for dissolving or dispersing the components of the ink pattern forming composition. (C) A quencher is a substance for preventing the diffusion of acid from the acid generator during exposure and making the resulting pattern highly precise. (D) A sensitizer is a substance for increasing exposure sensitivity. (E) The polymerizable compound is a substance for making the pattern forming film obtained after exposure harder. Each component is described below.

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 upon irradiation with light, can be used.

The (A) acid generator used as a component in the composition for forming an ink pattern of the present invention may be any compound that generates an acid upon irradiation with light, such as an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, and diazomethane. compounds, sulfone compounds, sulfonate ester compounds, or carboxylic acid esterification, and the like.

[Oxime sulfonate compound]
Examples of oxime sulfonate compounds include alkyl groups having 1 to 12 carbon atoms, fluoroalkyl groups having 1 to 12 carbon atoms, alicyclic hydrocarbon groups having 4 to 12 carbon atoms, and aryl groups having 6 to 20 carbon atoms. can be done. Some or all of the hydrogen atoms in these groups may be substituted with halogen atoms or substituents. Preferably, it is a linear or branched C 3-12 alkyl group having 1 to 12 carbon atoms. Examples of substituents include alicyclic groups including bridged cyclic alicyclic groups such as alkoxy groups having 1 to 10 carbon atoms and 7,7-dimethyl-2-oxonorbornyl groups.

Examples of C 1-12 fluoroalkyl groups include trifluoromethyl, pentafluoroethyl and heptylfluoropropyl groups. Examples of substituents 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 group, naphthyl group, tolyl group and xylyl group. Examples of substituents 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.

Oxime sulfonate compounds include (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]
Onium salts can include diphenyliodonium salts, triphenylsulfonium salts, alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, benzothiazonium salts or tetrahydrothiophenium salts.

<Diphenyliodonium salt>
Diphenyliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, and diphenyliodonium butyl. tris(2,6-difluorophenyl)borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis(4-t-butylphenyl)iodonium tetrafluoroborate, bis(4-t-butylphenyl)iodonium hexafluoroarsenate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium trifluoroacetate, bis(4-t-butylphenyl)iodonium-p-toluenesulfonate, or bis(4 -t-butylphenyl)iodonium camphorsulfonic acid can be exemplified.

<Triphenylsulfonium salt>
Triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, or triphenylsulfonium Butyltris(2,6-difluorophenyl)borate can be exemplified.

<Alkyl sulfonium salt>
Examples of alkylsulfonium salts include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4-(benzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate, dimethyl-4-( benzoyloxy)phenylsulfonium hexafluoroantimonate, dimethyl-4-(benzoyloxy)phenylsulfonium hexafluoroarsenate, or dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate.

<Benzylsulfonium salt>
Benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethyl sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, or 4-methoxybenzyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate can be exemplified.

<Dibenzylsulfonium salt>
The dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate. fluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, or benzyl-4-methoxybenzyl- 4-Hydroxyphenylsulfonium hexafluorophosphate can be exemplified.

<Substituted benzylsulfonium salt>
Substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, or o-chlorobenzyl-3- Chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate can be exemplified.

<Benzothiazonium salt>
Benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3-(p-methoxybenzyl) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, or 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate can be exemplified.

<Tetrahydrothiophenium salt>
Tetrahydrothiophenium salts include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate. , 1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiophenium-1,1, 2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate, 1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiophenium-2-(5-t-butoxycarbonyloxybicyclo[ 2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, or 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium-2-(6 -t-butoxycarbonyloxybicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate.

<Sulfonimide compound>
Sulfonimide compounds include 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-(2-trifluoromethyl phenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)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-(trifluoromethanesulfonyl oxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(nonafluorobutanesulfonyloxy)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-dicarboxy imide, 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-oxy-2 , 3-dicarboximide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo[ 2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy- 2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy ) naphthyldicarboximide, N-(camphorsulfonyloxy) naphthyldicarboximide, N-(4-methylphenylsulfonyloxy) naphthyldicarboximide, N-(phenylsulfonyloxy) naphthyldicarboximide, N-(2- trifluoromethylphenylsulfonyloxy)naphthyldicarboximide, N-(4-fluorophenylsulfonyloxy)naphthyldicarboximide, N-(pentafluoroethylsulfonyloxy)naphthyldicarboximide, N-(heptafluoropropylsulfonyloxy) naphthyldicarboximide, N-(nonafluorobutylsulfonyloxy)naphthyldicarboximide, N-(ethylsulfonyloxy)naphthyldicarboximide, N-(propylsulfonyloxy)naphthyldicarboximide, N-(butylsulfonyloxy) naphthyldicarboximide, N-(pentylsulfonyloxy)naphthyldicarboximide, N-(hexylsulfonyloxy)naphthyldicarboximide, N-(heptylsulfonyloxy)naphthyldicarboximide , N-(octylsulfonyloxy)naphthyldicarboximide, or N-(nonylsulfonyloxy)naphthyldicarboximide.

<Halogen-containing compound>
Halogen-containing compounds include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

<Diazomethane compound>
The diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-tolylsulfonyl)diazomethane, bis(2,4-xylylsulfonyl)diazomethane, bis (p-chlorophenylsulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl(1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, or phenylsulfonyl(benzoyl)diazomethane can be exemplified.

<Sulfone compound>
Sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and diaryldisulfone compounds.

<Sulfonic acid ester compound>
The sulfonate compounds may include alkylsulfonates, haloalkylsulfonates, arylsulfonates, or iminosulfonates.

<Carboxylic acid ester compound>
Carboxylic acid ester compounds include carboxylic acid o-nitrobenzyl esters.

<(A) Acid Generator Contained in the Ink Pattern Forming Composition of the Present Invention>
These (A) acid generators may be used alone or in combination of two or more. Oxime sulfonate compounds, onium salts, and sulfonate compounds are preferred, and oxime sulfonate compounds are particularly preferred, since they are highly effective in improving the exposure sensitivity of a film made of the ink pattern-forming composition.

[Containment of (A) Acid Generator in Ink Pattern Forming Composition]
The content of (A) the acid generator in the ink pattern forming composition of the present invention is preferably 0.1% or more and 10% by mass based on the fluorine-containing polymer (1) of the present invention. % or less, more preferably 1% or more and 5% or less. By setting the content of the acid generator (A) within the range described above, the composition for forming an ink pattern can have high exposure sensitivity, and a pattern forming film with higher definition can be obtained due to the lyophobic portion and the lyophilic portion. be done.

5-2. (B) Solvent The solvent (B) used as a component in the composition for forming an ink pattern of the present invention is not particularly limited as long as it can dissolve or disperse each component of the composition for forming an ink pattern. Organic solvents such as alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aliphatic hydrocarbons, aromatic hydrocarbons, ketones or esters can be mentioned. Each (B) solvent is shown below.

[Alcohol]
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>
Examples of long-chain alkyl alcohols include 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, or 1,8-octanediol.

<Aromatic alcohols>
Benzyl alcohol can be illustrated as aromatic alcohols. Examples of ethylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether.

<Propylene glycol monoalkyl ethers>
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

<Dipropylene glycol monoalkyl ethers>
Examples of dipropylene glycol monoalkyl ethers include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and 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.

[Ethers]
Examples of ethers include tetrahydrofuran, hexylmethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and 1,4-dioxane.

[Diethylene glycol alkyl ethers]
Examples of diethylene glycol alkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and the like.

<Ethylene glycol alkyl ether acetates>
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.

<Propylene glycol alkyl ether acetates>
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate.

<Propylene glycol monoalkyl ether propionates>
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, or propylene glycol monobutyl ether propionate. can be done.

[Aliphatic hydrocarbons]
Examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane, and decalin. .

[Aromatic hydrocarbons]
Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, and dichlorobenzene.

[Ketones]
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone.

[Esters]
Esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and ethyl 2-hydroxy-2-methylpropionate. , methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionate Butyl acid, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, propoxy ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Examples include butyl methoxypropionate, methyl 2-ethoxypropionate, or ethyl 2-ethoxypropionate.

[Content of solvent (B) in ink pattern forming composition]
These (B) solvents may be used alone or in combination of two or more.

The content of the (B) solvent in the ink pattern forming composition is preferably 200 parts by mass to 1600 parts by mass, more preferably 100 parts by mass of the ink pattern forming composition other than the (BC) solvent. 400 parts by mass to 1000 parts by mass. By using the solvent (B) within the range described above, it is possible to improve the wettability of the composition for forming an ink pattern on a glass substrate or the like, suppress the occurrence of coating unevenness, and obtain a uniform film.

5-3. (C) Quencher The (C) quencher used in the composition for forming an ink pattern of the present invention functions as an acid diffusion suppressing material that prevents diffusion of acid from the acid generator (A) during exposure when forming a film. A photodegradable base that is sensitized by exposure to generate a weak acid can be mentioned. The photodisintegrating base is preferably an onium salt compound.

The photodegradable base generates an acid in the exposed area, while the anion exhibits a high acid-capturing function in the unexposed area. quench the diffusing acid. The acid is deactivated only in the unexposed areas. In the pattern-forming film after exposure to the pattern-forming composition of the present invention, the boundary between the lyophobic portion and the lyophilic portion becomes clear, the contrast of the pattern after ink application is improved, and a fine pattern can be obtained. (C) A quencher may be used alone or in combination of two or more.

[Containment of (C) quencher in ink pattern-forming composition]
The content of (C) the quencher in the ink pattern-forming composition is preferably 0.001 to 5 parts by mass, more preferably 0.001 to 5 parts by mass, relative to 100 parts by mass of the fluoropolymer (1). 005 parts by mass to 3 parts by mass. (C) By setting the content of the quencher within the range described above, the boundary between the liquid-repellent portion and the lyophilic portion becomes clear in the pattern-forming film after exposure to the composition for forming an ink pattern of the present invention, and after the ink is applied, The contrast of the pattern is improved, and a fine pattern can be obtained.

5-4. (D) Sensitizer 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 desired to be further improved. (D) The sensitizer is preferably a compound that absorbs light or radiation and enters an excited state. (D) The sensitizer is in an excited state, and upon contact with the acid generator (A), causes electron transfer, energy transfer, heat generation, or the like, whereby the acid generator (A) decomposes to generate an acid. easier to generate. (D) Sensitizers may have an absorption wavelength in the region of 350 nm to 450 nm, polynuclear aromatics, xanthenes, xanthones, cyanines, merocyanines, rhodacyanines, oxonols, thiazines, acridine , acridones, anthraquinones, squariums, styryls, base styryls, or coumarins.
Each (D) sensitizer is shown below.

[Polynuclear aromatics]
Examples of polynuclear aromatics include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, and 9,10-dipropyloxyanthracene. be able to.

[Xanthenes]
Examples of xanthenes include fluorescein, eosin, erythrosine, rhodamine B, and rose bengal.

[Xanthones]
Examples of xanthones include xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, and isopropylthioxanthone.

[Cyanines]
Examples of cyanines include thiacarbocyanine and oxacarbocyanine.

[Merocyanines]
Examples of merocyanines include merocyanine and carbomerocyanine.

[thiazines]
Examples of thiazines include thionin, methylene blue, and toluidine blue.

[Acridines]
Examples of acridine include acridine orange, chloroflavin, and acriflavin.

[Acridones]
Examples of acridones include acridone and 10-butyl-2-chloroacridone.

[Anthraquinones]
Anthraquinones can be exemplified as anthraquinones.

[Squariums]
Squarium can be exemplified as the squarium.

[Base styryl]
Examples of base styryl compounds include 2-[2-[4-(dimethylamino)phenyl]ethenyl]benzoxazole.

[Coumarins]
Coumarins include 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, or 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[l]benzopyrano[6,7, 8-ij]quinolizin-11-nones can be exemplified.

These (D) sensitizers may be used alone or in combination of two or more.

