TWI675855B - Fluorine-containing monomer, fluoropolymer, pattern forming composition using the same, and pattern forming method thereof - Google Patents

Abstract

The present invention provides a fluoropolymer that does not contain a perfluoroalkyl group with a carbon number of 4 or more and provides a pattern with high sensitivity and high resolution. When the film is formed with a photoacid generator, it is displayed after film formation. Water-repellent, and the acid becomes a hydrophilic pattern-forming material by light irradiation. The fluoropolymer of the present invention is characterized by containing a repeating unit represented by formula (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, an alkyl group having 1 to 10 carbon atoms, and X is a single bond or a divalent group, Y is a fluorine-containing alkyl group or carboxylic acid ester group (-COOR) having 1 to 3 carbon atoms, and R is a fluorine-containing alkyl group having 1 to 3 carbon atoms; 7 or less hydrogen atoms contained in these groups may be subjected to fluorine Atomic substitution).

Description

Fluorinated monomer, fluorinated polymer and pattern forming composition using the same, and pattern forming method thereof

The present invention relates to a fluorine-containing monomer, a fluorine-containing polymer, a composition for pattern formation using the same, and a method for pattern formation thereof. In particular, the present invention relates to a fluoropolymer, a fluoromonomer as a precursor thereof, a pattern-forming composition using the same, and a pattern forming method thereof. The above-mentioned fluoropolymer can be used for lithography in semiconductor manufacturing. Resistive materials used, or printed electronic technology in which electronic circuits are formed by inks in the manufacture of electronic equipment, for example, by using conductive ink printing on a glass or resin substrate to form pattern circuits using conductive film inks ( Printed electronics).

It is known that a fluoropolymer has excellent properties because it has a fluorine atom in its chemical structure. Fluoropolymers with 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.

Regarding the fluorinated polymer having an acid-decomposable group used in a semiconductor manufacturing resist material, a photo-acid generator is added to form a resist film, and an acid is generated from the photo-acid generator by light irradiation. The acid- and acid-decomposable groups are dissociated from the fluoropolymer, thereby changing the properties of the developing solution that are soluble or insoluble, and forming a pattern on the resist film. In printed electronics, a fluoropolymer is used as a material for a pattern-forming film provided with a pattern that repels or does not repel ink.

Photolithography and printed electronics are common in the case where a fluoropolymer having a fluorine-containing acid-decomposable group is used as a pattern forming material, the formed fluoropolymer film shows a relatively small amount of light before light irradiation. The high water repellency causes the water repellency of the irradiated part to become hydrophilic due to the dissociation of the fluorine-containing acid-decomposable groups after light irradiation.

In printed electronics, if a film containing a pattern forming material is irradiated with light through a mask having a pattern formed thereon, a non-irradiated water-repellent portion and a hydrophilic portion after irradiation that are transferred with a mask pattern are formed. The pattern, and thereafter, when the ink is applied, the water repellent portion repels the ink, thereby forming a pattern using the ink.

For example, in Patent Literature 1 and Patent Literature 2, as a pattern forming material for printed electronic technology that provides a close-knit pattern, it is disclosed that carbon atoms having a carbon number of 6 or more are used to form a high-definition pattern to suppress wetting, diffusion, and penetration of ink. Resins of long-chain perfluoroalkyl groups are described by the dissociation of the perfluoroalkyl groups contained in these resins caused by light irradiation, forming patterns for the lyophilic and liquid-repellent portions of the ink.

However, there is a concern that resins having long-chain perfluoroalkyl groups are difficult to burn and decompose and accumulate in the environment. For example, perfluorooctanoic acid has been pointed out by the US Environmental Protection Agency to accumulate in the environment and has been requested to reduce its use. As described above, a fluorine compound having a perfluoroalkyl group having 6 or more carbon atoms is preferably avoided from the viewpoint of accumulation in the environment.

In addition, as a polymer having an acid-decomposable group used as a resist material in semiconductor manufacturing, a polymer having a cyclic acetal skeleton in an acid dissociation portion is known. The polymer having a cyclic acetal skeleton in the acid dissociation portion exhibits excellent acid dissociation properties, and thus has been developed in the field of electronic materials, particularly as a radiation-sensitive patterning composition.

For example, Patent Document 3 discloses a pattern forming method using a radiation-sensitive resin composition containing the fluorine-containing cyclic acetal monomer such as 2-tetrahydrofuran methacrylate as an acid dissociation. Polymer of monomer and photoacid generator. Further, in Patent Document 4, as a pattern forming material having a high sensitivity and a high resolution and a large residual film rate during development, it is disclosed that it contains a monomer having a cyclic acetal group containing no fluorine and has acid decomposability. A positive photosensitive composition comprising a base monomer, a polymer obtained by copolymerizing a monomer having a crosslinkable group, and a radiation-sensitive acid generator.

Patent Document 5 discloses a fluorinated polymer having a cyclic hemiacetal structure and a fluorinated monomer as a precursor. Further, Patent Document 6 discloses that a fluorinated monomer having a cyclic hemiacetal structure is modified with a substituent to modify the cyclic hemiacetal structure, and that the fluorinated polymerization can be adjusted by selecting a substituent. Water repellency, fat solubility and acid decomposability at the time of material. Prior Art Literature Patent Literature

Patent Document 1: Booklet of National Publication WO2014 / 178279 Patent Document 2: Japanese Patent Laid-Open No. 2016-87602 Patent Document 3: Japanese Patent Laid-Open No. 4-26850 Patent Document 4: Japanese Patent Laid-Open No. 2012-42837 Patent Document 5: Japanese Patent Laid-Open No. 2006-152255 Patent Document 6: Japanese Patent Laid-Open No. 2010-106138

[Problems to be solved by the invention]

The object of the present invention is to provide a fluoropolymer that does not contain a perfluoroalkyl group having a carbon number of 4 or more. When a film containing a photoacid generator is made in a photoresist or printed electronics technology, It exhibits water repellency before light irradiation, and becomes hydrophilic due to the action of the acid generated from the photoacid generator after light irradiation, whereby the contact angle to water before light irradiation is higher, and the contact angle after light irradiation is lower And a pattern forming composition for providing a pattern with high sensitivity and high resolution. Another object of the present invention is to provide a pattern forming composition containing the above-mentioned fluoropolymer as a pattern forming material, and a pattern forming method using the pattern forming composition. Furthermore, an object of the present invention is to provide a fluorine-containing monomer and a fluorine-containing compound as precursors of the above-mentioned fluorine-containing polymer, and a method for producing the same. [Technical means to solve the problem]

As shown in the examples of this specification, the present inventors have novelly synthesized a fluorinated polymer (hereinafter, sometimes referred to as a fluorinated polymer (1)) containing the following repeating unit (1), which repeats The unit (1) is an acid-decomposable group having a fluorine-containing cyclic acetal skeleton in which a trifluoromethyl group is bonded to a specific position. Next, the composition for pattern formation containing the fluoropolymer (1) of the present invention is spread on a substrate to form a film. [Chemical 1] (Wherein 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; X is A single bond or a divalent group; Y is a fluorine-containing alkyl or carboxylic acid ester group (-COOR) having 1 to 3 carbon atoms, and R is a fluorine-containing alkyl group having 1 to 3 carbon atoms. The fluoropolymer (1), the fluorinated polymer containing a repeating unit (A) described in Patent Document 6 shown below, and the fluorinated polymer containing a repeating unit (B) described in Patent Document 3, or as a general purpose A photoacid generator and a solvent are added to a fluorinated polymer containing a repeating unit (C), which is known as a resist material, to prepare each pattern-forming composition, which is then developed on a substrate, formed into a film, and cured by heating. Therefore, compared with the film containing the fluoropolymer (A) and the fluoropolymer (B), the film containing the fluoropolymer (1) showed a higher contact angle of about 10 ° with respect to water (refer to the implementation) Examples [Table 3] are Examples 1 to 7 and Comparative Examples 1 to 2). In addition, the sensitivity of the resist was measured, and as a result, the resist film containing the fluoropolymer (1) and the resist film containing the repeating unit (A) or the resist containing the repeating unit (B) Compared with the film, it showed a higher sensitivity. Compared with a resist film containing a copolymer having a repeating unit (A), a copolymer having a repeating unit (B), and a copolymer having a repeating unit (C), It exhibited high sensitivity (References 1 to 3 in [Table 4] of the reference example, and Comparative resists 1 to 3). Since a resist film containing a fluoropolymer (1) has a higher sensitivity than a resist film containing a fluoropolymer having a repeating unit (A), it is presumed that the resist film has a repeating unit (A) Compared with the fluoropolymer, the fluorinated polymer (1) of the present invention has a higher acid decomposability than the fluorinated polymer (A). [Chemical 2] Then, a photomask having a line and gap pattern of 30 nm was prepared, and each film was irradiated with ultraviolet light through the photomask. As a result, it was found that the photomask includes a fluoropolymer containing the fluoropolymer (1) of the present invention for pattern formation. The resist pattern of the composition has a higher sensitivity and a higher resolution than a resist pattern including other pattern-forming composition that does not belong to the scope of the present invention. (Refer to [Table 4] in Examples 1 to 3 and Comparative Resists 1 to 3)

In this way, the present inventors confirmed that a fluoropolymer containing no perfluoroalkyl group having a carbon number of 4 or more was obtained. When the film was made into a film containing a photoacid generator in photolithography and printed electronics, After the film, it shows high water repellency before light irradiation, and becomes hydrophilic due to the action of the acid generated from the photoacid generator after light irradiation. As a result, the contact angle to water before light irradiation is high, and light irradiation The latter has a low contact angle, and is a pattern-forming composition for providing a pattern with high sensitivity and high accuracy.

That is, the present invention includes the following inventions 1 to 16.

[Invention 1] A fluoropolymer containing a repeating unit represented by formula (1); (Wherein R ¹ is a hydrogen atom, a fluorine atom, or a linear or branched alkyl group having 1 to 10 carbon atoms, and 7 of the hydrogen atom bonded to the carbon atom in the alkyl group May be substituted with fluorine atoms; R ² to R ⁵ are hydrogen atoms, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms, and are bonded to carbon atoms in the alkyl group 7 or less of the hydrogen atoms may be replaced by fluorine atoms; X is a single bond or a divalent radical, and 7 or less hydrogen atoms contained in the divalent radical may be replaced by fluorine atoms; Y is 1 to 3 carbon atoms Fluorine-containing alkyl or carboxylic acid ester group (-COOR), fluorine-containing alkyl or carboxylic acid ester group containing 7 or less hydrogen atoms may be substituted by fluorine atoms; R is a fluorine-containing alkane having 1 to 3 carbon atoms base).

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

[Invention 3] The fluorinated polymer according to Invention 2, wherein Y in the formula (1) is a trifluoromethyl group.

[Invention 4] A composition for forming a resist pattern, comprising the fluorinated polymer according to any one of Inventions 1 to 3, an acid generator, a basic compound, and a solvent.

[Invention 5] A method for forming a resist pattern, including: a film-forming step, which forms a film by applying the composition for forming a resist pattern as in Invention 4, on a substrate; and an exposure step, which is performed through a photomask Electromagnetic waves or high-energy rays with an exposure wavelength below 300 nm are irradiated to transfer the pattern of the photomask to the film; and a development step, which uses a developing solution to develop the film to obtain a pattern.