[(D) Sensitizer contained in the composition for forming an ink pattern of the present invention]
As the sensitizer (D) used in the composition for forming an ink pattern of the present invention, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable because they are highly effective in improving exposure sensitivity. or xanthones, particularly preferably xanthones. Among xanthones, diethylthioxanthone and isopropylthioxanthone are preferred.

[Content of (D) sensitizer 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, relative to 100 parts by mass of the fluoropolymer (1). . (D) By setting the content of the sensitizer within the range described above, the exposure sensitivity of the ink pattern-forming composition is improved, and the liquid-repellent portion of the pattern-forming film after exposure with the pattern-forming composition of the present invention is The boundary between the lyophilic portion and the lyophilic portion becomes clear, the contrast of the ink pattern after ink application is improved, and a fine pattern can be obtained.

5-5. (E) Polymerizable compound The (E) polymerizable compound used as a component in the composition for forming an ink pattern of the present invention is contained in the composition for forming an ink pattern in order to make the resulting pattern-forming film harder. be. (E) The polymerizable compound is a compound having an ethylenically unsaturated bond other than the fluoropolymer (1). As such a polymerizable compound (E), since the polymerizable compound has good polymerizability and the pattern forming film obtained from the composition for forming an ink pattern becomes harder, a monofunctional or bifunctional or higher functional acrylic acid ester is used. and methacrylic acid esters.

Each (E) polymerizable compound is shown below.
[Monofunctional acrylate and methacrylate]

<Monofunctional acrylic acid ester>
Monofunctional acrylates include 2-hydroxyethyl acrylate, diethylene glycol monoethyl ether acrylate, (2-acryloyloxyethyl)(2-hydroxypropyl) phthalate, or (2-methacryloyloxyethyl)(2-hydroxypropyl) phthalate. can be exemplified.

<Monofunctional methacrylic acid ester>
Examples of monofunctional methacrylic acid esters include 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether methacrylate, and ω-carboxypolycaprolactone monoacrylate.

Monofunctional acrylic acid esters and methacrylic acid esters are commercially available, for example, Toagosei Co., Ltd., trade name, Aronix (registered trademark), product numbers M-101, M-111, M- 114, and M-5300, Nippon Kayaku Co., Ltd., trade name KAYARAD, product numbers TC-110S, TC-120S, and Osaka Organic Chemical Industry Co., Ltd., trade names Viscoat 158, 2311 Viscoat, etc. are commercially available. .

[Bifunctional acrylic acid ester and methacrylic acid ester]
Examples of bifunctional acrylic esters include ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol diacrylate, and 1,9-nonanediol diacrylate. can be done.

Examples of bifunctional methacrylic acid esters include propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, and 1,9-nonanediol dimethacrylate. can be done.

Bifunctional acrylic acid esters and methacrylic acid esters are commercially available, for example, from Toagosei Co., Ltd., trade name, Aronix (registered trademark), product number, M-210, M-240, M -6200, Nippon Kayaku Co., Ltd., product name, KAYARAD, product number, HDDA, HX-220, R-604, Osaka Organic Chemical Industry Co., Ltd., product name, Viscoat, product number, 260, 312, 335HP, Kyoeisha Chemical Co., Ltd. commercially available under the trade name of light acrylate 1,9-NDA.

[Trifunctional or higher acrylic acid ester and methacrylic acid ester]
Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol penta Acrylates, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, tri(2-acryloyloxyethyl) ) phosphate, tri(2-methacryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, tris(acryloxyethyl) isocyanurate, or linear alkylene groups and alicyclic A compound having a formula structure and having two or more isocyanate groups, and a compound having one or more hydroxyl groups in the molecule and having three, four or five (meth)acryloyloxy groups A polyfunctional urethane acrylate compound obtained by reacting with can be exemplified.

Tri- or more functional acrylates and methacrylates are commercially available, for example, Toagosei Co., Ltd., trade name, Aronix (registered trademark), product numbers, M-309, M-315, M-400, M-405, M-450, M-7100, M-8030, M-8060, TO-1450, from Nippon Kayaku Co., Ltd., trade name, KAYARAD, product number, TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12, from Osaka Organic Chemical Industry Co., Ltd., product name, Viscoat, product number, 295, 300, 360, GPT, 3PA, 400, from Kyoeisha Chemical Co., Ltd., Trade names such as light acrylate 1,9-NDA are commercially available. The polyfunctional urethane acrylate compound is from Daiichi Kogyo Seiyaku Co., Ltd., trade name New Frontier (registered trademark) R-1150, Nippon Kayaku Co., Ltd., trade name KAYARAD, product number DPHA-40H. etc., are commercially available.

As the polymerizable compound (E) used in the ink pattern-forming composition of the present invention, ω-carboxypolycaprolactone monoacrylate, 1,9 is preferable because it has a large effect of making the obtained pattern-forming film harder. - nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, mixtures of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene They are oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, or polyfunctional urethane acrylate compounds. Particularly preferred is a tri- or higher functional ac(meth)rylic acid ester, which is a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

[Content of (E) polymerizable compound in composition for ink pattern formation]
These (E) polymerizable compounds may be used alone or in combination of two or more. (E) The content of the polymerizable compound is preferably 1 part by mass to 300 parts by mass, more preferably 3 parts by mass to 200 parts by mass, relative to 100 parts by mass of the fluoropolymer (1), Particularly preferably, it is 5 parts by mass to 100 parts by mass. By setting the amount of the polymerizable compound (E) within the above range, the pattern forming film obtained from the ink pattern forming composition can be made harder.

6. Ink pattern formation method

The ink pattern forming method of the present invention includes the following two types of pattern forming methods (A) and (B). The ink pattern forming method (A) is a method using a photomask, and the ink pattern forming method (B) is a method using a drawing apparatus.

[Ink pattern forming method (A)]
The method (A) for forming an ink pattern of the present invention includes a film forming step of applying the composition for forming an ink pattern on a substrate to form a film; A film is irradiated with light, the pattern of the photomask is transferred to the film, and an exposure step of obtaining a patterned film having a lyophobic portion and a lyophilic portion is obtained. including a step of forming an ink pattern to obtain an ink pattern.

[Pattern Forming Method (B)]
The method (B) for forming an ink pattern of the present invention comprises a film forming step of applying the composition for forming an ink pattern onto a substrate and heating the resulting coating film; A drawing step of scanning and exposing the film with a drawing device to draw a pattern on the film to obtain a pattern forming film having a lyophobic portion and a lyophilic portion, and an ink pattern forming step of applying ink to the obtained pattern forming film. including.

6-1. Film Forming Process and Ink Pattern Forming Process of Ink Pattern Forming Method Hereinafter, the film forming process common to the ink pattern forming methods (A) and (B) of the present invention, and the exposure and fixation in the ink pattern forming method (A). , and (B), and the ink pattern forming process common to the ink pattern forming methods (A) and (B).

6-2. Film-Forming Step The film-forming step is a step of applying the ink pattern-forming composition of the present invention described above to a substrate and heating (pre-baking) the resulting coating film.

[substrate]
Substrates used in the film-forming process include resin substrates, glass substrates, quartz substrates, silicon substrates, and other semiconductor substrates conventionally used in electronic circuits. Examples of resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethersulfone, polycarbonate, and polyimide.

Before applying the composition for forming an ink pattern to the substrate, the surface of the substrate may be subjected to pretreatment such as washing, roughening, and providing a fine uneven surface, if necessary.

[Application method]
The method of applying the ink pattern-forming composition to the substrate is not particularly limited, and may be coating using a brush or brush, dipping, spraying, roll coating, spin coating, slit die coating. methods, bar coating methods, flexographic printing, offset printing, inkjet printing, or dispensing methods may be mentioned. In the pattern forming method of the present invention, spin coating is preferred.

[Thickness]
The thickness of the coating film formed in the above steps may be appropriately adjusted according to the desired application. In the ink pattern forming method of the present invention, the thickness is preferably 0.1 μm to 20 μm.

[Pre-bake]
The pre-baking conditions common to the ink pattern forming methods (A) and (B) of the present invention are preferably a heating temperature of 60° C. to 120° C. and a heating time of 1 minute to 10 minutes.

6-3. Exposure process and drawing process
[Exposure process]
In the exposure step in the ink pattern forming method (A), the film obtained in the film forming step is irradiated with light having a wavelength of 150 nm or more and 500 nm or less through a photomask, and the pattern of the photomask is transferred to the film. 2 is a step of obtaining a pattern forming film having a lyophobic portion and a lyophilic portion. Exposure is performed through a photomask having a predetermined pattern so that an exposed portion having a pattern similar to the desired pattern is formed.

[Drawing process]
In the drawing step in the ink pattern forming method (B), the film obtained in the film forming step is scanned and exposed to light having a wavelength of 150 nm or more and 500 nm or less by a drawing device to draw a pattern on the film to make it liquid-repellent. This is a step of obtaining a pattern forming film having a portion and a lyophilic portion. For example, it is performed by scanning a predetermined pattern using a direct writing exposure apparatus.

[Light used]
Visible light, ultraviolet light, X-rays or radiation that is a stream of charged particles can be used for exposure and writing. UV light with a wavelength of 150 nm or more and 500 nm or less is preferred, and UV light with a wavelength of 365 nm from a UV light emitting diode is particularly preferred.

Due to the effect of the acid generated from the acid generator (A) in the film by exposure and drawing, the acid dissociable groups of the fluoropolymer (1) are eliminated and volatilized. As a result, the film thickness of the exposed portion becomes thinner than the film thickness of the unexposed portion, and a concave pattern is formed. At that time, since the acid-dissociable group has a fluorine-containing atom, the unexposed area exhibits liquid repellency and the exposed area becomes lyophilic. Therefore, the film formed on the substrate is a patterned film having lyophobic unexposed areas and lyophilic exposed areas that are recessed patterns.

[heating]
It is preferable to heat the pattern forming film after exposure. By heating the pattern-formed film after exposure, it is possible to further volatilize the components of the acid-dissociable groups dissociated from the fluoropolymer (1) in the exposed areas, and the exposed concave portions and the unexposed convex portions can be further volatilized. A more precise pattern consisting of is obtained.

Examples of the method of heating the pattern-formed film include a method of heating the film-formed substrate using a hot plate, a batch-type oven, or a conveyor-type oven, a method of drying with hot air using a dryer or the like, and a method of vacuum baking. can be mentioned. The heating conditions vary depending on the composition of the composition, the thickness of the resulting coating film, etc., but are preferably 60° C. or higher and 150° C. or lower for 3 minutes or longer and 30 minutes or shorter.

6-4. Ink Pattern Forming Step The ink pattern is formed by applying ink to the obtained pattern forming film and obtaining a pattern with the ink.

The difference in contact angle between the hydrophilic and liquid-repellent portions and the liquid-repellent portions of the pattern forming film before and after exposure to water and hexadecane, which are ink solvents, is preferably 30° or more, more preferably 50° or more. When the contact angle difference is within the above range, even when ink is applied to the convex liquid-repellent portion, the ink is repelled and the ink easily moves to the concave portion which is the lyophilic portion, so that it is not exposed to light. A finer ink pattern can be obtained, which consists of the concave portions and the unexposed convex portions.

[Formation of conductive ink pattern]
In the method for forming an ink pattern of the present invention, a conductive ink pattern can be formed on a substrate by using a conductive ink as the ink.

6-5. Application to Electronic Circuits and Electronic Devices In the method of forming an ink pattern of the present invention, an electric circuit comprising a conductive ink pattern can be formed on a substrate to manufacture an electronic device.

An electronic circuit is wiring by a conductive ink pattern formed on a substrate. An electronic device is a device having an electronic circuit, and examples thereof include liquid crystal displays, mobile information devices such as mobile phones, digital cameras, organic displays, organic EL lighting, various sensors, and wearable devices.

7. Fluoromonomer The fluoropolymers (1) to (3) of the present invention are synthesized by homopolymerizing or copolymerizing the fluoromonomer (4) of the present invention shown below.

[Fluorine-containing monomer (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 a fluorine-containing It is obtained by homopolymerizing or copolymerizing the monomer (4). Hereinafter, it may be referred to as fluorine-containing monomer (4).

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Of the atoms, 7 or less may be substituted with fluorine atoms, and R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or 3 to 10 carbon atoms. Of the hydrogen atoms bonded to carbon atoms in the alkyl group, 7 or less may be substituted with fluorine atoms X is a single bond or a divalent group, including a divalent group 7 or less hydrogen atoms may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms.R is a fluorine-containing alkyl group having 1 to 3 carbon atoms.The same shall apply hereinafter.)

[Fluorine-containing monomer (5)]
The fluorine-containing monomer (1) of the present invention is preferably the fluorine-containing monomer (5) in which R ² , R ⁴ and R ⁵ in the formula (1) are hydrogen atoms.

When the fluoropolymer (1) obtained by polymerizing the fluoromonomer (4) is used as a component of the resist or ink pattern forming composition of the present invention to form a film on a substrate, the solubility in a solvent For this reason, R ² , R ⁴ and R ⁵ in the above formula (4) are preferably hydrogen atoms, preferably a fluorine-containing cyclic acetal structure represented by the following formula (5) It is a single unit. Hereinafter, it may be referred to as fluorine-containing monomer (5).

(R ¹ , R ³ , X, and Y in formula (5) are synonymous with formula (4).)

[Fluorine-containing monomer (6)]
The fluoromonomer (5) of the present invention is preferably the following fluoromonomer (6), wherein Y in the formula (5) is a trifluoromethyl group.

Furthermore, when the above-mentioned fluoropolymer (2) obtained by homopolymerizing or copolymerizing the fluoromonomer (5) is used as a composition for forming a resist or an ink pattern and formed on a substrate, it is dissolved in a solvent. Y in the above formula (4) is preferably a trifluoromethyl group, more preferably a fluorine-containing cyclic acetal structure represented by the following formula (6): It is a monomer. Hereinafter, it may be referred to as fluorine-containing monomer (6).

(R ¹ , R ³ and X in formula (6) are synonymous with formula (4).)
Specific examples of the fluorine-containing monomer (4) of the present invention are shown below, but the present invention is not limited thereto.

8. Method for Producing Fluoromonomer (4) The method for producing the fluoromonomer (4) of the present invention will be described.
The method for producing a fluoromonomer of the present invention comprises cyclizing a hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or hydroxyvinyl ester represented by the following formula (11), ) to obtain a cyclic hemiacetal compound represented by

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Of the atoms, 7 or less may be substituted with fluorine atoms, and R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or 3 to 10 carbon atoms. Of the hydrogen atoms bonded to carbon atoms in the alkyl group, 7 or less may be substituted with fluorine atoms X is a single bond or a divalent group, including a divalent group 7 or less hydrogen atoms may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms, R is a fluorine-containing alkyl group having 1 to 3 carbon atoms, and Z is a straight chain having 1 to 20 carbon atoms. , a branched or cyclic alkyl group with 3 to 20 carbon atoms, some or all of the hydrogen atoms in Z may be substituted with halogen atoms, and ether bonds, siloxane bonds, thioether bonds, carbonyl bonds (The same applies hereinafter.)

8-1. Acylation or Alkylation of Fluorinated Cyclic Hemiacetal Compound The fluorinated monomer (4) of the present invention is a fluorinated cyclic hemiacetal compound represented by the formula (7) (hereinafter referred to as a fluorinated cyclic hemiacetal compound (7 ) can be synthesized by introducing a polymerizable group into (sometimes referred to as ) to obtain a fluorine-containing monomer (4). This reaction is shown below.

(R ¹ , R ² to R ⁵ , X, and Y are the same as defined above, and A is a hydrogen atom, a halogen atom, an acryloyl group, or a methacryloyl group.)

This reaction is possible by acylating or alkylating the hydroxyl group of the fluorine-containing cyclic hemiacetal compound (7) having a hydroxyl group, in the presence of a base, in a solvent or without a solvent, in the acryloyl compound (12). , an acylating agent in which X is a single bond, or an alkylating agent in which X is a divalent organic group to synthesize the fluorine-containing monomer (4).

8-1-1. Acylation of fluorine-containing cyclic hemiacetal compounds [acylating agents]
Acylating agents may include carboxylic acid chlorides or carboxylic acid anhydrides.

Examples of acylating agents include acrylic acid chloride, methacrylic acid chloride, acrylic anhydride, methacrylic acid anhydride, 2-fluoroacrylic acid chloride, and 2-methacryloyloxyacetyl chloride.

The amount of the acylating agent used is preferably 0.5 mol or more and 10 mol or less, particularly 1 mol or more and 3 mol or less, per 1 mol of the fluorine-containing cyclic hemiacetal compound (7). It is preferable because it becomes expensive. The reaction with the acylating agent can be carried out in the presence of a base in the absence of solvent or in a solvent.

[base]
Examples of bases include inorganic bases and organic bases. The amount of the base used in the reaction is preferably 0.05 or more and 10 mol or less per 1 mol of the fluorine-containing cyclic hemiacetal compound (7), and particularly preferably 1 mol or more and 3 mol or less, because the yield is increased. .

<Inorganic base>
Examples of inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate.

<Organic base>
Examples of organic bases include triethylamine, diisopropylethylamine, pyridine, imidazole, triethylenediamine, dimethylaminopyridine and the like.

[solvent]
Examples of solvents include hydrocarbon solvents, ether solvents and chlorine solvents. You may use with water as needed.

<Hydrocarbon solvent>
Examples of hydrocarbon solvents include hexane, heptane, cyclohexane, methylcyclohexane, toluene, and xylene.

<Ether solvent>
Examples of ether solvents include diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol dimethyl ether.

<Chlorine-based solvent>
Examples of chlorinated solvents include methylene chloride, chloroform, and 1,2-dichloroethylene.

8-1-2. Alkylation of Fluorine-Containing Cyclic Hemiacetal Compound A polymerizable group can also be introduced by alkylating the hydroxyl group of the fluorine-containing cyclic hemiacetal compound (7). A catalyst may be used in the reaction to accelerate the reaction rate.
[Alkylating agent]
Alkylating agents include alkyl halides and sulfonic acid esters.

The reaction with the acylating agent can be carried out in the presence of a base in the absence of solvent or in a solvent. The amount of the alkylating agent to be used is preferably 0.5 mol or more and 10 mol or less per 1 mol of the fluorine-containing cyclic hemiacetal compound (7). preferable.

<Alkyl Halide>
Examples of alkyl halides include chloroethyl acrylate, chloroethyl methacrylate, bromoethyl acrylate, and bromoethyl methacrylate.

<Sulfonic acid ester>
Sulfonic acid esters include 2-methylsulfonyloxyethyl acrylate, 2-methylsulfonyloxyethyl methacrylate, 2-p-toluenesulfonyloxyethyl acrylate, and 2-p-toluenesulfonyl methacrylate. Niloxyethyl can be exemplified.

[base]
Examples of bases include inorganic bases and organic bases. Examples of organic bases include organic metal salts. The amount of the base used in the reaction is preferably 0.05 mol or more and 10 mol or less, and is particularly preferably 1 mol or more and 3 mol or less because the yield increases.

<Inorganic base>
Examples of inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride, and ammonia. can do.

<Organic base>
Examples of organic metal salts include organic lithium salts, Grignard reagents and alkali metal salts.

Examples of organic lithium salts include triethylamine, diisopropylethylamine, pyridine, imidazole, triethylenediamine, dimethylaminopyridine, methyllithium, and n-butyllithium.

Examples of Grignard reagents include methylmagnesium bromide.

Examples of alkali metal salts include sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[solvent]
As the solvent, a solvent that is generally considered to be good for nucleophilic substitution reactions is preferable, and examples include aprotic polar solvents and protic polar solvents. A two-layer system of these solvents and water may be used.

Examples of aprotic polar solvents include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.

Examples of protic polar solvents include acetone, methyl ethyl ketone, acetonitrile, propionitrile, diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, and dichloroethylene.

[catalyst]
Iodide or bromide may be added as a catalyst to accelerate the kinetics of the alkylation reaction. When the catalyst is added, it is preferably added in an amount of 0.001 to 1 mol, particularly 0.005 to 0.5 mol, per 1 mol of the hemiacetal compound (7).

<iodide>
Examples of iodides include sodium iodide, lithium iodide, and tetrabutylammonium iodide.

<Bromide>
Examples of bromides include sodium bromide, lithium bromide, and tetrabutylammonium bromide.

9. Fluorine-Containing Cyclic Hemiacetal The fluoropolymer (1) of the present invention is obtained by polymerizing the fluoromonomer (4). A fluorine-containing monomer is a fluorine-containing monomer having a fluorine-containing cyclic acetal structure. The fluorine-containing cyclic hemiacetal (7) is a compound as a precursor of the fluorine-containing monomer (4).

[Fluorine-containing cyclic hemiacetal (7)]

(Wherein, R ² to R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Among them, 7 or less may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (—COOR), and a fluorine-containing alkyl group or carboxylic 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms.R is a fluorine-containing alkyl group having 1 to 3 carbon atoms.)

[Fluorine-containing cyclic hemiacetal (8)]
The fluorine-containing hemiacetal (7) of the present invention is preferably the following fluorine-containing hemiacetal (8) in which R ² , R ⁴ and R ⁵ in the formula (7) are hydrogen atoms.

The fluoropolymer (2) of the present invention is obtained by polymerizing the fluoromonomer (5). A fluorine-containing monomer is a fluorine-containing monomer having a fluorine-containing cyclic acetal structure. Moreover, the following fluorine-containing cyclic hemiacetal (8) is a compound as a precursor of the fluorine-containing monomer (5).

(R ³ and X in formula (8) are synonymous with formula (7).)
[Fluorine-containing cyclic hemiacetal (9)]
The fluorine-containing hemiacetal (7) of the present invention is preferably the fluorine-containing hemiacetal (9) in which Y in the formula (8) is a trifluoromethyl group.

The fluorine-containing polymer (3) of the present invention is a fluorine-containing monomer obtained by polymerizing the fluorine-containing monomer (6) and has a fluorine-containing cyclic acetal structure. The following fluorine-containing cyclic hemiacetal (9) is a compound as a precursor of the fluorine-containing monomer (6).

(R ³ in formula (9) has the same meaning as formula (7).)

10. Synthesis of Fluorine-Containing Cyclic Hemiacetal (7) A method for producing the fluorine-containing cyclic hemiacetal (7) of the present invention will be described.

A hydroxycarbonyl compound represented by formula (10) or a hydroxyvinyl ether or hydroxyvinyl ester represented by formula (11) is cyclized to obtain a cyclic hemiacetal compound of invention 12 represented by formula (7). , a method for producing a cyclic hemiacetal compound.

(Wherein, R ² to R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Among them, 7 or less may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (—COOR), and a fluorine-containing alkyl group or carboxylic 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms, R is a fluorine-containing alkyl group having 1 to 3 carbon atoms, and Z is a straight chain having 1 to 20 carbon atoms. , a branched or cyclic alkyl group with 3 to 20 carbon atoms, some or all of the hydrogen atoms in Z may be substituted with halogen atoms, and ether bonds, siloxane bonds, thioether bonds, carbonyl bonds may contain.)
The fluorine-containing cyclic hemiacetal (7) of the present invention can be synthesized mainly through the following two steps.

10-1. 1st step The 1st step is a carbonyl-ene reaction of allyl alcohols, allyl ethers or allyl esters with hexafluoroacetone (hereinafter sometimes referred to as HFA) or trifluoropyruvate to react with the formula (10 ) or a hydroxyvinyl ether represented by formula (11).

Below, allyl alcohols, allyl ethers or allyl esters represented by formula (12) and a trifluorocarbonyl compound represented by formula (13) undergo a carbonyl-ene reaction, represented by formula (10). hydroxyvinylcarbonyl compound or hydroxyvinyl ether or hydroxyester represented by formula (11).