[Invention 6] A composition for forming an ink pattern, comprising the fluorinated polymer according to any one of Inventions 1 to 3, an acid generator, and a solvent.

[Invention 7] A method for forming an ink pattern, comprising: a film-forming step of applying the composition for forming an ink pattern as in Invention 6 on a substrate to form a film; an exposure step of applying a film through a photomask Irradiate light with an exposure wavelength above 150 nm and below 500 nm to transfer the pattern of the photomask to the film to obtain a pattern-forming film having a liquid-repellent portion and a lyophilic portion; and a pattern-forming step based on the obtained pattern The formed film is coated with ink.

[Invention 8] A method for forming an ink pattern, comprising: a film-forming step of applying the composition for forming an ink pattern according to Invention 6 on a substrate and heating (pre-baking) the obtained coating film; The pattern forming step is to scan the film and expose the light with 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 pattern forming film having a liquid-repellent portion and a lyophilic portion. The pattern forming film is coated with ink.

[Invention 9] A fluorine-containing monomer, which is represented by formula (4); (Wherein R ¹ is a hydrogen atom, a fluorine atom, or a linear or branched alkyl group having 1 to 10 carbon atoms, and 7 of the hydrogen atom bonded to the carbon atom in the alkyl group May be substituted with fluorine atoms; R ² to R ⁵ are hydrogen atoms, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms, and are bonded to carbon atoms in the alkyl group 7 or less of the hydrogen atoms may be replaced by fluorine atoms; X is a single bond or a divalent radical, and 7 or less hydrogen atoms contained in the divalent radical may be replaced by fluorine atoms; Y is 1 to 3 carbon atoms Fluorine-containing alkyl or carboxylic acid ester group (-COOR), fluorine-containing alkyl or carboxylic acid ester group containing 7 or less hydrogen atoms may be substituted by fluorine atoms; R is a fluorine-containing alkane having 1 to 3 carbon atoms base).

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

[Invention 11] The fluorine-containing monomer according to Invention 10, wherein Y in the formula (4) is a trifluoromethyl group.

[Invention 12] A method for producing a fluorine-containing monomer represented by Formula (4) according to Invention 9, which comprises using a hydroxycarbonyl compound represented by the following formula (10) or a hydroxy vinyl ether represented by the formula (11) Cyclization to obtain a cyclic hemiacetal compound represented by formula (7); (Wherein R ¹ is a hydrogen atom, a fluorine atom, or a linear or branched alkyl group having 1 to 10 carbon atoms, and 7 of the hydrogen atom bonded to the carbon atom in the alkyl group May be substituted with fluorine atoms; R ² to R ⁵ are hydrogen atoms, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms, and are bonded to carbon atoms in the alkyl group 7 or less of the hydrogen atoms may be replaced by fluorine atoms; X is a single bond or a divalent radical, and 7 or less hydrogen atoms contained in the divalent radical may be replaced by fluorine atoms; Y is 1 to 3 carbon atoms Fluorine-containing alkyl or carboxylic acid ester group (-COOR), fluorine-containing alkyl or carboxylic acid ester group containing 7 or less hydrogen atoms may be substituted by fluorine atoms; R is a fluorine-containing alkane having 1 to 3 carbon atoms Z is a linear chain having 1 to 20 carbon atoms and a branched or cyclic alkyl group having 3 to 20 carbon atoms. Part or all of the hydrogen atoms in Z may be substituted by halogen atoms, and may also contain ether bonds. , Siloxane bond, thioether bond, carbonyl bond).

[Invention 13] A fluorine-containing cyclic hemiacetal represented by the 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 of a hydrogen atom bonded to a carbon atom in the alkyl group. 7 or less can be substituted with fluorine atoms; Y is a fluorine-containing alkyl or carboxylic acid ester group (-COOR) having 1 to 3 carbon atoms, and the fluorine-containing alkyl or carboxylic acid ester group contains 7 or less hydrogen atoms It may be substituted by a fluorine atom; R is a fluorine-containing alkyl group having 1 to 3 carbon atoms).

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

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

[Invention 16] A method for producing a fluorinated cyclic hemiacetal by cyclizing a hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or a hydroxyvinyl ester represented by the formula (11), and Obtaining a fluorine-containing cyclic hemiacetal represented by the formula (7) according to any one of the inventions 13 to 15; (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 of a hydrogen atom bonded to a carbon atom in the alkyl group. 7 or less can be substituted with fluorine atoms; Y is a fluorine-containing alkyl or carboxylic acid ester group (-COOR) having 1 to 3 carbon atoms, and the fluorine-containing alkyl or carboxylic acid ester group contains 7 or less hydrogen atoms It can be substituted by fluorine atom; R is a fluorine-containing alkyl group having 1 to 3 carbon atoms; Z is a linear chain having 1 to 20 carbon atoms and a branched or cyclic alkyl group having 3 to 20 carbon atoms; Part or all of the hydrogen atom may be substituted with a halogen atom, and may also contain an ether bond, a siloxane bond, a thioether bond, and a carbonyl bond). [Effect of the invention]

According to the present invention, a fluorine-containing polymer containing no perfluoroalkyl group having a carbon number of 4 or more is obtained. When a film containing a photoacid generator is made in a photoresist or printed electronics technology, The film shows water repellency before irradiation, and the fluorine-containing acid-decomposable group dissociates due to the action of the acid generated from the photoacid generator after light irradiation, thereby making the film hydrophilic, thereby taking the contact angle to water before light irradiation. A pattern forming composition for providing a pattern with a high sensitivity and a high resolution with a low contact angle after light irradiation. In addition, a pattern forming composition containing the above-mentioned fluoropolymer as a pattern forming material and a pattern forming method using the pattern forming composition were obtained. Further, a fluorine-containing monomer and a fluorine-containing compound as precursors of the above-mentioned fluorine-containing polymer, and a method for producing the same were obtained.

Since the polymer having a fluorinated 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 fear of accumulation in the environment.

Hereinafter, the best mode for carrying out the present invention will be described. However, the present invention is not limited to the following embodiments. It should be understood that the following embodiments are appropriately implemented based on the general knowledge of the industry without departing from the spirit of the present invention. Changes, improvements, and the like also fall within the scope of the present invention.

1. Fluoropolymer [Fluoropolymer (1)] The fluoropolymer of the present invention is a polymer containing a repeating unit represented by formula (1) and having a fluorinated cyclic acetal structure. Hereinafter, it may be referred to as a fluoropolymer (1). [Chemical 8] (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 or carboxylic acid ester group (-COOR) having 1 to 3 carbon atoms (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 described.

[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, and a hydrogen bonded to a carbon atom in the alkyl group. Among the atoms, 7 or less hydrogen atoms may be substituted by fluorine atoms.

Examples of R ¹ include a hydrogen atom, methyl, ethyl, propyl, isopropyl, fluorine atom, trifluoromethyl, trifluoroethyl, trifluoropropyl, 1,1,1,3,3,3 -Hexafluoroisopropyl (-C (CF ₃ ) ₂ H), heptafluoroisopropyl. In terms of 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 a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a hydrogen bonded to a carbon atom in the alkyl group Seven or less of the atoms may be substituted with fluorine atoms.

Regarding R ² to R ⁵ , in terms of ease of synthesis, an electron-donating alkyl group is preferred to an electron-withdrawing substituent, and an unhindered hydrogen atom or methyl group is preferred.

[X] X is a single bond or a divalent radical, and a divalent radical containing 7 or less hydrogen atoms may be substituted with a fluorine atom.

X is preferably a divalent group having 2 to 10 carbon atoms, and examples include methylene, an alkylene group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a divalent group having 6 to 10 carbon atoms. Aryl group or divalent alicyclic hydrocarbon group having 4 to 10 carbon atoms. The alkylene or alkenyl group may contain an ether bond (-O-), a carbonyl group (-(C = O-), a carboxyl group (-(C = O) O-, or -O (C = O)-. If the price is 2 Since the base is a long chain, the liquid repellency is lowered, and therefore, it is preferably a single bond, oxyethyl (-O-CH ₂ -CH _2- ), or oxyethylfluorenyl (-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). The fluorine-containing alkyl group or the carboxylic acid ester group may have 7 or less hydrogen atoms substituted by fluorine atoms.

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

Moreover, in the fluorine-containing monomer (1) of the present invention, depending on the types and combinations of the substituents shown above, there may be asymmetric hydrocarbons in the molecule, and enantiomers and non-mirrors may exist. Isomers (isomers with more than 2 asymmetric carbon atoms, stereoisomers without mirror image relationship). However, formula (1) represents and represents all of these stereoisomers. The stereoisomers can be used alone or as a mixture.

[Fluoropolymer (2)] The fluoropolymer (1) of the present invention is preferably one containing the repeating unit (2) in which R ² , R ⁴ , and R ⁵ in the above formula (1) are hydrogen atoms or less. Fluoropolymer. Considering the solubility of the fluoropolymer (1) as a composition for pattern formation on a substrate, it is preferable that R ² , R ⁴ , and R ⁵ in the formula (1) are hydrogen atoms. The polymer preferably used in the present invention is preferably a polymer containing a repeating unit represented by formula (2) and having a fluorine-containing cyclic acetal structure. Hereinafter, it may be referred to as a fluoropolymer (2). [Chemical 9] (R ¹ , R ³ , X, Y in the formula have the same meaning as formula (1))

[Fluoropolymer (3)] The fluoropolymer (1) of the present invention is more preferably a fluoropolymer containing a repeating unit (3) in which Y in the formula (1) is a trifluoromethyl group or less (3). Furthermore, in consideration of the solubility in a solvent, it is preferable that Y in the above formula (1) is a trifluoromethyl group, and it is more preferable that it contains a repeating unit represented by the formula (3) and has a fluorine-containing cyclic acetal structure polymer. Hereinafter, it may be referred to as a fluoropolymer (3). [Chemical 10] (R ¹ , R ³ , and X in the formula contain the same as in formula (1))

1-1. Decomposition of fluoropolymer (1) by acid It is known that a cyclic acetal structure is decomposed by an acid generated from an acid generator in the same manner as a normal acetal. It is estimated that the fluorinated cyclic acetal structure of the fluorinated polymer (1) of the present invention is similarly reacted as shown below.

It is presumed that the reaction by acid has two reaction paths shown in the following formula, that is, the acid-decomposable group (1B) is dissociated from the fluoropolymer (1) and the repeating unit represented by the formula (1A) remains, or The ring opening of the fluorine-containing cyclic acetal structure generates a repeating unit represented by formula (1C), and it is speculated that a hydrophilic repeating unit represented by formula (1A) is generated from a water-repellent fluoropolymer (1) or The fluorinated polymer of the repeating unit represented by the formula (1C), thereby reducing the contact angle of the ink to the film, exhibits the function of forming a pattern by the ink. [Chemical 11]

1-2. Monomers Providing Other Repeating Units The fluoropolymer (1) of the present invention may contain other repeating units other than the repeating unit (1). The repeating unit other than the repeating unit (1) is adjusted to adjust the solvent solubility of the fluoropolymer (1) when the pattern-forming composition containing the fluoropolymer (1) is used as a film, or is prepared as When the film is used, the hardness of the film is added to the structure of the fluoropolymer (1) for the purpose.