Hereinafter, they may be referred to as hydroxycarbonyl compounds (10), hydroxyvinyl ethers (11), allyl alcohols (12), allyl ethers (12), allyl esters (12), and trifluorocarbonyl compounds (13).

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Of the atoms, 7 or less may be substituted with fluorine atoms, and R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or 3 to 10 carbon atoms. Of the hydrogen atoms bonded to carbon atoms in the alkyl group, 7 or less may be substituted with fluorine atoms Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (—COOR), and 7 or less hydrogen atoms contained in the fluorine-containing alkyl group or the carboxylic acid ester group may be substituted with fluorine atoms, and R is a fluorine-containing alkyl group having 1 to 3 carbon atoms; Z is a linear, C3-20 branched or cyclic alkyl group having 1 to 20 carbon atoms, and even if some or all of the hydrogen atoms in Z are substituted with halogen atoms It may contain an ether bond, a siloxane bond, a thioether bond, and a carbonyl bond.)

Allyl alcohols (12) in which Z is a hydrogen atom, or allyl ethers (12) or allyl esters (12) in which Z is an alkyl group and a hydroxyl group is protected, and an HFA in which Y is a trifluoromethyl group It is possible to selectively synthesize hydroxyvinyl ester (10) or hydroxyvinyl ether (11) by mixing and, if necessary, heating under closed pressure in an autoclave or the like. Furthermore, even when trifluoropyruvate is used instead of HFA, the reaction proceeds efficiently.

This reaction is an ene reaction between the allyl moiety of allyl alcohol (12), allyl ether (12) or allyl ester (12) and fluorine-containing carbonyl compound (13). The higher the electron density of the olefin moiety on the ether (12) or allyl ester (12) side, the easier the reaction proceeds, and the reaction can proceed selectively with less side reactions. Rather than all of R ² to R ⁵ in allyl alcohols (12), allyl ethers (12) or allyl esters (12) being hydrogen atoms, some are substituted with electron donating groups is preferred, and the electron-donating group is preferably a methyl group.

The amount of HFA or trifluoropyruvate used per 1 mol of allyl alcohol (12), allyl ether (12) or allyl ester (12) is preferably 0.5 mol or more and 10 mol or less, particularly 1 mol or more and 3 mol or less are preferable.

[Allyl alcohols]
Examples of allyl alcohols (12) in which Z is a hydrogen atom include allyl alcohol, β-methallyl alcohol, 1-buten-3-ol, crotyl alcohol, and 3-methyl-2-buten-1-ol. can do.

[Allyl ethers]
As the allyl ethers (12) or allyl esters (12) in which Z is other than a hydrogen atom, those obtained by introducing a protecting group to the hydroxyl group of the above-mentioned allyl alcohols (12) are preferable. , acetals, acyls, benzyls, or carbamates. In order to improve the electron density of the olefin portion and promote the reaction, the protecting group is preferably an acetal, silyl, carbamate or benzyl group.

<Silyl groups>
Examples of silyl groups include trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group and t-butyldiphenylsilyl group.

<Acetals>
Examples of acetals include tetrahydropyranyl group, ethoxyethyl group, butoxyethyl group, methoxymethyl group, methylthiomethyl group, benzyloxymethyl group and methoxyethoxymethyl group.

<Acyls>
Examples of acyl group include formyl group, acetyl group, trifluoroacetyl group, propionyl group, benzoyl group, pivaloyl group, acrylyl group and methacrylyl group.

<Benzils>
Examples of benzyls include a benzyl group and a p-methoxybenzyl group.

<Carbamates>
Examples of carbamates include a t-butoxycarbonyl group and a benzyloxycarbonyl group.

10-2. 1st Step The reaction in the 1st step proceeds without a catalyst or solvent, but an acid catalyst can be used in a solvent to promote the reaction. In order to produce more inexpensively, it is carried out without a solvent and without a catalyst, and from the reaction product, a hydroxy aldehyde represented by the following formula (10), a ketone, or a hydroxy vinyl ether represented by the formula (11), It is preferable to isolate the hydroxyvinyl esters by a purification operation such as distillation.

Whether or not the catalyst is used is not particularly limited, and when used, any of inorganic acids, organic acids and Lewis acids can be used.

Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and zeolite. Examples of organic acids include carboxylic acids, sulfonic acids, cation exchange resins, and Lewis acids. Specifically, formic acid, acetic acid or trifluoroacetic acid as carboxylic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfone as sulfonic acid, aluminum chloride, tetrafluoroacetic acid as Lewis acid Titanium chloride or tin chloride can be exemplified.

The reaction proceeds without the use of a solvent, but when it is used, allyl alcohol (12), allyl ether (12), or allyl ester (12) as raw materials, and HFA or trifluoropyruvate (13) Any solvent that is inert to the target fluorine-containing compound represented by the formula (10) or (11) may be used. Examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons or ethers.

[Aliphatic hydrocarbon]
Examples of aliphatic hydrocarbons include hexane, heptane, cyclohexane, and methylcyclohexane which is a cyclic aliphatic hydrocarbon.

[Aromatic hydrocarbon]
Examples of aromatic hydrocarbons include benzene, toluene and xylene.

[Halogenated hydrocarbon]
Methylene chloride can be exemplified as the halogenated hydrocarbon.

[Ethers]
Examples of ethers include diethyl ether, dibutyl ether, tetrahydrofuran and ethylene glycol dimethyl ether.

10-3. Second step The second step is a step of intramolecularly cyclizing hydroxycarbonyl compound (10), hydroxyvinyl ether or hydroxyvinyl ester (11) to obtain cyclic hemiacetal compound (7) represented by formula (9). be.

The three methods (Methods 1 to 3) shown above can be used, although they vary depending on the type of product and substituents in the first step.

10-3-1. Method-1
In Method-1, as shown in the following reaction scheme, the hydroxycarbonyl compound (10) is selectively intramolecularly cyclized by the action of an acid or base in a solvent to form a fluorine-containing cyclic hemiacetal (7). is a method of obtaining

The method is preferably carried out in a solvent under acidic or basic conditions.

Any of inorganic acids, organic acids and Lewis acids can be used as the acid. The amount of the acid used in the reaction is preferably 0.01 mol or more and 1 mol or less, particularly preferably 0.05 mol or more and 0.2 mol or less, per 1 mol of the hydroxycarbonyl compound (10).

Examples of bases include inorganic bases and organic bases. It is particularly preferable to use sodium hydroxide or potassium hydroxide under basic conditions in a two-layer system of water-organic solvent, which is capable of removing unreacted raw materials and trace fluorine-containing alcohols. The amount of the base used in the reaction is preferably 0.5 mol or more and 10 mol or less per 1 mol of the hydroxycarbonyl compound (10), and is particularly preferably 1 mol or more and 3 mol or less because the yield is high.

[Inorganic acid]
Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and zeolite.

[Organic acid]
Examples of organic acids include carboxylic acids, sulfonic acids, cation exchange resins, and Lewis acids. Carboxylic acid: formic acid, acetic acid or trifluoroacetic acid; sulfonic acid: methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfone; Lewis acid: aluminum chloride, titanium tetrachloride or tin chloride can be exemplified.

[Inorganic base]
Examples of inorganic bases include lithium salt hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride, and ammonia. be able to.

[Organic base]
Examples of organic bases include organic lithium salts, Grignard reagents, and organic alkali metal salts.

Examples of organic lithium salts include triethylamine, diisopropylethylamine, pyridine, imidazole, triethylenediamine, dimethylaminopyridine, methyllithium and n-butyllithium. Examples of Grignard reagents include methylmagnesium bromide. Examples of organic alkali metal salts include sodium methoxide, sodium ethoxide and potassium t-butoxide.

[solvent]
Although the reaction proceeds without the use of a solvent, any solvent that is inert to the raw material hydroxycarbonyl compound (10) and the product fluorine-containing cyclic hemiacetal (7) may be used. Examples include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and ethers.

Examples of aliphatic hydrocarbons include hexane, heptane, cyclohexane, and methylcyclohexane, which is a cyclic aliphatic hydrocarbon. Examples of aromatic hydrocarbons include benzene, toluene and xylene. Examples of halogenated hydrocarbons include methylene chloride, and examples of ethers include diethyl ether, dibutyl ether, tetrahydrofuran, and ethylene glycol dimethyl ether.

10-3-2. Method-2
In method-2, as shown in the following reaction formula, after deprotection of hydroxyvinyl ether (11) or hydroxyvinyl ester (11), the hydrogen atom of the hydroxyl group is removed by the action of an acid or base in a solvent. In this method, intramolecular cyclization proceeds selectively to obtain a fluorine-containing cyclic hemiacetal (7) by abstraction. This reaction is shown below.

Hydroxyvinyl ether (11) or hydroxyvinyl ester (11) is a compound in which the hydroxyl group is protected, and hydroxyvinyl ether (11) or hydroxyvinyl ester (11) deprotects the protective group. , hydroxyvinyl ether (11), or hydroxyvinyl ester (11) is converted to hydroxycarbonyl compound (10), followed by intramolecular cyclization in the same manner as method-1 to form a fluorine-containing cyclic hemiacetal ( 7) can be obtained. A common deprotection method can be used for deprotection. The acid, base or solvent to be used is the same as in Method-1.

10-3-2. Method-3
Method-3, as shown in the following reaction formula, is selected by abstracting a hydrogen atom from a hydroxyl group in a solvent of hydroxyvinyl ether (11) or hydroxyvinyl ester (11) under the action of an acid or base. In this method, the intramolecular cyclization proceeds to obtain the fluorine-containing cyclic acetal intermediate (14), followed by deprotection to obtain the fluorine-containing cyclic hemiacetal (7). This reaction is shown below.

[Intramolecular cyclization]
Hydroxyvinyl ether (11) or hydroxyvinyl ester (11) is added with an acid catalyst in the absence of solvent or in the presence of a solvent, and heated to about the boiling point of the solvent to give a fluorine-containing cyclic acetal intermediate represented by formula (14). you can get a body

Particularly preferred are trifluoroacetic acid, methanesulfonic acid and sulfuric acid, since they give a high yield of the fluorine-containing cyclic acetal intermediate (14). The amount of acid used in the reaction is preferably 0.01 mol or more and 1 mol or less, particularly 0.05 mol or more and 0 .2 mol or less is preferred.

[acid]
Any of inorganic acids, organic acids and Lewis acids can be used as the acid used in Method-3.

<Inorganic acid>
Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and zeolite.

<Organic acid>
Examples of organic acids include carboxylic acids, sulfonic acids, cation exchange resins, and Lewis acids.

Examples of carboxylic acids include formic acid, acetic acid and trifluoroacetic acid, and examples of sulfonic acids include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfone. Examples of Lewis acids include aluminum chloride, titanium tetrachloride and tin chloride.

[Deprotection]
The fluorine-containing cyclic acetal intermediate (14) is a form in which the hydroxyl group of the fluorine-containing cyclic hemiacetal (7) is protected with another substituent, and the protective group is deprotected to obtain the fluorine-containing cyclic hemiacetal (7). can be obtained. A general deprotection method can be used for deprotection.

On the other hand, when Z of hydroxyvinyl ether (11) is a fluorine-containing compound (15) having a polymerizable group, the fluorine-containing monomer (4) can be synthesized by intramolecular cyclization in the first stage of Method-3. . This reaction is shown below.

The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples.

1. Synthesis of fluorine-containing cyclic hemiacetal Fluorine-containing cyclic hemiacetal-1 to belonging to the fluorine-containing monomer represented by the above formula (7), as a precursor for obtaining the fluorine-containing monomer (4) 7 was synthesized by the following method.