The fluoropolymer (1) containing a repeating unit (1) and other repeating units is obtained by copolymerizing a fluoromonomer (1) providing a repeating unit (1) and a monomer providing another repeating unit.

The monomers that provide other repeating units may be copolymerized with the fluorine-containing monomer (1) that provides repeating units (1) as long as they have polymerizable unsaturated bonds. As monomers that provide other repeating units, examples include: providing adhesion Monomers, acrylates, fluorine-containing acrylates, methacrylates, fluorine-containing methacrylates, and hexafluoroisopropanol groups (-C (CF ₃ ) ₂ OH, sometimes referred to as hereinafter (HFIP-based) monomers, styrenes, fluorinated styrenes, vinyl ethers, allyl ethers, fluorinated vinyl ethers, fluorinated allyl ethers, olefins, fluorinated olefins, norbornene Type, fluorine-containing norbornenes, or other monomers having a polymerizable unsaturated bond.

[Monomer with Adhesive Group] When a fluorinated polymer (1) is used as a resist component, it is possible to obtain better adhesion to the substrate in lithography by introducing an adhesive group into the chemical structure. Examples of the adhesive group include a group containing a lactone structure.

When an adhesive group is introduced into the fluoropolymer (1) of the present invention, a monomer containing a group having a monocyclic or polycyclic lactone structure that can be copolymerized with the fluorinated monomer (1) can be used. body.

Examples of the monocyclic lactone structure include a polyhydric lactone structure by removing one hydrogen atom from γ-butyrolactone or mevalonic lactone to form a bond. As an example, one hydrogen atom is removed from the norbornyl lactone to form a bonding bond. The lactone structure is introduced into the fluoropolymer (1) of the present invention by copolymerizing an acrylate or methacrylate containing a lactone structure. Accordingly, when the fluoropolymer (1) is used as a resist component in lithography, not only the adhesion to the substrate is improved, but also the affinity with the developing solution is expected to be improved.

The following repeating units can be exemplified as repeating units that provide adhesion to the substrate when forming a resist film. [Chemical 12]

In terms of easiness of acquisition, 5-methacryloxy-2,6-norkanalactone (hereinafter sometimes referred to as MNLA) is particularly preferred. The figure above is represented by MNLA.

[Acrylic esters] Examples of 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-hydroxyethyl acrylate or 2-hydroxypropyl acrylate, or acrylates with ethylene glycol, propylene glycol, or 1,4-butanediol, or as Acrylamide of saturated ammonium, N-methylol acrylamide or diacetone acrylamide, or third butyl acrylate, 3-oxocyclohexyl acrylate, adamantyl acrylate, methyl adamantyl acrylate , Ethyladamantyl acrylate, hydroxyadamantyl acrylate, cyclohexyl acrylate or tricyclodecyl acrylate, or an acrylate having a ring structure such as a lactone ring or a norbornene ring, or one having a cyano group at the α position And so on.

[Fluorine-Containing Acrylates] Examples of the fluorine-containing acrylates include fluorine-containing acrylates having a fluorine-containing organic group at the α position of the acrylic portion or the ester portion. It may have a fluorine-containing organic group at both the α-position and the ester portion, or may have a cyano group at the α-position and a fluorine-containing alkyl group at the ester portion.

Examples of the fluorine-containing organic group which the fluorine-containing acrylates have at the α-position include trifluoromethyl, trifluoroethyl, and nonafluoron-butyl.

Examples of the fluorine-containing organic group as the ester portion of the fluorine-containing acrylates include perfluoro or a fluorine-containing alkyl group containing a hydrogen atom, or a hydrogen atom containing a cyclic structure substituted by a fluorine atom, a trifluoromethyl group, or a HFIP group. The resulting fluorine-containing benzene ring, fluorine-containing cyclopentane ring, fluorine-containing cyclohexane ring or fluorine-containing heptane ring.

Examples of the fluorine-containing acrylates include 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 1,1,1,3,3,3-hexaacrylate Fluoroisopropyl ester, Heptafluoroisopropyl acrylate, 1,1-Dihydroheptafluoron-butyl acrylate, 1,1,5-Trihydrooctafluoron-pentyl acrylate, 1,1,2,2-Tetraacrylate N-octadecahydrofluoron-octyl ester, 1,1,2,2-tetrahydroheptafluoro-n-decyl acrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) ) Propyl] bicyclo [2.2.1] heptan-2-yl ester, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] bicyclo [2.2.1 ] Heptan-2-yl-2- (trifluoromethyl) ester, 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.

[Methacrylates] Examples of methacrylates 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-hydroxyethyl methacrylate, 2-methacrylate Hydroxypropyl ester, or a methacrylic acid ester having ethylene glycol, propylene glycol, or 1,4-butanediol group, or methacrylamide, N-hydroxymethacrylamine, N- Hydroxymethyl methacrylamide or diacetone acrylamide, or tert-butyl methacrylate, 3-oxocyclohexyl methacrylate, adamantyl methacrylate, methadamantyl methacrylate , Ethyladamantyl methacrylate, hydroxyadamantyl methacrylate, cyclohexyl methacrylate or tricyclodecyl methacrylate, or methacrylates having a ring structure such as a lactone ring or a norbornene ring .

[Fluorine-containing methacrylates] Examples of the fluorine-containing methacrylates include fluorine-containing methacrylates having a fluorine-containing organic group in the ester portion.

Examples of such a fluorine-containing organic group include a fluorine-containing benzene ring substituted with a fluorine atom, a trifluoromethyl group, a HFIP group, or the like, such as a perfluoro or a fluorine-containing alkyl group containing a hydrogen atom, or a hydrogen atom of a cyclic structure. , Fluorine-containing cyclopentane ring, fluorine-containing cyclohexane ring or fluorine-containing heptane ring.

Examples of the fluorine-containing acrylates include 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and 1,1,1,3 methacrylate , 3,3-hexafluoroisopropyl ester, heptafluoroisopropyl methacrylate, 1,1-dihydroheptafluoron-butyl methacrylate, 1,1,5-trihydrooctafluoron-pentyl methacrylate Ester, 1,1,2,2-tetrahydrotridecane-n-octyl methacrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decyl methacrylate, perfluorocyclohexyl methyl acrylate, Perfluorocyclohexyl methyl methacrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] bicyclo [2.2.1] heptyl-2 -Yl ester or 1,4-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl methacrylate.

[Monomer having HFIP group] Examples of the monomer having a HFIP group include the monomers shown below. [Chemical 13] (R ⁹ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group; and as a HFIP group, a part or all of it may be protected by a protecting group)

[Styrene, fluorinated styrene] Examples of the styrene include styrene and hydroxystyrene.

Examples of the fluorine-containing styrenes include pentafluorostyrene, trifluoromethylstyrene, bis (trifluoromethyl) styrene, and a fluorine atom or a trifluoromethyl group substituted by a hydrogen atom of an aromatic ring structure. Styrene, styrene obtained by replacing a hydrogen atom of an aromatic ring structure with a HFIP group protecting a HFIP group or a hydroxy group of a hydroxyl group thereof, styrenes having a halogen atom, an alkyl group, or a fluorine-containing alkyl group bonded to an α position , Or styrene containing perfluorovinyl.

[Vinyl ethers, allyl ethers, fluorinated vinyl ethers, fluorinated allyl ethers] The vinyl ethers or allyl ethers may be methyl, ethyl, n-propyl, isopropyl, n-propyl Alkyl vinyl ether or alkyl allyl ether of butyl, isobutyl, second butyl, third butyl, hydroxyethyl or hydroxybutyl. In the case of a vinyl ether containing a hydroxyethyl group or a hydroxybutyl group, an alcohol moiety may form an ester bond through an ethyl fluorenyl group, a butyl fluorenyl group, and a propyl fluorenyl group. It may also be a cyclopentyl, cyclohexyl, noryl, aromatic ring, a cyclic vinyl ether or a cyclic allyl ether having a hydrogen atom or a carbonyl bond in its cyclic structure. Examples of the fluorinated vinyl ether and fluorinated allyl ether include a fluorinated vinyl ether or a fluorinated allyl ether in which a part or all of hydrogen atoms in the vinyl ether or allyl ether are replaced by fluorine atoms.

[Olefins, fluorinated olefins] Examples of the olefins include ethylene, propylene, isobutylene, cyclopentene, and cyclohexene. Examples of fluorine-containing olefins include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene or hexafluoroisobutylene, 1-chloro-2,3,3,4, 4,5,5-Heptafluorocyclopentene, octafluorocyclopentene or decafluorocyclohexene.

[Norene, fluorinated norene] The norene and fluorinated norene need only have a polymerizable group, and they may have a plurality of norene skeletons instead of only one norene skeleton. The norbornenes or fluorinated norbornenes are produced by the Diels-Alder addition reaction of 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, and α-trifluoromethyl Acrylic acid, methacrylic acid, the above acrylates, methacrylates, fluorine-containing acrylates or fluorine-containing methacrylates, 2- (benzyloxy) pentafluoropropane, 2- (methoxyethoxymethyl) Methoxy) pentafluoropropene, 2- (tetrahydroxypyranyloxy) pentafluoropropene, 2- (benzyloxy) trifluoroethylene or 2- (methoxymethyloxy) trifluoroethylene. Examples of the diene compound include cyclopentadiene and cyclohexadiene.

Examples of the fluorine-containing norbornene compound include 3- (5-bicyclo [2.2.1] hepten-2-yl) -1,1,1-trifluoro-2- (trifluoromethyl) -2-propene alcohol.

[Other monomers having a polymerizable unsaturated bond] Examples of other monomers having a polymerizable unsaturated bond include acrylic acid, methacrylic acid, acrylonitrile, maleic acid, fumaric acid, and maleic acid. Oxalic anhydride.

As a monomer, when the length of the organic group at the self-polymerized site becomes a long chain or when it contains a large number of heteroatoms, there is a concern that the influence of organic groups derived from other repeating units becomes stronger, The effect of the fluoroalkyl group in reducing liquid repellency is reduced, and the solubility of the polymer is reduced. Therefore, as other monomers, acrylates and methacrylates having a carbon number of less than 10 are preferred, and methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and isomethacrylate are particularly preferred. Propyl, 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) to the total amount of the fluoropolymer (1) is 10 mol% or more and 100 mol % Or less, more preferably 10 mol% or more and 90 mol% or less. If the content of the repeating unit (1) in the fluoropolymer (1) is less than 10 mol%, the unexposed portion of the pattern-forming film obtained by exposing the film containing the fluoropolymer (1) cannot obtain water repellency. .

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

Repeating units derived from other monomers are used to improve the solubility of the fluoropolymer (1) in an organic solvent, the adhesion to the substrate or the hardness when the film is made into a film, and the like. If it is not necessary, it may not be used, but if it is less than 10 mol%, the adhesion or hardness with the substrate will not be improved when it is made into a film. If it exceeds 90 mol%, the content of the repeating unit (1) will be reduced and it will be difficult to obtain The unexposed portion of the pattern-forming film obtained by exposing the film containing the fluoropolymer (1) has the effect of water repellency, and the exposed portion has the effect of hydrophilicity.