1-1-1. Synthesis of fluorine-containing cyclic hemiacetal-1 (Part 1)
Allyl alcohol (manufactured by Tokyo Kasei Co., Ltd., 11.6 g (0.2 mol) was charged into a reactor equipped with a stirrer, and the reactor was sealed. Next, after degassing the inside of the reactor with a vacuum pump, While stirring the content with a stirrer, 66.4 g (0.40 mol) of HFA was introduced in. Then, the temperature inside the reactor was raised to 150° C., and stirring was continued for 40 hours. 50 ml of hydrochloric acid with a concentration of 3.5% by mass was added, and after stirring for 2 hours, the organic layer and the aqueous layer were separated, and 50 ml of sodium hydroxide solution with a concentration of 4% by mass was added to the organic layer. After stirring for 1 hour, the organic layer was separated and distilled under reduced pressure at a pressure of 3.0 kPa and a temperature of 60° C. to 62° C. to obtain 22.4 g of a fluorine-containing cyclic hemiacetal-1 represented by the following formula, yield 50. %.This reaction is shown below.

<NMR analysis result>
The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below.
¹ H-NMR (solvent: deuterated chloroform, reference material: TMS); δ (ppm) 2.32-2.59 (2H, m), 2.65-2.78 (2H, m), 4.11 ( 1H, br), 6.20 (1H, d)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) -77.5 (3F, s), -79.5 (3F, s)

1-1-2. Synthesis of fluorine-containing cyclic hemiacetal-1 (Part 2)
A reactor equipped with a stirrer was charged with 11.6 g (0.2 mol) of allyl alcohol and 0.2 g (0.0002 mol) of methanesulfonic acid, and the reactor was sealed. was deaerated, 66.4 g (0.40 mol) of HFA was introduced while stirring the contents with a stirrer, the temperature in the reactor was raised to 120° C., and stirring was continued for 20 hours. After that, the content was extracted and transferred to a separating funnel, 50 ml of sodium hydroxide solution having a concentration of 4% by mass was added, and after stirring for 1 hour, the organic layer was separated and the pressure was reduced under the conditions of a pressure of 3.0 kPa and a temperature of 60°C to 62°C. Distillation gave 28 g of a fluorine-containing cyclic hemiacetal-1 represented by the following formula with a yield of 63%.The reaction is shown below.

1-2. Synthesis of fluorine-containing cyclic hemiacetal-2 A reactor equipped with a stirrer was charged with β-methallyl alcohol (manufactured by Tokyo Kasei Co., Ltd., 14.4 g (0.2 mol), and the reactor was sealed. Next, After degassing the inside of the reactor with a vacuum pump, 66.4 g (0.40 mol) of HFA was introduced while stirring the contents with a stirrer, then the inside of the reactor was heated to 40° C., and then 2 hours. After the reaction was completed, the content was extracted and transferred to a separating funnel, 50 ml 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. 50 ml of sodium hydroxide solution with a concentration of 4% by mass was added, and after stirring for 1 hour, the organic layer was separated and distilled under reduced pressure at a pressure of 3.0 kPa and a temperature of 68° C. to 69° C. to obtain a fluorine-containing cyclic hemi 43.7 g of acetal-2 was obtained with a yield of 92%.The reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference material: TMS); δ (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)
¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ (ppm) -77.5 (3F, m), -79.5 (3F, m)

1-3. Synthesis of fluorine-containing cyclic hemiacetal-3 Except for using 3-buten-2-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of β-methallyl alcohol used in the synthesis of fluorine-containing cyclic hemiacetal-2 , the reaction represented by the following formula was carried out in the same procedure as in the synthesis of fluorine-containing cyclic hemiacetal-2 to obtain fluorine-containing cyclic hemiacetal-3 with a yield of 87%. This reaction is shown below.

1-4. Synthesis of fluorine-containing cyclic hemiacetal-4 Except for using crotyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of β-methallyl alcohol used in the synthesis of fluorine-containing cyclic hemiacetal-2, a fluorine-containing cyclic In the same procedure as in the synthesis of hemiacetal-2, the reaction represented by the following formula was carried out to obtain fluorine-containing cyclic hemiacetal-4 with a yield of 75%. This reaction is shown below.

1-5. Synthesis of fluorine-containing cyclic hemiacetal-5 3-methyl-2-buten-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in place of β-methallyl alcohol used in the synthesis of fluorine-containing cyclic hemiacetal-2. The reaction represented by the following formula was carried out in the same procedure as in the synthesis of fluorine cyclic hemiacetal-2, except that it was used, to obtain fluorine cyclic hemiacetal-5 in a yield of 65%. This reaction is shown below.

1-6. Synthesis of fluorine-containing cyclic hemiacetal-6 1.86 g (0.01 mol) of β-methallyl-t-butyldimethylsilyl ether in which β-methallyl alcohol was protected with t-butyldimethylsilyl was placed in a 100 ml glass flask equipped with a stirrer according to the standard method. ) was mixed with 2.92 g (0.01 mol) of separately synthesized 1,1,1,3,3,3-hexafluoroisopropyl trifluoropyruvate. Then, after the inside of the reactor was heated to 50° C., stirring was continued for 18 hours. After completion of the reaction, the contents were extracted and transferred to a separating funnel, 10 ml 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. 10 ml of sodium hydroxide solution having a concentration of 4% by mass was added to the organic layer, and after stirring for 1 hour, the organic layer was separated by silica gel column chromatography. 19.0 g of a fluorine-containing cyclic hemiacetal-6 represented by the following formula was obtained with a yield of 52%. This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference material: TMS); δ (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)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) -77.1 (6F, m), -78.5 (3F, m)

[Synthesis of 1,1,1,3,3,3-hexafluoroisopropyl trifluoropyruvate] Trifluoropyruvate 1,1,1,3,3, A procedure for synthesizing 3-hexafluoroisopropyl is shown below.

50 ml of 10% by mass sodium hydroxide solution was added to 17.0 g (0.1 mol) of ethyl trifluoropyruvate (Central Glass Co., Ltd., trade name: E-TFPA) in a 100 ml glass flask equipped with a stirrer and stirred for 2 hours. did. After concentrating under reduced pressure and distilling off ethanol, 55 ml of 10% by mass hydrochloric acid was added for neutralization, and then 30 ml of dichloromethane was added to extract the generated trifluoropyruvic acid into the dichloromethane layer. After separating the dichloromethane layer and removing moisture with a drying agent, 16.2 g (0.1 mol) of CDI (carbonyldiimidazole) (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 1 hour. 16.8 g (0.1 mol) of HFIP (manufactured by Central Glass Co., Ltd.) was added, and the mixture was further stirred for 2 hours. 30 ml of hydrochloric acid having a concentration of 3.5% by mass was added to the reaction solution, and the reaction solution was washed twice with 30 ml of pure water. The organic layer was separated and distilled under reduced pressure at a pressure of 40 kPa and a temperature of 65° C. to obtain 16 g of 1,1,1,3,3,3-hexafluoroisopropyl trifluoropyruvate with a yield of 55%. This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 5.65 (1
H, m)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) -76.6
(6F,s), -83.1 (3F,s)

1-7. Synthesis of fluorine-containing cyclic hemiacetal-7 Instead of 1,1,1,3,3,3-hexafluoroisopropyl trifluoropyruvate used in the synthesis of fluorine-containing cyclic hemiacetal-6, a separately synthesized tri Fluorine-containing cyclic hemiacetal-7 was obtained by the reaction shown in the following formula in the same procedure as in the synthesis of fluorine-containing cyclic hemiacetal-6, except that 2,2,2-trifluoroethyl fluoropyruvate was used. Obtained with a yield of 61%. This reaction is shown below.

[Synthesis of 2,2,2-trifluoroethyl trifluoropyruvate]
The procedure for synthesizing 2,2,2-trifluoroethyl lifluoropyruvate used in the synthesis of the fluorine-containing cyclic hemiacetal-7 is shown below.

16.2 g (0.1 mol) of CDI (carbonyldiimidazole) was added to the dichloromethane solution of trifluoropyruvic acid shown in the synthesis example above in a 100 ml glass flask equipped with a stirrer and stirred at room temperature for 1 hour. 10.0 g (0.1 mol) of 2,2-trifluoroethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred for 2 hours. 30 ml of hydrochloric acid having a concentration of 3.5% by mass was added to the reaction solution, and the reaction solution was washed twice with 30 ml of pure water. The organic layer was separated and distilled under reduced pressure at a pressure of 30 kPa and a temperature of 65° C. to obtain 11 g of 2,2,2-trifluoroethyl trifluoropyruvate with a yield of 50%. This reaction is shown below.

2. Synthesis of Fluorine-Containing Monomer Fluorine-containing monomer (4) was synthesized using the fluorine-containing cyclic hemiacetal-1, 2, 6, and 7 of formula (7).

2-1. Synthesis of fluorine-containing monomer-1 In a 300 ml glass flask equipped with a stirrer, 22.4 g (0.1 mol) of fluorine-containing cyclic hemiacetal-1, 15.1 g (0.15 mol) of triethylamine, and methoxyphenol ( 1000 ppm) was added, and 16.9 g (0.11 mol) of methacrylic anhydride was added dropwise at an internal temperature of 30°C or less. After stirring for 2 hours, 40 ml of diisopropyl ether and 30 ml of pure water were added, and after stirring and liquid separation, 20 ml of 1% by weight aqueous sodium hydroxide was added, stirred for 1 hour, and then separated. After the organic layer was washed twice with 30 ml of pure water, it was distilled under reduced pressure under conditions of 1.1 kPa and a temperature of 70° C. to 72° C. to obtain a fluorine-containing monomer-1 with a yield of 85%. This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference material: 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)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) -77.5 (3F, s), -79.5 (3F, s)

2-2. Synthesis of fluorine-containing monomer-2 Except for using fluorine-containing cyclic hemiacetal-2 instead of fluorine-containing cyclic hemiacetal-1 used in the synthesis of fluorine-containing monomer-1, The reaction represented by the following formula was carried out in the same procedure as in the synthesis of body-1 to obtain fluorine-containing monomer-2 with a yield of 93%. This reaction is shown below.

The results of nuclear magnetic resonance analysis are shown below.
<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 1.19 (3H, s) (isomer A), 1.23 (3H, s) (isomer B), The isomeric peaks were not separated and assigned as a 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)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) -77.3 (3F, s), -79.0 (3F, s)

2-3. Synthesis of fluorine-containing monomer-3 Except for using 2-fluoroacrylic acid chloride in place of the methacrylic anhydride used in the synthesis of fluorine-containing monomer-2, the synthesis of fluorine-containing monomer-2 was carried out. In the same procedure as in the synthesis, the reaction represented by the following formula was carried out to obtain fluorine-containing monomer-3 with a yield of 70%. This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 1.17 (3H, s) (isomer A), 1.22 (3H, s) (isomer B), The isomeric peaks were not separated and assigned as a 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)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) -10.3 (1F, S), -77.3 (3F, s), -79.0 (3F, s)

2-4. Synthesis of fluorine-containing monomer-4 Fluorine-containing monomer-2 except that 2-methacryloyloxyacetyl chloride was used instead of methacrylic anhydride used in the synthesis of fluorine-containing monomer-2. Fluorine-containing monomer-4 was obtained in a yield of 80% by carrying out the reaction represented by the following formula in the same procedure as in the synthesis of . This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference 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)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) -77.7 (3F, s), -79.6 (3F, s)

2-5. Synthesis of fluorine-containing monomer-5 In a 300 ml glass flask equipped with a stirrer, 22.4 g (0.1 mol) of fluorine-containing cyclic hemiacetal-2, 15.1 g (0.15 mol) of triethylamine, potassium iodide, and 0.1 g (0.1 mol) of triethylamine were added. 8 g (0.05 mol), 20 ml of dimethylformamide, and methoxyphenol (1000 ppm) as a polymerization inhibitor were added, and 16.3 g (0.11 mol) of chloroethyl methacrylate was added dropwise at an internal temperature of 30°C or lower. After stirring for 2 hours, 40 ml of diisopropyl ether and 30 ml of pure water were added, and after stirring and liquid separation, 50 ml of 5% by weight aqueous hydrochloric acid was added and stirred for 30 minutes, followed by liquid separation. After the organic layer was washed twice with 50 ml of pure water, it was distilled under reduced pressure under conditions of 1.0 kPa and a temperature of 89° C. to 91° C. to obtain fluorine-containing monomer-5 with a yield of 45%. This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference 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)
¹⁹ F-NMR (solvent: deuterated chloroform, reference material: C ₆ D ₆ ); δ (ppm) -77.0 (3F, s), -79.3 (3F, s)