1-4. Molecular weight of the 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 dispersion is 1 or more and 4 or less, and preferably 1 or more and 2.5 or less. When the number average molecular weight is less than 1,000, the film containing the pattern-forming composition containing the fluoropolymer (1) as a component becomes soft, and it is difficult to form a film having a desired thickness. In addition, in the pattern-forming film after exposure, it is difficult to form a fine pattern including a liquid-repellent portion and a lyophilic portion, and the durability of the pattern may be poor. If the number average molecular weight is more than 100,000, it is difficult to dissolve the fluoropolymer (1) in a solvent, cracks may occur after film formation, and it is difficult to form a pattern-forming composition containing the fluoropolymer (1) as a coating film. Of the film.

2. Synthesis of fluorinated polymer [Synthesis of fluorinated polymer (1)] The synthesis of the fluorinated polymer (1) of the present invention can be selected from polymerization methods generally used. Radical polymerization and ionic polymerization are preferred. Depending on the situation, coordination anion polymerization, living anion polymerization, and cationic polymerization can be selected. The reactor used in the polymerization reaction is not particularly limited. In the polymerization, a polymerization solvent can be used. Hereinafter, radical polymerization will be described.

The radical polymerization can be carried out in the presence of a radical polymerization initiator or a radical starting source by a known polymerization method such as block polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, in a batch, semi-continuous, or Either continuous operation is performed.

<Radical Polymerization Initiator> Examples of the radical polymerization initiator include an azo compound, a peroxide compound, and a redox compound.

Examples of the azo-based compound include azobisisobutyronitrile. Examples of the peroxide-based compound include tert-butyl pervalerate, di-tert-butyl peroxide, isobutylperoxide, lauryl peroxide, succinate peroxide, and dicinnayl peroxide. Compounds, di-n-propyl peroxydicarbonate, tert-butyl perallyl monocarbonate, benzamidine peroxide, hydrogen peroxide or ammonium persulfate.

<Polymerization Solvent> The polymerization solvent is preferably one that does not inhibit radical polymerization, and examples thereof include an ester-based solvent, a ketone-based solvent, a hydrocarbon-based solvent, and an alcohol-based solvent. Other solvents such as water, ether-based, cyclic ether-based, chlorofluorocarbon (CFC) -based or aromatic solvents can be used.

Examples of the polymerization solvent 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, and alcohol as a solvent. Methanol, isopropanol, or ethylene glycol monomethyl ether.

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

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

In addition, as a method for removing the above-mentioned polymerization solvent such as an organic solvent or water from the solution or dispersion liquid containing the fluoropolymer (1) after polymerization, a known method can be used, and examples thereof include reprecipitation, filtration, and filtration under reduced pressure. Heated distillation.

When the fluoropolymer (1) of the present invention is used as a resist component, depending on the molecular weight of the fluoropolymer (1), the solubility of the developing solution of the fluoropolymer (1) is different. Patterning conditions are variable. If the molecular weight of the fluoropolymer (1) is high, the dissolution rate to the developing solution is slow, and if 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. Composition for forming resist pattern The composition for forming resist pattern 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), Can be used for lithography. Hereinafter, the composition for forming a resist pattern may be simply referred to as a resist.

The fluoropolymers (1) to (3) of the present invention are particularly preferably used as a component of a photosensitive positive resist. The resist of the present invention provides a resist containing a fluoropolymer (1) to (3), especially a photosensitive positive resist material.

The resist of the present invention preferably contains (A) any one of the fluoropolymers (1) to (3) of the present invention, (B) a photoacid generator, (C) a basic compound, and (D) A solvent is used as a resist component. Moreover, you may add (E) surfactant as needed.

3-1. (B) Photoacid generator The photoacid generator used in the resist of the present invention is not particularly limited, and any one of the acid generators used as the chemically amplified resist can be used. Examples include onium sulfonate and sulfonate. For example, sulfonate sulfonate, sulfonium sulfonate, N-fluorenimine sulfonate, N-oxime sulfonate, o-nitrobenzyl sulfonate, or trimethylsulfonate of catechol.

Acid alkane sulfonic acid, aryl sulfonic acid, or partially or completely fluorinated aryl sulfonic acid or alkane sulfonic acid produced by the photoacid generator by exposure in lithography. Among these photoacid generators, a photoacid generator that generates partially or completely fluorinated alkanesulfonic acid is preferred. For example, triphenylsulfonium triflate or triphenylsulfonium perfluoron-butanesulfonate can be exemplified.

3-2. (C) Basic compound A basic compound may be formulated in a resist containing any of the fluoropolymers (1) to (3) of the present invention. The basic compound has a function of reducing the diffusion rate of the acid generated from the photoacid generator when the acid diffuses in the resist film. The formulation of basic compounds is expected to have the following effects: adjust the acid diffusion distance, improve the shape of the resist pattern, and improve the stability of the resist pattern with the required accuracy even after the resist film has a long storage time until exposure. .

Examples of such basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Among these amines, secondary or tertiary aliphatic amines or alkanolamines are preferred. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, and tris (dodecyl) amine. , Dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, di (dodecyl) amine, diamine Cyclohexylamine, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, diethanolamine, triethanolamine, diisopropanolamine , Triisopropanolamine, dioctanolamine, trioctanolamine, aniline, pyridine, methylpyridine, dimethylpyridine, bipyridine, pyrrole, piperidine, piperidine, indole, or hexamethylenetetramine. These basic compounds may be used alone or in combination of two or more.

The compounding quantity of the basic compound in the resist of this invention is 0.001-2 mass parts with respect to 100 mass parts of fluoropolymers (1), Preferably it is 0.01 with respect to 100 mass parts of fluoropolymers (1). ~ 1 part by mass. If the blending 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, resolution or sensitivity may be reduced.

3-3. (D) Solvent in the resist of the present invention except (A) any one of the fluoropolymers (1) to (3) of the present invention, (B) photoacid generator and (C) In addition to basic compounds, (D) solvents are also formulated. The solvent may be prepared by dissolving a resist component containing (A) any of the fluoropolymers (1) to (3) of the present invention, (B) a photoacid generator, and (C) a basic compound. A homogeneous solution is sufficient, and it can be selected and used from the previous resist solvents. It is also possible to use a mixture of two or more solvents.

Examples of such solvents include ketones, alcohols, polyhydric alcohols, esters, aromatic solvents, ethers, fluorine solvents, and turpentine solvents that are high boiling point solvents for the purpose of improving coating properties. Naphtha solvent or paraffin-based solvent.

For example, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isobutyl ketone, methyl isopentanone or 2-heptanone as ketones, isopropyl alcohol as alcohols, Butanol, isobutanol, n-pentanol, isoamyl alcohol, tertiary pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2- Amyl alcohol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, second pentanol, third pentanol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, Hexyldecanol or oleyl alcohol, ethylene glycol as a 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), and derivatives of these polyols Compounds, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, or ethoxy Ethyl propionate, as an aromatic solvent Toluene or xylene, diethyl ether as ethers, dioxane, anisole or diisopropyl ether, or hexafluoroisopropanol as a fluorine-based solvent.

As the resist of the present invention, among these solvents, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are particularly preferred.

The amount of the solvent to be formulated in the resist of the present invention is not particularly limited, and the solid component concentration at the time of making 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 or less. The thickness of the resin film to be formed can be adjusted by adjusting the solid component concentration of the resist.

In addition, the fluoropolymers (1) to (3) of the present invention are excellent in solubility in a wide range of solvents, and among the above-mentioned alcohol-based solvents, emphasis should be placed on alcohol-based solvents having 5 to 20 carbon atoms. Examples of such alcohols include n-pentanol, isoamyl alcohol, tertiary pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, and 2,3-dimethyl-2. -Pentyl alcohol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, second pentanol, third pentanol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol , Hexyldecanol or oleyl alcohol.

3-4. (E) Surfactant In the resist of the present invention, a surfactant may also be added as needed. Examples of the surfactant include a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom, and may contain two or more.

3-5. Resist The resist of the present invention can be made into a solution by using an alcohol-based solvent having 5 to 20 carbon atoms that cannot dissolve ordinary resist materials. Thereby, it can be used as an upper resist for a double patterning process. In addition, the resist of the present invention has high water resistance, moderate water repellency, and affinity for a developing solution.

The resist of the present invention has a moderate water repellency to water before exposure, and shows rapid solubility in a developing solution after exposure. Therefore, it is speculated that it is not only used in dry exposure, but also between the resist and the lens. A pattern with excellent resolution without roughness can also be formed in a liquid immersion exposure that is filled with a medium having a refractive index greater than air, such as water. In photolithography using liquid immersion exposure, there are cases where a topcoat film is used as a protective film of a resist and a topcoat film is not used. It is speculated that the resist of the present invention is adjusted by composition and formulation. , Can also be applied to liquid immersion exposure.

As the medium for the liquid immersion exposure, in addition to water, a fluorine-based solvent, a silicon-based solvent, a hydrocarbon-based solvent, a sulfur-containing solvent, and the like may be cited. The fluoropolymer (1) -containing resist of the present invention may also be used In these media.

4. Method for forming a resist pattern The method for forming a resist pattern of the present invention includes: a film-forming step, which is to form a film by coating the resist of the present invention on a substrate; an exposure step, which is irradiated through a photomask The pattern of the photomask is transferred to a film by exposing electromagnetic waves or high-energy rays with a wavelength below 300 nm; and a developing step, which uses a developing solution to develop the film to obtain a pattern. In addition, in the present invention, the high energy ray refers to an electron beam or a soft X-ray.

The method for forming a resist pattern of the present invention is a pattern forming method using lithography using a resist containing any of the fluoropolymers (1) to (3), and includes: (A) a film forming step , Which forms a resist film by applying a resist on the substrate; (B) an exposure step, which is to irradiate the resist film with an electromagnetic wave having an exposure wavelength of 300 nm or less through a patterned photomask after heating the resist film; High energy line; (C) Development step, which develops the exposed resist film using an alkaline developer to obtain a resist pattern with a mask pattern transferred on the substrate.

For example, in the film forming step (A), the resist containing any of the fluoropolymers (1) to (3) of the present invention is coated on a silicon wafer as a substrate by spin coating. , Pre-baking the silicon wafer on a hot plate at 60 to 200 ° C. for 10 seconds to 10 minutes, preferably at 80 ° C. to 150 ° C. for 30 seconds to 2 minutes, so that A resist film is formed on the substrate. Next, in the (B) exposure step, a patterned mask is set on the exposure device so that the exposure amount is 1 mJ / cm ² or more and 200 mJ / cm ² or less, preferably 10 mJ / cm ² or more and After irradiating the resist film with high energy rays such as ultraviolet rays, excimer lasers, and X-rays or electron beams through a photomask under a method of 100 mJ / cm ² or lower, if necessary, the temperature on the heating plate is at a temperature of 60 ° C or higher and 150 ° C or lower. Post-exposure baking (PEB) is performed at a temperature of 80 ° C. or higher and 130 ° C. or lower for 30 seconds or more and 3 minutes or less. Next, in the (C) developing step, a developing solution of a tetramethylammonium hydroxide (TMAH) aqueous solution based on a concentration of 0.1% by mass or more and 5% by mass or less, preferably 2% by mass or more and 3% by mass or less is used. And obtain the development by contacting the resist film for 10 seconds or more and 3 minutes or less, preferably 30 seconds or more and 2 minutes or less by the existing methods such as the immersion method, the liquid coating method, and the spray method. Target's resist pattern.

In addition to the silicon wafer, the substrate may be a metal or glass substrate. In addition, an organic or inorganic film may be provided on the substrate. For example, an anti-reflection film, an underlayer of a plurality of resists may be present, and a resist pattern may be formed.

Furthermore, in the photolithography of the resist of the present invention, the wavelength of the electromagnetic wave used for the exposure is not limited, and it can be selected: use KrF excimer laser UV (ultraviolet) light (wavelength 248 nm), use The UV light (wavelength 193 nm), extreme ultraviolet lithography (EUV), and X-rays of the ArF excimer laser, in particular, the UV light using the ArF excimer laser can be preferably used.

The resist of the present invention has moderate water repellency to water before exposure, and exhibits rapid solubility in a developing solution after exposure, and can form a pattern with excellent resolution without roughness.

A semiconductor device can be manufactured by a pattern forming method using lithography using the resist of the present invention. The device is not particularly limited, and examples thereof include a CPU (Central Processing Unit) formed on a silicon wafer, a compound semiconductor substrate, an insulating substrate, and the like, and a Static Random Access Memory (SRAM). A semiconductor device manufactured by microfabrication such as DRAM (Dynamic Random Access Memory) and DRAM (Dynamic Random Access Memory).

5. Composition for forming ink pattern The composition for forming ink pattern of the present invention is formed by adding an acid generator and a solvent to any of the fluoropolymers (1) to (3), and can be used in printed electronic equipment. The ink pattern is formed. Hereinafter, a pattern formed with ink is sometimes referred to as an ink pattern.

The composition for forming an ink pattern of the present invention contains any of the fluoropolymers (1) to (3), (A) an acid generator, and (B) a solvent as its components. It preferably contains other (C) quencher (D) sensitizer, (E) polymerizable compound, and may optionally contain a surfactant, a storage stabilizer, an adhesive, or a heat resistance improver .

(A) An acid generator is a compound which produces | generates an acid by light irradiation at the time of exposure in the film formed from the composition for ink pattern formation. (B) The solvent is a substance for dissolving or dispersing the components of the composition for forming an ink pattern. (C) The quencher is a substance for preventing the diffusion of the acid from the acid generator during exposure to make the obtained pattern high-definition. (D) Sensitizer is a substance used to increase the sensitivity of exposure. (E) The polymerizable compound is a substance for making the pattern-forming film obtained after exposure harder. Hereinafter, each component is disclosed.

5-1. (A) Acid generator As the (A) acid generator used as a component of the ink pattern forming composition of the present invention, a photoacid generator that is a compound that generates an acid by light irradiation can be used.

The (A) acid generator used as a component in the ink pattern-forming composition of the present invention may be any compound that generates an acid upon irradiation with light, and examples thereof include an oxime sulfonate compound, an onium salt, and a sulfonylurea Amine compounds, halogen-containing compounds, diazomethane compounds, amidine compounds, sulfonate compounds, carboxylic acid ester compounds, and the like.

[Oxime sulfonate compound] Examples of the oxime sulfonate compound include an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a carbon number 6 to 20 aryl groups. Some or all of the hydrogen atoms possessed by these groups may be substituted with a halogen atom or a substituent. A linear alkyl group having 1 to 12 carbons or a branched alkyl group having 3 to 12 carbons is preferred. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms, and an alicyclic group containing a bridged cyclic alicyclic group such as a 7,7-dimethyl-2- pendant oxyalkyl group.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms include trifluoromethyl, pentafluoroethyl, or heptylfluoropropyl. Examples of the substituent which the alicyclic hydrocarbon having 4 to 12 carbon atoms may have include an alkyl group or alkoxy group having 1 to 5 carbon atoms.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, a tolyl group, and a xylyl group. Examples of the substituent which the aryl group having 6 to 20 carbon atoms may have include an alkyl group or alkoxy group having 1 to 5 carbon atoms or a halogen atom.

As the oxime sulfonate compound, (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyl) Oxyimino-5H-thiophen-2-yl)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-yl)-(2-methyl Phenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile or (5-octylsulfonyloxyimine) )-(4-methoxyphenyl) acetonitrile.

[Onium salt] Examples of the onium salt include diphenylphosphonium salt, triphenylphosphonium salt, alkylphosphonium salt, benzylphosphonium salt, dibenzylphosphonium salt, substituted benzylphosphonium salt, and benzothiazolium salt. Or tetrahydrothiophenynium salt.

<Diphenylphosphonium salt> Examples of the diphenylphosphonium salt include diphenylphosphonium tetrafluoroborate, diphenylphosphonium hexafluorophosphonate, diphenylphosphonium hexafluoroarsenate, and diphenylphosphonium Trifluoromethanesulfonate, diphenylphosphonium trifluoroacetate, diphenylphosphonium p-toluenesulfonate, diphenylphosphonium butyl tris (2,6-difluorophenyl) borate, 4-methoxy Phenylphenyl phenyl tetrafluoroborate, bis (4-third butylphenyl) tetrafluoroborate, bis (4-third butylphenyl) hexafluoroarsenate, bis (4- Tertiary butylphenyl), triflate, bis (4-thirdbutylphenyl), trifluoroacetate, bis (4-thirdbutylphenyl), p-toluenesulfonate or Bis (4-tert-butylphenyl) hydrazone camphorsulfonate.

<Triphenylsulfonium salt> Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium tetrafluoroborate, and triphenylsulfonium Trifluoroacetate, triphenylphosphonium p-toluenesulfonate or triphenylphosphonium butyl tris (2,6-difluorophenyl) borate.

<Alkyl sulfonium salt> Examples of the alkyl sulfonium salt include 4-ethoxyloxyphenyldimethylsulfonium hexafluoroantimonate, 4-ethoxyloxyphenyldimethylsulfonium hexafluoroarsenate , Dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzyloxy) phenylsulfonium hexafluoroantimonate, dimethyl- 4- (benzyloxy) phenylsulfonium hexafluoroarsenate or dimethyl-3-chloro-4-ethenyloxyphenylsulfonium hexafluoroantimonate.

<Benzylphosphonium salt> Examples of the benzylphosphonium salt include benzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, 4- Ethyloxyphenylbenzylmethylfluorene hexafluoroantimonate, benzyl-4-methoxyphenylmethylfluorene hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl Sulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethyl fluorinated hexafluoroarsenate, or 4-methoxybenzyl-4-hydroxyphenylmethyl fluorinated hexafluorophosphate.

<Dibenzylphosphonium salt> Examples of the dibenzylphosphonium salt include dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4- Acetyloxyphenyl dibenzyl hexafluoroantimonate, dibenzyl-4-methoxyphenyl hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenyl hexafluoride Arsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate or benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium Fluorophosphate.

<Substituted benzylsulfonium salts> Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-nitrobenzyl-4-hydroxyphenylmethylsulfonium Hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylfluorene hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylfluorene hexafluoroantimonate, 3 , 5-Dichlorobenzyl-4-hydroxyphenylmethylfluorene hexafluoroantimonate or o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylfluorene hexafluoroantimonate.

<Benzothiazolium salt> Examples of the benzothiazolium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, and 3-benzylbenzo Thiazolium tetrafluoroborate, 3- (p-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, or 3-benzyl Methyl-5-chlorobenzothiazolium hexafluoroantimonate.

<Tetrahydrothienium salt> Examples of the tetrahydrothienium salt include 4,7-di-n-butoxy-1-naphthyltetrahydrothienium trifluoromethanesulfonate, 1- (4-n-butane Oxynaphthalen-1-yl) tetrahydrothienium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothienium nonafluoron-butanesulfonate, 1- (4 -N-butoxynaphthalen-1-yl) tetrahydrothienium-1,1,2,2-tetrafluoro-2- (norkane-2-yl) ethanesulfonate, 1- (4-n-butoxy Naphthyl-1-yl) tetrahydrothienium-2- (5-tert-butoxycarbonyloxybicyclo [2.2.1] heptane-2-yl) -1,1,2,2-tetrafluoroethyl Sulfonate or 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothienium-2- (6-third-butoxycarbonyloxybicyclo [2.2.1] heptane-2-yl) -1,1,2,2-tetrafluoroethanesulfonate.

<Sulfoimide compound> Examples of the sulfonylimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenyl Sulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethyl Sulfofluorenyloxy) diphenylcisbutenedifluoreneimine, N- (camphorsulfonyloxy) diphenylcisbutenedifluoreneimine, 4-methylphenylsulfonyloxy) diphenyl Maleicimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenyl maleimide, N- (4-fluorophenylsulfonyloxy) diphenyl Cis-butenedifluorenimine, N- (4-fluorophenylsulfonyloxy) diphenylcis-butenedifluoreneimine, N- (phenylsulfonyloxy) bicyclo [2.2.1] heptane -5-ene-2,3-dicarboxyfluorenimine, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyfluorenimine, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine, N- (nonafluorobutanesulfonyloxy) ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboximidine, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine, N- (trifluoromethylsulfonium (Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyfluorenimine, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxyamidoimine, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyamidoimine, N- (2- Trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine, N- (4-fluorophenylsulfonyloxy) ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxyamidine, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxo-2,3-dicarboxyamidine, N- (Camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxo-2,3- Dicarboxyamidine, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxo-2,3-dicarboxyamidine, N- (2- Trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxo-2,3-dicarboxyfluorenimine, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxo-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboximide, N- (camphorsulfonium (Oxy) naphthyldicarboximide, N- (4-methylphenylsulfonyloxy) naphthyldicarboximide, N- (phenylsulfonyloxy) naphthyldicarboximide , N- (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboximide, N- (4-fluorophenylsulfonyloxy) naphthyldicarboximide, N- (penta Fluoroethylsulfonyloxy) naphthyldicarboxyfluorenimine, N- (heptafluoropropylsulfonyloxy) naphthyldicarboxyfluorenimine, N- (nonafluorobutylsulfonyloxy) naphthyl Dicarboxyfluorenimine, N- (ethylsulfonyloxy) naphthyldicarboximine, N- (propylsulfonyloxy) naphthyldicarboximine, N- (butylsulfonyloxy) ) Naphthyldicarboximide, N- (pentylsulfonyloxy) naphthyldicarboximide, N- (hexylsulfonyloxy) naphthyldicarboximide, N- (heptyl Sulfonyloxy) naphthyl dicarboximide N- (Sulfonic group-octyl) naphthyl dicarboxylic acyl imide or N- (Sulfonic group-nonyl) naphthalene carboxamide (PEI).

<Halogen-containing compound> Examples of the halogen-containing compound include a hydrocarbon compound containing a halogenated alkyl group and a heterocyclic compound containing a halogenated alkyl group.

<Diazomethane compounds> Examples of diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane. N-methane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonate Fluorenyl p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diamine Nitromethane or phenylsulfonyl (benzylidene) diazomethane.

<Amidine compound> As a amidine compound, a β-ketone amidine compound, a β-sulfo amidine compound, and a diaryl diamidine compound are mentioned.

<Sulfonate Compound> Examples of the sulfonate compound include an alkyl sulfonate, a haloalkyl sulfonate, an aryl sulfonate, and an imine sulfonate.