2-6. Synthesis of fluorine-containing monomer-6 Except for using fluorine-containing cyclic hemiacetal-6 instead of fluorine-containing cyclic hemiacetal-2 used in the synthesis of fluorine-containing cyclic monomer-2, The reaction represented by the following formula was carried out in the same procedure as in the synthesis of monomer-2 to obtain fluorine-containing monomer-6 with a yield of 78%. This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference 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)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) -77.5 (6F, m), -79.5 (3F, m)

2-7. Synthesis of fluorine-containing monomer-7 Except for using fluorine-containing cyclic hemiacetal-7 instead of fluorine-containing cyclic hemiacetal-2 used in the synthesis of fluorine-containing monomer-2, The reaction represented by the following formula was carried out in the same procedure as in the synthesis of compound-7 to obtain fluorine-containing monomer-7 with a yield of 74%. This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference 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)
¹⁹ F-NMR (solvent: deuterated chloroform, reference material: C ₆ D ₆ ); δ (ppm) -77.9 (3F, m), -78.5 (3F, m)

2-8. Synthesis of fluorine-containing monomer-8 Except for using 2-fluoroacrylic acid chloride instead of methacrylic anhydride used in the synthesis of fluorine-containing monomer-6, the synthesis of fluorine-containing monomer-6 was performed. In the same procedure as in the synthesis, the reaction shown in the following formula was carried out to obtain fluorine-containing monomer-8 with a yield of 68%. This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference 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)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) −10.1 (1F, S), −77.9 (6F, m), −79.0 (3F, m)

2-9. Synthesis of fluorine-containing monomer-9 Except for using 2-fluoroacrylic acid chloride instead of methacrylic anhydride used in the synthesis of fluorine-containing monomer-7, the synthesis of fluorine-containing monomer-7 was carried out. In the same procedure as in the synthesis, the reaction shown in the following formula was carried out to obtain fluorine-containing monomer-9 with a yield of 65%. This reaction is shown below.

<NMR analysis result>
¹ H-NMR (solvent: deuterated chloroform, reference 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 (1 H, q), 6.42 (1 H, q), 6.68 (1 H, dd)
¹⁹ F-NMR (solvent: deuterated chloroform, reference substance: C ₆ D ₆ ); δ (ppm) −10.4 (1F, S), −77.1 (6F, m), −79.3 (3F, m)

3. Synthesis of Comparative Monomer In order to compare with the fluoromonomers-1 to 7 of the present invention, a comparative monomer 1-3 not belonging to the fluoromonomer represented by formula (6) was synthesized. .

3-1. Synthesis of Comparative Monomer-1 Comparative monomer-1 was synthesized using the method described in Patent Document 3.

In a 1000 ml glass flask equipped with a stirrer, 30.0 g of methacrylic acid and 58.6 g of dihydroxypyran were dissolved in 450 ml of ethylene dichloride, 0.1 g of p-toluenesulfonic acid was added, and the mixture was stirred for 1 hour. 3 ml of triethylamine was added to stop the reaction. The resulting reaction mixture was washed with 50 ml of water, dried over anhydrous magnesium sulfate, and distilled under reduced pressure at 0.4 kPa and a temperature of 66° C. to 67° C. to obtain 50 g of Comparative Monomer-1. Obtained. This reaction is shown below. This reaction is shown below.

3-2. Synthesis of Comparative Monomer-2 Comparative monomer-2 was synthesized using the method described in Patent Document 5.

To a mixture of 16.8 g of HFIP and 120 g of tetrahydrofuran, 129 ml of butyl lithium (1.6 M hexane solution) was added at 5°C under a nitrogen atmosphere, and the mixture was stirred at 5°C for 1 hour. Then 14.2 g of 2-oxopropyl methacrylate was added at 5°C. After stirring for 10 hours, dilute hydrochloric acid was added to stop the reaction and neutralize. After ordinary aqueous work-up, purification was carried out by silica gel column chromatography to obtain 25.3 g of triol, which is a synthetic intermediate. A mixture of 24 g of triol compound, 15.6 g of triethylamine and 15 g of toluene was stirred at 70° C. for 4 hours. After cooling to room temperature, the mixture was neutralized with dilute hydrochloric acid, and the organic layer was separated. 20 g of hemiacetal was obtained by distillation under reduced pressure of the crude product obtained by normal post-treatment of washing, drying and concentration.

A mixture of 3.2 g of the hemiacetal obtained above, 2.8 g of methyl iodide, 2.8 g of silver (I) oxide and 150 g of ethyl acetate was stirred at 40° C. for 24 hours. After removing the insoluble matter by filtration and concentrating under reduced pressure, purification was performed by silica gel column chromatography to obtain Comparative Monomer-2, 3 g. This reaction is shown below.

3-3. Synthesis of Comparative Monomer-3 In a 300 ml glass flask equipped with a stirrer, 33.6 g (0.3 mol) of vinyl methacrylate (manufactured by Tokyo Kasei Co., Ltd., the same applies hereinafter) and 52.9 g (0.315 mol) of HFIP were added. After adding, 0.74 g (7.5 mmol) of sulfuric acid was gradually added and stirred at a reaction temperature of 40° C. for 6 hours to carry out the reaction represented by the following formula. This reaction is shown below.

After cooling the reaction solution to room temperature, 50 ml of sodium bicarbonate water having a concentration of 6% by mass was added and stirred. Then, the reaction solution was transferred to a separatory funnel, allowed to stand and separated, and the organic layer was collected. The collected organic layer was distilled under reduced pressure to obtain 39 g of Comparative Monomer-3 with a yield of 47%. The obtained comparative monomer-3 had a boiling point of 62° C. at a pressure of 4.0 kPa.

4. Polymer synthesis Hexafluoroisopropyl methacrylate as fluorine-containing monomers-1 to 9, comparative monomers-1 to 3, and comparative monomer 4 (manufactured by Central Glass Co., Ltd., trade name, HFIP-M) were used to synthesize fluoropolymers-1 to 12 and comparative polymers-1 to 7. Fluoropolymers-1 to 12 belong to fluoropolymer (4). Comparative monomers-1 to 7 are for comparison with the fluoropolymers-1 to 12 of the present invention and do not belong to the fluoropolymer (4).

The fluoropolymers-1 to 9 and the comparative polymers-1 to 4 were synthesized self-polymers so that the effects of the monomers and the difference in performance could be clearly seen, and their performances were compared. Fluoropolymers-10 to 12 and Comparative Polymers-5 to 7 were obtained by fixing a copolymer monomer to 5-methacryloyloxy-2,6-norbornanecarbolactone (MNLA) to obtain the fluorine-containing polymer of the present invention. This was done to compare the performance of the monomer and the comparative monomer as resist materials.

[Analysis of polymer]
<NMR>
The composition of the repeating composition in the polymer was determined by NMR measurements of ¹ H-NMR and ¹⁹ F-NMR.
<Molecular weight>
Polymer number average molecular weight Mn and molecular weight dispersion (ratio of number average molecular weight Mn and mass average molecular weight Mw = Mw/Mn) are measured by high-speed gel permeation chromatography (hereinafter sometimes referred to as GPC. Manufactured by Tosoh Corporation, format HLC-8320 GPC), ALPHA-M column and ALPHA-2500 column manufactured by Tosoh Corporation were connected in series, and measurement was performed using tetrahydrofuran as a developing solvent. A refractive index difference measurement detector was used as the detector.

4-1. Synthesis of fluoropolymer-1 Into a 300 ml glass flask equipped with a stirrer, 29.2 g (0.1 mol) of fluoromonomer-1 and 60 g of 2-butanone as a solvent were added at room temperature to give a concentration of 33 mass. % butanone solution. 0.8 g (0.005 mol) 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 degassed while stirring. After that, the inside of the flask was replaced with nitrogen gas, the temperature was raised to 80° C., and the reaction was carried out for 6 hours. After completion of the reaction, the content was added dropwise to 500 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 60° C. to give 25.6 g of a white solid of fluoropolymer-1 containing repeating units based on fluoromonomer-1, yield 88%. I got it in

<GPC measurement results>
Mw=22,000, Mw/Mn=2.0

4-2. Synthesis of fluoropolymer-2 Except for using fluoromonomer-2 instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above, fluoropolymer- A fluoropolymer-2 containing the following repeating unit was synthesized in the same manner as in the synthesis of 1 to obtain a fluoropolymer-2 with a yield of 87%.

<GPC measurement results>
Mw=23,100, Mw/Mn=2.1

4-3. Synthesis of fluoropolymer-3 Instead of the fluoromonomer-1 used in the synthesis of the fluoropolymer-1 described above, the fluoropolymer-3 was used except that the fluoromonomer-3 was used. A fluoropolymer-3 containing the following repeating unit was synthesized in the same manner as in the synthesis of 1 to obtain a fluoropolymer-3 with a yield of 93%.
<GPC measurement results>
Mw=21,200, Mw/Mn=2.3

4-4. Synthesis of fluoropolymer-4 Fluoropolymer-1 except that fluoromonomer-4 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above. A fluorine-containing polymer-4 containing the following repeating unit was synthesized in the same procedure as in the synthesis of , to obtain a fluorine-containing polymer-4 in a yield of 92%.

<GPC measurement results>
Mw=22,500, Mw/Mn=2.1

4-5. Synthesis of fluoropolymer-5 Fluoropolymer-1 except that fluoromonomer-5 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above. A fluorine-containing polymer-5 containing the following repeating unit was synthesized in the same procedure as in the synthesis of , to obtain a fluorine-containing polymer-5 with a yield of 90%.

<GPC measurement results>
Mw=24,200, Mw/Mn=2.3

4-6. Synthesis of fluorine-containing polymer-6 Except for using the fluorine-containing cyclic monomer-6 instead of the fluorine-containing monomer-1 used in the synthesis of the fluorine-containing polymer-1 described above, the fluorine-containing polymer- A fluoropolymer-6 containing the following repeating unit was synthesized in the same manner as in the synthesis of 1 to obtain a fluoropolymer-6 with a yield of 72%.

<GPC measurement results>
Mw=20,700, Mw/Mn=2.5

4-7. Synthesis of fluoropolymer-7 Fluoropolymer-1 except that fluoromonomer-7 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above. A fluorine-containing polymer-7 containing the following repeating unit was synthesized in the same procedure as in the synthesis of , to obtain a fluorine-containing polymer-7 with a yield of 78%.

<GPC measurement results>
Mw=20,100, Mw/Mn=2.2

4-8. Synthesis of fluoropolymer-8 Fluoropolymer-1 except that fluoromonomer-8 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above. A fluorine-containing polymer-8 containing the following repeating unit was synthesized in the same procedure as in the synthesis of , to obtain a fluorine-containing polymer-8 in a yield of 90%.

<GPC measurement results>
Mw=19,700, Mw/Mn=2.3

4-9. Synthesis of fluoropolymer-9 Fluoropolymer-1 except that fluoromonomer-9 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above. A fluorine-containing polymer-9 containing the following repeating unit was synthesized in the same procedure as in the synthesis of , to obtain a fluorine-containing polymer-9 with a yield of 89%.