<Carboxylate compound> Examples of the carboxylate compound include o-nitrobenzyl carboxylic acid.

<(A) acid generator contained in the ink pattern formation composition of this invention> These (A) acid generator can be used individually or in combination of 2 or more types. An oxime sulfonate compound, an onium salt, and a sulfonate compound are preferable from the point that the improvement effect of the exposure sensitivity of the film containing the ink pattern formation composition is large, and an oxime sulfonate compound is especially preferable.

[Inclusion of (A) acid generator in ink pattern forming composition] The (A) acid generator in ink pattern forming composition of the present invention contains the fluoropolymer (1) of the present invention The mass% as a reference is preferably 0.1% or more and 10% or less, and more preferably 1% or more and 5% or less. By setting the content of the (A) acid generator to the above range, a higher exposure sensitivity of the composition for forming an ink pattern can be obtained, and a finer pattern-forming film can be obtained by a liquid-repellent site and a lyophilic site.

5-2. (B) Solvent As the (B) solvent used as a component of the ink pattern-forming composition of the present invention, it is sufficient to dissolve or disperse each component of the ink pattern-forming composition, and examples thereof include alcohols. , Ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aliphatic hydrocarbons, aromatic hydrocarbons Organic solvents such as ketones, ketones or esters. Hereinafter, each (B) solvent is disclosed.

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

<Aromatic alcohols> Examples of the aromatic alcohols include benzyl alcohol. Examples of the ethylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, or ethylene glycol monobutyl ether.

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

From the viewpoint of easily dissolving the ink pattern-forming composition of the present invention and forming a film, among these alcohols, benzyl alcohol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol mono are preferred. Methyl ether or propylene glycol monoethyl ether.

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

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

[Glycol alkyl ether acetates] Examples of glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, and ethylene glycol monobutyl ether. Acid ester or 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, or propylene glycol monobutyl ether ethyl Acid ester.

[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 monopropionate Butyl propionate.

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

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

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

[Esters] Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, and 2-hydroxy-2-methylpropionic acid. Methyl ester, 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxyl Methyl propionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, methyl Ethyl ethoxylate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxylate Methyl acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butoxy Butyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2-ethoxypropionate Methyl ester or ethyl 2-ethoxypropionate.

These (B) solvents can be used individually or in combination of 2 or more types.

[Content ratio of (B) solvent in ink pattern forming composition]

The content of the (B) solvent in the ink pattern-forming composition is preferably 100 parts by mass, more preferably 200 parts by mass to 1600 parts by mass, and more preferably 400 parts by mass to 100 parts by mass of the ink pattern forming composition other than (B) solvent. 1000 parts by mass. When the use of the (B) solvent is within the above range, the wettability of the composition for forming an ink pattern to a glass substrate or the like can be improved, and the occurrence of uneven coating can be suppressed, and a uniform film can be obtained.

5-3. (C) Quenching agent The (C) quenching agent used in the ink pattern forming composition of the present invention is an acid that prevents the acid from the (A) acid generator when exposed to a film. Examples of the function of the diffusing acid diffusion suppressing material include photo-disintegrable bases which generate light due to light exposure by exposure. The photo-disintegrable base is preferably an onium salt compound.

The photo-disintegrable base generates an acid in the exposed portion, and exerts a higher acid-capturing function brought about by anions in the unexposed portion, and captures the acid from the (A) acid generator to diffuse from the exposed portion. Acid inactivation to unexposed areas. Acid was inactivated only in the unexposed portions. In the pattern-forming film after exposing the pattern-forming composition of the present invention, the boundary between the liquid-repellent portion and the lyophilic portion becomes clear, and the contrast of the pattern after the ink coating is improved to obtain a delicate pattern. (C) The quencher may be used alone or in combination of two or more kinds.

[Content of (C) Quenching Agent in Ink Pattern Formation Composition] The content of (C) quencher in ink pattern forming composition is preferably 100 parts by mass with respect to the fluoropolymer (1). 0.001 to 5 parts by mass, more preferably 0.005 to 3 parts by mass. By setting the content of the (C) quencher to the above range, in the pattern-forming film after exposing the ink pattern-forming composition of the present invention, the boundary between the liquid-repellent site and the lyophilic site becomes clear. After the ink is applied, The contrast of the pattern is increased to obtain a delicate pattern.

5-4. (D) Sensitizer (D) The sensitizer used in the ink pattern forming composition of the present invention is added when it is desired to further increase the exposure sensitivity of the ink pattern forming composition. (D) The sensitizer is preferably a compound that absorbs light or radiation and becomes excited. By bringing the (D) sensitizer into an excited state, electron transfer, energy transfer, or heat generation occurs when in contact with the (A) acid generator, whereby the (A) acid generator is easily decomposed to generate an acid. (D) The sensitizer only needs to have an absorption wavelength in the region of 350 nm to 450 nm, and examples thereof include polynuclear aromatics, Ketones, ketones, cyanines, merocyanines, rhodamines, oxoxane, thiazines, acridines, acridinones, anthraquinones, squarylates, styryls, benzenes And styryl or coumarins.

Hereinafter, each (D) sensitizer is disclosed.

[Polynuclear aromatics] Examples of polynuclear aromatics include pyrene, pyrene, bitriphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 3,7- Dimethoxyanthracene or 9,10-dipropoxyanthracene.

[ Class] as Examples can be exemplified: luciferin, eosin, red algae red, rose red B, Bengal rose red.

[Ketones] Examples of the ketones include ketones and 9-oxysulfur Dimethyl-9-oxysulfur Diethyl-9-oxysulfur Or isopropyl-9-oxysulfur .

[Cyanines] Examples of cyanines include thiocyanine and oxacarbocyanine.

[Merocyanine] Examples of merocyanine include merocyanine and carbomerocyanine.

[Thioides] Examples of the thios include thionine, methylene blue, and toluidine blue.

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

[Acridinones] Examples of the acridinones include acridinone and 10-butyl-2-chloroacridone.

[Anthraquinones] Examples of the anthraquinones include anthraquinones.

[Squaric acid cyanine] Examples of the squaric acid cyanine include squaric acid cyanine.

[Benzene vinyls] Examples of the benzovinyls include 2- [2- [4- (dimethylamino) phenyl] vinyl] benzoxazole.

[Coumarins] Examples of coumarins include 7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin, or 2,3,6,7-tetracycline Hydrogen-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quine -11-one.

These (D) sensitizers can be used individually by 1 type or in combination of 2 or more types.

[(D) Sensitizer contained in the composition for forming an ink pattern of the present invention] As the (D) sensitizer used in the composition for forming an ink pattern of the present invention, the effect of improving the sensitivity of exposure is large. In other words, polynuclear aromatics, acridinones, styryls, benzovinyls, coumarins or ketones are preferred, and ketones are particularly preferred. Of the ketones, diethyl-9-oxysulfur is preferred Isopropyl-9-oxysulfur .

[Content ratio of (D) sensitizer in the ink pattern forming composition] The content of (D) sensitizer is preferably 0.1 to 8 parts by mass based on 100 parts by mass of the fluoropolymer (1). , More preferably 1 to 4 parts by mass. When the content of the (D) sensitizer is in the above range, the exposure sensitivity of the composition for forming an ink pattern can be improved. In the pattern-forming film after exposing the composition for pattern formation of the present invention, the liquid-repellent site and the lyophilic The boundary between the parts becomes clear, and the contrast of the ink pattern after the ink application is improved, and a delicate pattern is obtained.

5-5. (E) Polymerizable compound (E) The polymerizable compound used as a component of the ink pattern forming composition of the present invention is contained in the ink pattern forming composition in order to make the obtained pattern forming film harder. In the middle. (E) The polymerizable compound is a compound having an ethylenically unsaturated bond other than the fluoropolymer (1). Examples of such (E) polymerizable compounds include those having a good polymerizability and a harder pattern-forming film obtained from the ink pattern-forming composition, including monofunctional or difunctional acrylates and Methacrylate.

Hereinafter, each (E) polymerizable compound is disclosed.

[Monofunctional acrylate and methacrylate] <monofunctional acrylate> Examples of the monofunctional acrylate include 2-hydroxyethyl acrylate, diethylene glycol monoethyl ether acrylate, and (2-propenyloxy) (Ethyl) (2-hydroxypropyl) phthalate or (2-methacryloxyethyl) (2-hydroxypropyl) phthalate.

<Monofunctional methacrylate> Examples of the monofunctional methacrylate include 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether methacrylate, or ω-carboxy polycaprolactone monoacrylate.

Monofunctional acrylates and methacrylates are available on the market. For example, commercially available: ARONIX (registered trademark) from East Asia Synthetic Co., Ltd., product numbers M-101, M-111, M-114, and M-5300, trade names KAYARAD from Nippon Kayaku Co., Ltd., product numbers TC-110S, TC-120S, trade names Viscoat 158, 2311 Viscoat, etc. from Osaka Organic Chemical Industry Co., Ltd.

[Bifunctional acrylate and methacrylate] Examples of the bifunctional acrylate include ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, 1 , 6-hexanediol diacrylate or 1,9-nonanediol diacrylate.

Examples of the bifunctional methacrylate include propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,6 -Hexanediol dimethacrylate or 1,9-nonanediol dimethacrylate.

Commercial products are available for bifunctional acrylates and methacrylates. For example, commercially available: ARONIX (registered trademark) from East Asia Synthetic Co., Ltd., product numbers M-210, M-240, M-6200, Trade name KAYARAD from Nippon Kayaku Co., Ltd., product numbers HDDA, HX-220, R-604, trade name Viscoat from Osaka Organic Chemical Industry Co., Ltd., product numbers 260, 312, 335HP, from Kyoeisha Chemical The company's trade name is Light Acrylate 1,9-NDA.

[Tri- or higher-functional acrylate and methacrylate] Examples of the tri- or higher-functional acrylate and methacrylate include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol. Triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and di Mixture of pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tris (2-propenyloxyethyl) phosphate, tris (2-methacryl) phosphate Oxyethyl) ester, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified pentaerythritol pentaacrylate, tris (acryloxyethyl) isocyanurate, or a Compounds having a cyclic structure and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule and having three, four, or five (a ) Bing Xixi oxy compound obtained by reacting as much of the functional urethane acrylate-based compound.

Commercial products can be obtained from trifunctional or higher acrylates and methacrylates. For example, commercially available: ARONIX (registered trademark) from East Asia Synthetic Co., Ltd., product numbers M-309, M-315, M-400 , M-405, M-450, M-7100, M-8030, M-8060, TO-1450, trade names KAYARAD from Nippon Kayaku Co., Ltd., product numbers TMPTA, DPHA, DPCA-20, DPCA-30 , DPCA-60, DPCA-120, DPEA-12, trade names Viscoat from Osaka Organic Chemical Industry Co., Ltd., product numbers 295, 300, 360, GPT, 3PA, 400, products from Kyoeisha Chemical Co., Ltd. Name Light Acrylate 1,9-NDA and so on. Polyfunctional urethane acrylate compounds are commercially available: New Frontier (registered trademark) from Daiichi Kogyo Co., Ltd., product number R-1150, and KAYARAD from Japan Chemical Co., Ltd. , Product number DPHA-40H and so on.

The (E) polymerizable compound used in the ink pattern-forming composition of the present invention is preferably an ω-carboxy polycaprolactone monomer in terms of the effect of making the obtained pattern-forming film harder. Acrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate Mixture of acrylate and dipentaerythritol pentaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate or polyfunctional urethane acrylic acid Esters. Especially preferred is a mixture of trifunctional or higher (meth) acrylates, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

[Content Ratio 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 to 300 parts by mass, more preferably 3 to 200 parts by mass, and even more preferably 5 parts by mass based on 100 parts by mass of the fluoropolymer (1). ~ 100 parts by mass. When the amount of the (E) polymerizable compound used is within the above range, the pattern-forming film obtained from the ink pattern-forming composition can be made harder.

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

[Formation method of ink pattern (A)] The formation method (A) of the ink pattern of the present invention includes the following steps: a film forming step of coating the above-mentioned composition for forming an ink pattern on a substrate to form a film; The film is irradiated with light having a wavelength of above 150 nm and below 500 nm for exposure, and an exposure step of transferring a pattern of the photomask to the film to obtain a pattern-forming film having a liquid-repellent portion and a lyophilic portion; and coating the resulting pattern-forming film An ink pattern forming step of fabricating ink to obtain a pattern formed by the ink.

[Pattern forming method (B)] The ink pattern forming method (B) of the present invention includes the following steps: a film forming step of applying the composition for forming an ink pattern on a substrate and heating the obtained coating film; A drawing device for exposing light having a scanning wavelength of 150 nm to 500 nm, and drawing a pattern on the film to obtain a drawing step of a pattern forming film having a liquid-repellent portion and a lyophilic portion; and forming a pattern on the obtained pattern An ink pattern forming step of applying the ink.

6-1. Film formation step and ink pattern formation method of the ink pattern formation method The following are common film formation steps and ink pattern formation method (A) of the ink pattern formation method (A) and (B) of the present invention. The exposure fixation in (B), the drawing step in (B), and the ink pattern forming method (A) and (B) are common to the ink pattern forming step.

6-2. Film-forming step The film-forming step is a step of applying the composition for forming an ink pattern of the present invention on a substrate and heating (pre-baking) the obtained coating film.

[Substrate] Examples of the substrate used in the film formation process include resin substrates, glass substrates, semiconductor substrates such as quartz, and silicon, which have been conventionally used in electronic circuits. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyether fluorene, polycarbonate, or polyimide.

Before applying the composition for forming an ink pattern on a substrate, if necessary, pretreatments such as cleaning, roughening, and providing a small number of uneven surfaces can be performed on the substrate surface.

[Coating method] The coating method for coating the ink pattern forming composition on the substrate is not particularly limited, and examples thereof include coating using a brush or a brush, dipping method, spray method, roll coating method, and rotation Coating method (spin coating method), slit die coating method, bar coating method, flexographic printing, offset printing, inkjet printing, or dispensing method. In the pattern forming method of the present invention, a spin coating method is preferred.

[Film thickness] The thickness of the coating film formed in the above steps can be appropriately adjusted according to the intended use. In the ink pattern forming method of the present invention, it is preferably 0.1 μm to 20 μm.

[Pre-baking] The 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, but it is also based on The composition of the ink pattern-forming composition used varies.

6-3. Exposure step and drawing step [Exposure step] The exposure step in the method of forming the ink pattern (A) is to expose the film obtained in the film-forming step to light having a wavelength of 150 nm or more and 500 nm or less through a photomask. A step of transferring a pattern of a photomask to a film to obtain a pattern-forming film having a liquid-repellent portion and a lyophilic portion. The exposure is performed through a mask having a specific pattern in such a manner that an exposure portion having the same pattern as the desired pattern is formed.

[Drawing step] The drawing step in the method of forming the ink pattern (B) is to expose the light obtained by the film scanning step at a scanning wavelength of 150 nm or more and 500 nm or less by a drawing device, and draw the pattern on the film. A step of obtaining a pattern-forming film having a liquid-repellent portion and a lyophilic portion. For example, it is performed by scanning a specific pattern using a direct drawing type exposure device.

[Using light] Radiation that is visible light, ultraviolet rays, X-rays, or a stream of charged particles can be used for exposure and drawing. It is preferably ultraviolet light having a wavelength of 150 nm or more and 500 nm or less, and particularly preferably 365 nm ultraviolet light by an ultraviolet light emitting diode.

By exposure and drawing, using the effect of the acid generated by the (A) acid generator in the film, the acid-dissociable group of the fluoropolymer (1) is detached and volatilized. As a result, the film thickness of the exposed portion becomes thinner than that of the unexposed portion, and a concave pattern is formed. At this time, since the acid-dissociable group has a fluorine atom, the unexposed portion exhibits liquid repellency, and the exposed portion becomes lyophilic. Therefore, the film formed on the substrate becomes a pattern forming film of a liquid-repellent unexposed portion and a lyophilic exposed portion that is a concave pattern.

[Heating] The pattern-forming film after exposure is preferably heated. By heating the pattern-forming film after exposure, the components generated from the acid-dissociable group dissociated from the fluoropolymer (1) in the exposed portion can be further volatilized to obtain more of the exposed concave portion and the unexposed convex portion. Delicate pattern.

Examples of the method for heating the pattern-forming film include a method of heating the film-forming substrate using a hot plate, a batch oven, or a conveying oven, a method of hot air drying using a dryer, and a method of vacuum baking. . The heating conditions also differ depending on the composition of the composition or the thickness of the coating film to be obtained, and are preferably 60 ° C or higher, 150 ° C or lower, 3 minutes or longer and 30 minutes or shorter.

6-4. Ink pattern formation step The formation of an ink pattern is performed by applying an ink to the obtained pattern forming film to obtain a pattern formed by the ink.

The difference between the contact angle between the water-repellent portion and the liquid-repellent portion of the pattern-forming film before and after exposure to water and hexadecane as an ink solvent is preferably 30 ° or more, and more preferably 50 ° or more. By setting the contact angle difference to the above range, the ink is repelled even when the ink is applied to the convex liquid-repellent portion, and the ink easily moves to the concave portion that is the lyophilic portion, and the exposed concave portion and the unexposed portion are obtained. More delicate ink pattern on the convex part.

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

6-5. Application in electronic circuits and electronic devices In the method for forming an ink pattern of the present invention, a motor circuit including a conductive ink pattern is formed on a substrate, so that an electronic device can be manufactured. The electronic circuit is a wiring using a conductive ink pattern formed on a substrate. The electronic device is a device having an electronic circuit. Examples include portable information devices such as liquid crystal displays, mobile phones, digital cameras, organic displays, organic EL (Electroluminescence) lighting, various sensors, or portable 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 represented by the following formula (4) of the fluorine-containing monomer system of the present invention has a fluorine-containing cyclic acetal structure, and the fluorine-containing polymer (1) is Obtained by homopolymerizing or copolymerizing a fluorine-containing monomer (4). Hereinafter, it may be referred to as a fluorine-containing monomer (4). [Chemical 14] (In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group. 7 or less can be substituted with fluorine atoms; R ² to R ⁵ are hydrogen atoms, linear 1 to 10 carbons or branched alkyls with 3 to 10 carbons, and carbon atoms in the alkyl bond Seven or less of the hydrogen atoms of the knot can be replaced by fluorine atoms; X is a single bond or a divalent radical, and 7 or less hydrogen atoms contained in the divalent radical can be replaced by fluorine atoms; Y is a carbon number of 1 ～ 3 fluorine-containing alkyl or carboxylic acid ester group (-COOR), fluorine-containing alkyl or carboxylic acid ester group containing 7 or less hydrogen atoms may be substituted by fluorine atom; R is a carbon containing 1 to 3 Fluoroalkyl; the same below)

[Fluorine-containing monomer (5)] The fluorine-containing monomer (1) of the present invention is preferably a 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 fluorinated monomer (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, solubility in a solvent is considered. In the above formula (4), R ² , R ⁴ , and R ^{5 are} preferably hydrogen atoms, and more preferably a fluorine-containing monomer having a fluorine-containing cyclic acetal structure represented by the following formula (5). Hereinafter, it may be referred to as a fluorine-containing monomer (5). [Chemical 15] (R ¹ , R ³ , X, Y in formula (5) have the same meaning as formula (4))

[Fluorine-containing monomer (6)] The fluorine-containing monomer (5) of the present invention is a fluorine-containing monomer (6) in which Y in the above formula (5) is a trifluoromethyl group or less. When the above-mentioned fluoropolymer (2) obtained by homopolymerizing or copolymerizing a fluoromonomer (5) is used as a resist or a composition for forming an ink pattern to form a film on a substrate, considering the solubility to a solvent, the above Y in the formula (4) is preferably a trifluoromethyl group, and more preferably a fluorine-containing monomer having a fluorine-containing cyclic acetal structure represented by the following formula (6). Hereinafter, it may be referred to as a fluorine-containing monomer (6). [Chemical 16] (R ¹ , R ³ , and X in formula (6) have the same meaning as formula (4))

As the fluorine-containing monomer (4) of the present invention, specific examples are exemplified below, but are not limited thereto. [Chemical 17]

8. Manufacturing method of fluorine-containing monomer (4) The manufacturing method of the fluorine-containing monomer (4) of this invention is disclosed. The method for producing a fluorine-containing monomer of the present invention includes cyclizing a hydroxycarbonyl compound represented by the following formula (10) or a hydroxy vinyl ether or hydroxy vinyl ester represented by the formula (11) to obtain the compound represented by the formula (7): Step of cyclic hemiacetal compound. [Chemical 18] (In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group. 7 or less can be substituted with fluorine atoms; R ² to R ⁵ are hydrogen atoms, linear 1 to 10 carbons or branched alkyls with 3 to 10 carbons, and carbon atoms in the alkyl bond Seven or less of the hydrogen atoms of the knot can be replaced by fluorine atoms; X is a single bond or a divalent radical, and 7 or less hydrogen atoms contained in the divalent radical can be replaced by fluorine atoms; Y is a carbon number of 1 ～ 3 fluorine-containing alkyl or carboxylic acid ester group (-COOR), fluorine-containing alkyl or carboxylic acid ester group containing 7 or less hydrogen atoms may be substituted by fluorine atom; R is a carbon containing 1 to 3 Fluoroalkyl; Z is a straight chain having 1 to 20 carbon atoms, and a branched or cyclic alkyl group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in Z may be substituted by halogen atoms, and may contain ether. Bond, siloxane bond, thioether bond, carbonyl bond; the same below)

8-1. Halidation or alkylation of fluorinated cyclic hemiacetal compound The fluorinated monomer (4) of the present invention can be synthesized as follows: The fluorinated cyclic hemicondensation represented by formula (7) An aldehyde compound (hereinafter, sometimes referred to as a fluorine-containing cyclic hemiacetal compound (7)) is introduced with a polymerizable group to obtain a fluorine-containing monomer (4). This reaction is shown below. [Chemical 19] (R ¹ , R ² to R ⁵ , X, Y have the same meaning as in the above formula, and A is a hydrogen atom, a halogen atom, an acrylfluorenyl group, or a methacrylfluorenyl group)

This reaction system can carry out the halogenation or alkylation reaction of the hydroxyl group of the fluorinated cyclic hemiacetal compound (7) having a hydroxyl group, in the presence of a base, in a solvent or without a solvent, on an acrylfluorenyl compound ( In 12), a reaction of synthesizing the fluorinated monomer (4) by reacting with a halogenating agent in which X is a single bond or an alkylating agent in which X is a divalent organic group.