<GPC measurement results>
Mw=20,900, Mw/Mn=2.1

4-10. Synthesis of fluoropolymer-10 Into a glass flask at room temperature (approximately 20°C), 29.2 g (0.1 mol) of fluoromonomer-1 is added to provide a repeating unit of adhesion when used as a resist. 11.1 g (0.05 mol) of 5-methacryloyloxy-2,6-norbornanecarboractone (MNLA) and 0.67 g of n-dodecylmercaptan (manufactured by Tokyo Kasei Co., Ltd.) were charged, and 82.8 g of 2-butanone was added. was added and dissolved. As a polymerization initiator, 1.7 g of 2,2'-azobis(isobutyronitrile) (hereinafter sometimes referred to as AIBN, manufactured by Wako Pure Chemical Industries, Ltd.) was added and deaerated while stirring, and then nitrogen gas was introduced into the flask. and the reaction was continued for 16 hours after the temperature was raised to 75°C. After completion of the reaction, the content was added dropwise to 620.0 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 60° C. to obtain a fluoropolymer-8 containing repeating units derived from the fluoromonomer-1 and repeating units derived from the MNLA shown below, 34 g was obtained as a white solid in 85% yield.

<NMR measurement result>
The composition ratio of each repeating unit in the fluoropolymer-10 was measured by NMR. The measurement result, expressed in mol %, was repeating units of fluorine-containing monomer-10:repeating units of MNLA=67:33.
<GPC measurement results>
Mw=8,500, Mw/Mn=1.7

4-11. Synthesis of fluoropolymer-11 Instead of the fluoromonomer-1 used in the synthesis of the fluoropolymer-10 described above, the fluoropolymer-1 was used except that the fluoromonomer-2 was used. A fluorine-containing polymer-11 was synthesized in the same procedure as the synthesis of 10, and a fluorine-containing polymer-11 containing the following repeating units was obtained with a yield of 86%.

<NMR measurement result>
The composition ratio of each repeating unit in the fluoropolymer-11 was measured by NMR. The measurement result, expressed in mol %, was repeating units of fluorine-containing monomer-11:repeating units of MNLA=65:35.
<GPC measurement results>
Mw=8,700, Mw/Mn=1.6

4-12. Synthesis of fluoropolymer-12 Instead of fluoromonomer-1 used in the synthesis of fluoropolymer-10 described above, fluoromonomer-6 was used, except that fluoromonomer A fluorine-containing polymer-12 was synthesized in the same procedure as the synthesis of -10, and a fluorine-containing polymer-12 containing the following repeating units was obtained with a yield of 73%.

<NMR measurement result>
The composition ratio of each repeating unit in the fluoropolymer-12 was measured by NMR. The measurement result, expressed in mol %, was repeating units of fluorine-containing monomer-12:repeating units of MNLA=64:36.
<GPC measurement results>
Mw=7,700, Mw/Mn=1.7

5. Synthesis of Comparative Polymers For comparison with the fluoropolymers-1 to 10 of the present invention, comparative polymers-1 to 7 not belonging to the fluoropolymer (4) were synthesized.

5-1. Synthesis of Comparative Polymer-1 Synthesis of fluoropolymer-1 except that comparative monomer-1 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above. Comparative polymer-1 containing the following repeating units was synthesized in the same manner as above.

<GPC measurement results>
Mw=20,100, Mw/Mn=2.2

5-2. Synthesis of Comparative Polymer-2 Synthesis of fluoropolymer-1 except that comparative monomer-2 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above. Comparative polymer-2 containing the following repeating units was synthesized in the same manner as above.

<GPC measurement results>
Mw=23,400, Mw/Mn=2.1

5-3. Synthesis of Comparative Polymer-3 Synthesis of fluoropolymer-1 except that comparative monomer-3 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above. A comparative polymer-3 containing the following repeating units was synthesized in the same manner as above.

<GPC measurement results>
GPC measurement results were Mw=22,800 and Mw/Mn=2.1.

5-4. Synthesis of Comparative Polymer-4 Synthesis of fluoropolymer-1 except that comparative monomer-4 was used instead of fluoromonomer-1 used in the synthesis of fluoropolymer-1 described above. Comparative polymer-4 containing the following repeating units was synthesized in the same manner as above.

<GPC measurement results>
Mw=20,100, Mw/Mn=2.1

5-5. Synthesis of Comparative Polymer-5 Instead of the fluoromonomer-1 used in the synthesis of the above-mentioned fluoropolymer-8, the fluoromonomer-8 was used except that the comparative monomer-1 was used. A comparative polymer-5 containing the following repeating unit was synthesized in the same procedure as in the synthesis of No. 1, and a comparative polymer-5 was obtained with a yield of 89%.

<NMR measurement result>
The composition ratio of each repeating unit in Comparative Polymer-5 was measured by NMR. The measurement result, expressed in mol %, was repeating units of comparative monomer-1: repeating units of MNLA=67:33.
<GPC measurement results>
Mw=8, 300, Mw/Mn=1.7

5-6. Synthesis of Comparative Polymer-6 Instead of the fluoromonomer-1 used in the synthesis of the above-mentioned fluoropolymer-8, the fluoromonomer-8 was used except that the comparative monomer-2 was used. A comparative polymer-6 containing the following repeating unit was synthesized in the same procedure as in the synthesis of No. 1, and a comparative polymer-6 was obtained in a yield of 83%.

<NMR measurement result>
The composition ratio of each repeating unit in Comparative Polymer-6 was measured by NMR. The measurement result, expressed in mol %, was repeating units of comparative monomer-2: repeating units of MNLA=65:35.
<GPC measurement results>
Mw=8, 900, Mw/Mn=1.6

5-7. Synthesis of Comparative Polymer-7 Fluoromonomer-8 except that Comparative Monomer-4 was used instead of Fluoromonomer-1 used in the synthesis of Fluoropolymer-8 described above. Comparative polymer-7 containing the following repeating unit was synthesized in the same procedure as in the synthesis of Comparative polymer-7 with a yield of 81%.

<NMR measurement result>
The composition ratio of each repeating unit in Comparative Polymer-7 was measured by NMR. The measurement result, expressed in mol %, was repeating units of comparative monomer-3: repeating units of MNLA=66:34.
<GPC measurement results>
Mw=8, 100, Mw/Mn=1.6

5-8. Repeating Units of Fluoropolymers-1 to 10 and Comparative Polymers-1 to 7 The repeating units contained in fluoropolymers-1 to 10 and comparative polymers 1 to 7 are shown below.

5-9. Compositions, molecular weights and yields of fluoropolymers-1 to 10 and comparative polymers-1 to 7 ), weight average molecular weight, molecular weight distribution and yield.

5-10. Glass transition points and 5% weight loss of fluoropolymers-1 to 9 and comparative polymers-1 to 4 Glass transition points and 5% weight loss of fluoropolymers-1 to 9 and comparative polymers-1 to 4 Reduction rate was measured by the following method.

[Measurement method of glass transition point and 5% weight loss rate]
Thermophysical properties of fluorine-containing polymers-1 to 9 and comparative polymers-1 to 4 were measured.
Glass transition point (hereinafter referred to as Tg) using a differential scanning calorimeter (hereinafter sometimes referred to as DSC) and a simultaneous differential thermal thermogravimetric analyzer (hereinafter sometimes referred to as DTA) manufactured by Hitachi High-Tech Science Co., Ltd. ) and a 5% weight loss rate (hereinafter sometimes referred to as Td5) in thermogravimetry were measured.

[Measurement result]
Table 2 shows the measurement results of Tg and Td5 of fluoropolymers-1 to 9 and comparative polymers-1 to 4. In pattern forming materials for lithography and printed electronics, it is known that the higher Tg and Td5, the more faithfully the mask pattern is transferred, and the resulting pattern tends to have better line edge roughness and line width roughness. there is

Fluoropolymers-1 to 9 having a cyclic acetal structure and Comparative polymers-1 to 2 had a Tg higher by nearly 25.degree.
Fluoropolymers 1 to 3, 8 and 9 exhibited a higher Tg than Comparative Polymer 1 having a similar skeleton and no fluorine atom.

6. Pattern-forming composition for printed electronics 6-1. Preparation of Pattern-Forming Composition for Printed Electronics Pattern-forming composition-1 of the present invention was prepared using fluorine-containing polymers-1 to 9 and comparative polymers-1 to 4 containing the repeating units shown below. 9, Comparative Compositions-1-4 for comparison thereof were prepared.

For fluoropolymers-1 to 9 and comparative polymers-1 to 4, (A) N-hydroxynaphthalimide-trifluoromethanesulfonate as an acid generator and (D) 2-isopropyl as a sensitizer Thioxanthone, (C) 2-phenylbenzimidazole as a quencher, and (B) diethylene glycol methyl ethyl ether as an organic solvent were added to prepare Pattern Forming Compositions-1 to 9 and Comparative Compositions-1 to 4.
Each composition ratio of Pattern Forming Compositions-1 to 9 and Comparative Compositions-1 to 4 is expressed in parts by mass, polymer: (A) acid generator: (D) sensitizer: (C) citric Char: (B) organic solvent is 100:
The ratio was 2:1:0.05:300.

6-2. Film formation of pattern-forming composition for printed electronics On a glass substrate, the prepared pattern-forming compositions-1 to 9 and comparative compositions-1 to 4 were applied with a spinner, and a hot plate heated to 100 ° C. It was dried on top for 2 minutes to form a film with a thickness of 0.5 μm. The film was then irradiated with a high pressure mercury lamp. Also, the pattern of the photomask was transferred to the film by irradiating the film with ultraviolet light using a high-pressure mercury lamp through the photomask, and then the film was dried by heating at a temperature of 100° C. for 5 minutes using a hot plate. In this manner, a glass substrate having a pattern (parent/repellent pattern) formed of hydrophilic portions and water-repellent portions was obtained.

6-3. Measurement of contact angle of film composed of pattern-forming composition before and after exposure, and formation of pattern with water-based ink

[Measurement of contact angle]
A water droplet is placed on the film on the glass substrate, and a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) is used to measure the static contact angle of the ultraviolet light unirradiated area and the ultraviolet light irradiated area by the droplet method. A dynamic receding angle was measured in a portion not irradiated with ultraviolet light. In the present invention, the static contact angle refers to the angle formed with the film surface when a water droplet is placed on the film surface and the dynamic receding angle is the contraction of the water droplet when the water droplet is sucked with a needle or the like. The dynamic advancing angle is the contact angle when a water droplet is ejected with a needle or the like and expands.

In pattern-forming materials for lithography and printed electronics, it is preferable that the pattern-forming film has a high static contact angle in the non-irradiated area, so that the mask pattern can be transferred more faithfully, and the line edge roughness and line width roughness of the resulting pattern can be improved. A high-resolution pattern can be obtained. Moreover, when the static contact angle of the irradiated portion is low and the difference between the contact angles of the non-irradiated portion and the irradiated portion is large, it is easier to cut the pattern.

The higher the dynamic receding angle of the non-irradiated portion of the pattern forming film, the more faithfully the mask pattern is transferred, and the resulting pattern has good line edge roughness and line width roughness, and a high resolution pattern can be obtained. In order to obtain a high-resolution pattern, it is preferable that both the dynamic advancing angle and the dynamic receding angle are high and the hysteresis (dynamic advancing angle - dynamic receding angle) is small in the unirradiated area.

[Ink pattern]
Using an automatic minimal contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number MCA-2), 50 pl of water-based ink was dropped on the resulting hydrophilic/repellent pattern on the glass substrate using a borosilicate glass capillary (microcapillary). , the pattern was observed microscopically after 5 seconds. Then, if the water-based ink can be patterned along the hydrophilic/repellent pattern, it is acceptable, and if it overflows the pattern, it is not acceptable.

[Measurement result]
Table 3 shows the measurement results of the static contact angle and dynamic contact angle of the above pattern forming compositions-1 to 9 and Comparative Examples 1 to 4. In Table 3, Examples 1 to 9 correspond to Pattern Forming Compositions-1 to 9, and Comparative Examples 1 to 4 correspond to the measured values of Comparative Compositions-1 to 4.

[Contact angle]
The pattern-forming compositions containing trifluoromethyl groups of Examples 1 to 9 exhibited good water repellency with a large contact angle on the area not irradiated with ultraviolet light.

The non-irradiated portion of the film formed from Comparative Composition-1 using Comparative Polymer-1 containing no fluorine atom of Comparative Example 1 had a contact angle of 73° and a receding contact angle of 58°. The film formed from Comparative Composition-2 using Comparative Polymer-2 containing a fluorine atom of Comparative Example 2 had a contact angle of 94 degrees at the UV-unirradiated portion. The films formed from -1 to -9 were inferior in water repellency.

Comparative Composition-4 of Comparative Example 4 used Comparative Polymer-4 having a hexafluoroisopropyl group having no acid dissociation property, and did not exhibit hydrophilicity due to the large contact angle of the ultraviolet light irradiated portion.
[Ink pattern]
The difference between the contact angle of the unirradiated area and the contact angle of the irradiated area was 40 in the hydrophilic and repellent patterns formed by the respective pattern forming compositions-1 to 9 using the fluoropolymers-1 to 9 of Examples 1 to 9. ° or more and the receding contact angle is high, the water-based ink in the water-repellent portion quickly flows to the hydrophilic portion.

On the other hand, in the parent-repellent pattern of Comparative Composition-2 using Comparative Polymer-2, the difference between the unirradiated portion and the irradiated portion of the parent-repellent pattern was about 30°, and the receding contact angle was 80°. It was low, and residual water-based ink was observed in the water-repellent portion.

In Comparative Example 1, Comparative Polymer-1 does not contain fluorine atoms. The water repellency of the water repellent part was not sufficient and water wettability was present, and the water-based ink remained. A water-based ink film was formed on the film surface without forming a hydrophilic/repellent pattern.

7. Resist 7.1 Preparation of Resist Using fluorine-containing polymers-10 to 12 and comparative polymers-5 to 7 containing the following repeating units shown below, resist-1 to 3 and comparative resist- as resist solutions 1-3 were prepared.

A resist solution was prepared by adding triphenylsulfonium nonafluorobutanesulfonate as a photoacid generator, triethanolamine as a basic compound, and propylene glycol monomethyl ether acetate (PGMEA) as a solvent to each of the above polymers. Each resist solution was prepared by blending the resist so that the composition ratio of the resist, expressed in parts by mass, was 100:5:1:900 (polymer:photoacid generator:basic substance:solvent).

[Formation of resist film]
A silicon wafer was coated with an antireflection film solution (manufactured by Nissan Chemical Industries, Ltd., product number ARC29A) and then dried at 200° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. Then, after each resist solution was filtered through a 0.2 μm membrane filter, it was applied onto the antireflection film using a spinner at a rotation speed of 1,500 rpm, dried on a hot plate at 100° C. for 90 seconds, A resist film was formed.

7.2 Evaluation of Resist Solubility in Developer and Resolution of Resist Pattern For each resist film, the solubility of the resist in developer and the resolution of the resist pattern were evaluated, and the contact angle was measured. The measurement method is shown below.

[Developer solubility]
The silicon wafer on which the resist film was formed was immersed in an alkaline developer at room temperature for 60 seconds to test the solubility in the developer. As an alkaline developer, a tetramethylammonium hydroxide aqueous solution (hereinafter sometimes referred to as TMAH) having a concentration of 2.38% by mass, which is commonly used in lithography, was used. The solubility of the resist film was determined by measuring the film thickness of the resist film after immersion with a light interference film thickness meter. When the resist film disappeared completely, it was evaluated as "soluble", and when the film thickness of the resist film did not change, it was evaluated as "insoluble".

[Sensitivity and resolution of resist pattern]
A photomask having a line-and-space pattern with a wiring width of 30 nm and an interval between adjacent wirings of 30 nm was prepared.

After pre-baking the silicon wafer on which the resist film was formed at 100° C. for 60 seconds, an argon fluoride excimer laser was used to emit ultraviolet light at an oscillation wavelength of 193 nm through the photomask so that the pattern of the photomask was transferred. Irradiated to expose the resist film. Pure water was dropped for 2 minutes while rotating the silicon wafer. Thereafter, post-exposure baking was performed at 120° C. for 60 seconds, followed by development using TMAH as an alkaline developer, immersion in pure water for 30 seconds, and drying with an air knife. Subsequently, post-baking was performed by drying at 100° C. for 45 seconds to obtain a silicon wafer having a resist pattern formed thereon.

<Sensitivity>
In the above operation, the optimum exposure dose Eop (mj/cm ² ) for forming a 30 nm line-and-space pattern once was determined and used as a measure of sensitivity.

<Resolution>
The obtained pattern-transferred silicon wafer was cut, and the resist pattern on the wafer, to which the 30 nm line-and-space pattern of the photomask was transferred, was observed under a microscope. The resolution was rated as "good" when the line edge roughness was noticeable but was rated as "improper".

[Method for measuring contact angle]
The contact angle of a water droplet on the obtained resist film on the silicon wafer was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).

A resist film with a high contact angle allows the mask pattern to be transferred more faithfully, and the obtained pattern has good line edge roughness and line width roughness, and a high resolution pattern can be obtained. Also, in liquid immersion lithography, water does not enter the film, and watermark defects are less likely to occur.

Table 4 shows the evaluation results of the developer solubility of the resist, the sensitivity and resolution of the resist pattern, and the measurement results of the contact angle.

[Evaluation of developer solubility]
As shown in Table 4, resists-1 to 3 and comparative resists-1 to 3 were all insoluble in an alkaline developer in the unexposed state, but became soluble after exposure. From this, it was shown that all the tested resists as photosensitive resins have a dissolution contrast with respect to TMAH as an alkaline developer.

[Evaluation of resist pattern sensitivity and resolution]
<Sensitivity>
As for the sensitivity, the optimum exposure doses of the comparative resists-1 to 3 were all lower than the optimum exposure doses of the resists-1 to 3. The value was lower than that of the cyclic acetal structure of Comparative Example Resist-2. Furthermore, the optimum exposure dose of Comparative Resist-1, which has a cyclic acetal structure having no fluorine atoms, is low, and the optimum exposure dose of Comparative Resist-3, which has a non-cyclic acetal structure, is the lowest.

<Resolution>
As shown in Table 4, when resists-1 to 3 and comparative resist-2 were used, a pattern having a desired 30 nm line-and-space pattern was formed, exhibiting good resolution, and was rated as "good." Judged. On the other hand, in the case of the comparative resist-1, line edge roughness was confirmed, and it was judged as "improper". In the case of Comparative Resist-3, fine line edge roughness was confirmed, and it was judged as "acceptable" because it was inferior to Resists-1 to 3 and Comparative Resist-2.

[Measurement result of contact angle]
The water receding contact angles of Resist 1-3 were all higher than those of Comparative Resist 1-2. Comparative resist 2, which contains a polymer having a fluorine-containing cyclic acetal structure, was inferior to resist 1-3.

Claims (16)

A fluoropolymer comprising a repeating unit represented by formula (1).

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Of the atoms, 7 or less may be substituted with fluorine atoms, and R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or 3 to 10 carbon atoms. Of the hydrogen atoms bonded to carbon atoms in the alkyl group, 7 or less may be substituted with fluorine atoms X is a single bond or a divalent group, including a divalent group 7 or less hydrogen atoms may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms.R is a fluorine-containing alkyl group having 1 to 3 carbon atoms.) 2. The fluoropolymer according to claim 1, wherein ^R2 , ^R4 and R5 in formula ( ¹ ) are hydrogen atoms. 3. The fluoropolymer according to claim 2, wherein Y in formula (1) is a trifluoromethyl group. A composition for forming a resist pattern, comprising the fluoropolymer according to any one of claims 1 to 3, an acid generator, a basic compound and a solvent. A film-forming step of applying the composition for forming a resist pattern according to claim 4 onto a substrate to form a film;
A resist comprising an exposure step in which an electromagnetic wave having a wavelength of 300 nm or less or a high-energy beam is irradiated through a photomask to transfer the pattern of the photomask onto the film, and a development step in which the film is developed using a developer to obtain a pattern. How the pattern is formed. An ink pattern-forming composition comprising the fluoropolymer according to any one of claims 1 to 3, an acid generator and a solvent. A film-forming step of applying the composition for forming an ink pattern according to claim 6 onto a substrate to form a film;
an exposure step of irradiating and exposing the film to light having a wavelength of 150 nm or more and 500 nm or less through a photomask to transfer the pattern of the photomask onto the film to obtain a patterned film having a lyophobic portion and a lyophilic portion;
A method of forming an ink pattern, comprising an ink pattern forming step of applying ink to the obtained pattern forming film. A film-forming step of applying the composition for forming an ink pattern according to claim 6 onto a substrate and heating the resulting coating film;
Next, a drawing step of scanning and exposing the film to light having a wavelength of 150 nm or more and 500 nm or less with a drawing device to draw a pattern on the film to obtain a pattern forming film having a lyophobic portion and a lyophilic portion;
A method for forming an ink pattern, comprising an ink pattern forming step of applying ink to the obtained pattern forming film. A fluorine-containing monomer represented by formula (4).

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Of the atoms, 7 or less may be substituted with fluorine atoms, and R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or 3 to 10 carbon atoms. Of the hydrogen atoms bonded to carbon atoms in the alkyl group, 7 or less may be substituted with fluorine atoms X is a single bond or a divalent group, including a divalent group 7 or less hydrogen atoms may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms.R is a fluorine-containing alkyl group having 1 to 3 carbon atoms.) 10. The fluoromonomer according to claim 9, wherein ^R2 , ^R4 and R5 in the formula ( ⁴ ) are hydrogen atoms. Furthermore, the fluorine-containing monomer according to claim 10, wherein Y in said formula (4) is a trifluoromethyl group. A step 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) ,
10. A method for producing a fluorine-containing monomer represented by formula (4) according to claim 9.

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Of the atoms, 7 or less may be substituted with fluorine atoms, and R ² to R ⁵ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or 3 to 10 carbon atoms. Of the hydrogen atoms bonded to carbon atoms in the alkyl group, 7 or less may be substituted with fluorine atoms X is a single bond or a divalent group, including a divalent group 7 or less hydrogen atoms may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms, R is a fluorine-containing alkyl group having 1 to 3 carbon atoms, and Z is a straight chain having 1 to 20 carbon atoms. , a branched or cyclic alkyl group with 3 to 20 carbon atoms, some or all of the hydrogen atoms in Z may be substituted with halogen atoms, and ether bonds, siloxane bonds, thioether bonds, carbonyl bonds may contain.)
A fluorine-containing cyclic hemiacetal represented by formula (7).

(Wherein, R ² to R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Among them, 7 or less may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (—COOR), and a fluorine-containing alkyl group or carboxylic 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms.R is a fluorine-containing alkyl group having 1 to 3 carbon atoms.) 14. The fluorine-containing cyclic hemiacetal according to claim 13, wherein ^R2 , ^R4 , and R5 in formula ( ⁷ ) are hydrogen atoms. 15. The fluorine-containing cyclic hemiacetal according to claim 14, wherein Y in formula (7) is a trifluoromethyl group. A hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or hydroxyvinyl ester represented by the formula (11) is cyclized, and the formula according to any one of claims 13 to 15 ( 7) obtaining a fluorine-containing cyclic hemiacetal compound represented by
A method for producing a fluorine-containing cyclic hemiacetal compound.

(Wherein, R ² to R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group Among them, 7 or less may be substituted with fluorine atoms, Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (—COOR), and a fluorine-containing alkyl group or carboxylic 7 or less hydrogen atoms contained in the acid ester group may be substituted with fluorine atoms, R is a fluorine-containing alkyl group having 1 to 3 carbon atoms, and Z is a straight chain having 1 to 20 carbon atoms. , a branched or cyclic alkyl group with 3 to 20 carbon atoms, some or all of the hydrogen atoms in Z may be substituted with halogen atoms, and ether bonds, siloxane bonds, thioether bonds, carbonyl bonds may contain.)