8-1-1. Halogenation of fluorine-containing cyclic hemiacetal compound [Hydrogenating agent] Examples of the halogenating agent include carboxylic acid chloride and carboxylic acid anhydride. Examples of the halogenating agent include acrylic acid chloride, methacrylic acid chloride, acrylic acid anhydride, methacrylic acid anhydride, 2-fluoropropylene acid chloride, or 2-methacrylic acid oxyacetic acid chloride.

The amount of the halogenating agent is preferably 0.5 mol or more and 10 mol or less relative to 1 mol of the fluorinated cyclic hemiacetal compound (7). In terms of improving the yield of the hydration, it is particularly preferred that Above 1 mole and below 3 moles. The reaction with the halogenating agent can be performed in the presence of a base, and the reaction can be performed in a solvent-free or solvent-free manner.

[Base] Examples of the base include inorganic bases and organic bases. The amount of the base used in the reaction is preferably 0.05 mol or more and 10 mol or less relative to 1 mol of the fluorine-containing cyclic hemiacetal compound (7). Preferably it is 1 mole or more and 3 moles or less.

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

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

[Solvent] Examples of the solvent include a hydrocarbon-based solvent, an ether-based solvent, and a chlorine-based solvent. Can be used with water if needed.

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

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

<Chlorine-based solvent> Examples of the chlorine-based solvent include dichloromethane, chloroform, and 1,2-dichloroethylene.

8-1-2. Alkylation of fluorine-containing cyclic hemiacetal compound A polymerizable group may be introduced by alkylation of a hydroxyl group of the fluorine-containing cyclic hemiacetal compound (7). During the reaction, a catalyst may be used to promote the reaction speed.

[Alkylating Agent] Examples of the alkylating agent include halogenated alkyls and sulfonates.

The reaction with the halogenating agent can be performed in the presence of a base, and the reaction can be performed in a solvent-free or solvent-free manner. The amount of the alkylating agent is preferably 0.5 mol or more and 10 mol or less relative to 1 mol of the fluorinated cyclic hemiacetal compound (7), and particularly preferably 1 in terms of improving the yield. Above Mohr and below 3 Mohr.

<Halogenated alkyl group> Examples of the halogenated alkyl group include chloroethyl acrylate, chloroethyl methacrylate, bromoethyl acrylate, and bromoethyl methacrylate.

<Sulfonate> Examples of the sulfonate include 2-methylsulfonyloxyethyl acrylate, 2-methylsulfonyloxyethyl methacrylate, and 2-p-toluenesulfonyloxy acrylate Ethyl ester, 2-p-toluenesulfonyl ethyl methacrylate.

[Base] Examples of the base include inorganic bases and organic bases. Examples of the organic base 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 in terms of improving the yield, it is particularly preferably 1 mol or more and 3 mol or less.

<Inorganic base> Examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium hydride, sodium hydride, potassium hydride, ammonia.

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

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

Examples of Grignard reagents include methyl magnesium bromide.

Examples of the alkali metal salt include sodium methoxide, sodium ethoxide, and potassium tert-butoxide.

[Solvent] The solvent is usually preferably a solvent that is favorable for the nucleophilic substitution reaction, and examples thereof include aprotic polar solvents and protic polar solvents. It can also be the combination of these solvents with water.

Examples of the aprotic polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfinium, and N-methylpyrrolidone.

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

[Catalyst] To promote the reaction speed of the alkylation reaction, iodide or bromide can be added as a catalyst. When the catalyst is added, the amount added is 0.001 to 1 mol, particularly preferably 0.005 to 0.5 mol, relative to 1 mol of the hemiacetal compound (7).

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

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

9. Fluorinated cyclic hemiacetal [Fluorinated cyclic hemiacetal (7)] The fluorinated polymer (1) of the present invention is obtained by polymerizing a fluorinated monomer (4). A fluorine-containing single system fluorine-containing monomer having a fluorine-containing cyclic acetal structure. Fluorinated cyclic hemiacetal (7) is a compound that is a precursor of fluorinated monomer (4) [Chem. 20] (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 of a hydrogen atom bonded to a carbon atom in the alkyl group. 7 or less can be substituted with fluorine atoms; Y is a fluorine-containing alkyl or carboxylic acid ester group (-COOR) having 1 to 3 carbon atoms, and the fluorine-containing alkyl or carboxylic acid ester group contains 7 or less hydrogen atoms Can be substituted by fluorine atom; 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 a fluorine-containing hemiacetate in which R ² , R ⁴ , and R ⁵ in the above formula (7) are hydrogen atoms or less Acetal (8).

The fluorine-containing polymer (2) of the present invention is obtained by polymerizing a fluorine-containing monomer (5). A fluorine-containing single system fluorine-containing monomer having a fluorine-containing cyclic acetal structure. In addition, the following fluorine-containing cyclic hemiacetal (8) is a compound that is a precursor of the fluorine-containing monomer (5). [Chemical 21] (R ³ and X in formula (8) have the same meaning as formula (7))

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

The fluorinated polymer (3) of the present invention is a fluorinated monomer obtained by polymerizing the fluorinated monomer (6), and has a fluorinated cyclic acetal structure. The following fluorine-containing cyclic hemiacetal (9) is a compound that is a precursor of the fluorine-containing monomer (6). [Chemical 22] (R ³ in formula (9) has the same meaning as formula (7))

10. Synthesis of fluorine-containing cyclic hemiacetal (7) The method for producing the fluorine-containing cyclic hemiacetal (7) of the present invention will be described.

It is a method for producing a cyclic hemiacetal compound by cyclizing a hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or hydroxyvinyl ester represented by the formula (11) to obtain the compound represented by the formula (7) The cyclic hemiacetal compound of the invention 12 shown. [Chemical 23] (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 of a hydrogen atom bonded to a carbon atom in the alkyl group. 7 or less can be substituted with fluorine atoms; Y is a fluorine-containing alkyl or carboxylic acid ester group (-COOR) having 1 to 3 carbon atoms, and the fluorine-containing alkyl or carboxylic acid ester group contains 7 or less hydrogen atoms It can be substituted by fluorine atom; R is a fluorine-containing alkyl group having 1 to 3 carbon atoms; Z is a linear chain having 1 to 20 carbon atoms and a branched or cyclic alkyl group having 3 to 20 carbon atoms; Some or all of the hydrogen atoms may be substituted by halogen atoms, and may contain ether bonds, siloxane bonds, thioether bonds, and carbonyl bonds)

The fluorine-containing cyclic hemiacetal (7) of the present invention can be synthesized mainly through two steps shown below.

10-1. First step The first step is the following step: the carbonyl group of allyl alcohols, allyl ethers or allyl esters with hexafluoroacetone (hereinafter sometimes referred to as HFA) or trifluoropyruvate -An ene reaction to obtain a hydroxy vinyl ester represented by the formula (10) or a hydroxy vinyl ether represented by the formula (11).

Hereinafter, it is revealed that the carbonyl-ene reaction of the allyl alcohols, allyl ethers, or allyl esters represented by the formula (12) and the trifluorocarbonyl compound represented by the formula (13) is obtained to obtain the compound represented by the formula (10). The reaction of the hydroxy vinyl carbonyl compound or the hydroxy vinyl ether or hydroxy ester represented by the formula (11). Hereinafter, they are sometimes referred to as hydroxycarbonyl compounds (10), hydroxyvinyl ethers (11), allyl alcohols (12), allyl ethers (12), allyl esters (12), and trifluorocarbonyl compounds (13 ). [Chemical 24] (In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkyl group. 7 or less can be substituted with fluorine atoms; R ² to R ⁵ are hydrogen atoms, linear 1 to 10 carbons or branched alkyls with 3 to 10 carbons, and carbon atoms in the alkyl bond 7 or less of the hydrogen atoms of the structure may be substituted by fluorine atoms; Y is a fluorine-containing alkyl group or carboxylic acid ester group (-COOR) having 1 to 3 carbon atoms, and the fluorine-containing alkyl group or carboxylic acid ester group contains 7 or less hydrogen atoms may be substituted by fluorine atoms; R is a fluorine-containing alkyl group having 1 to 3 carbon atoms; Z is a straight chain having 1 to 20 carbon atoms and a branched or cyclic having 3 to 20 carbon atoms Alkyl, some or all of the hydrogen atoms in Z may be substituted by halogen atoms, and may contain ether bonds, siloxane bonds, thioether bonds, carbonyl bonds)

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 are mixed with HFA in which Y is a trifluoromethyl group, and The hydroxyvinyl ester (10) or the hydroxyvinyl ether (11) can be optionally synthesized by heating under an enclosed pressure of an autoclave or the like as necessary. Furthermore, when trifluoropyruvate is used instead of HFA, the reaction proceeds efficiently.

This reaction is a reaction of an allylic moiety of allyl alcohols (12), allyl ethers (12) or allyl esters (12) with an olefin of a fluorine-containing carbonyl compound (13). Allyl alcohols (12) The higher the electron density of the olefin portion on the allyl ether (12) or allyl ester (12) side, the easier the reaction is to proceed, and the reaction can be selectively performed with fewer side reactions. Compared with all of R ² to R ⁵ in allyl alcohols (12), allyl ethers (12) or allyl esters (12), all of them are hydrogen atoms, and it is preferable that several of them are substituted with electron-donating groups. As the electron-donating group, a methyl group is preferable.

The amount of HFA or trifluoropyruvate relative to 1 mol of allyl alcohol (12), allyl ether (12) or allyl ester (12) is preferably 0.5 mol or more and 10 mol Hereinafter, it is particularly preferred that it is 1 mol or more and 3 mol or less.

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

[Allyl ethers] As allyl ethers (12) or allyl esters (12) other than a hydrogen atom, preferably a protective group is introduced into the hydroxyl group of the allyl alcohols (12) as protection Examples of the type of the group include a silyl group, an acetal group, a fluorenyl group, a benzyl group, or a urethane group. In order to increase the electron density of the olefin portion and promote the reaction, the protecting group is preferably an acetal-based, silane-based, urethane-based, or benzyl-based system.

<Silyls> Examples of the silyls include trimethylsilyl, triethylsilyl, tributylsilyl, tert-butyldimethylsilyl, or tert-butyldiphenylsilyl. .

<Acetals> Examples of the acetals include tetrahydropyranyl, ethoxyethyl, butoxyethyl, methoxymethyl, methylthiomethyl, benzyloxymethyl, or methyl Ethoxyethoxymethyl.

<Amyl groups> Examples of amyl groups include methylamyl, ethylamyl, trifluoroethylamyl, propylamyl, benzamyl, trimethylethylamyl, acrylamyl, or methacryl醯 基.

<Benzyls> Examples of the benzyls include benzyl and p-methoxybenzyl.

<Carbamates> Examples of the carbamates include a third butoxycarbonyl group and a benzyloxycarbonyl group.

10-2. First step The reaction in the first step described above can also be carried out without a catalyst or a solvent, but in order to promote the reaction, an acid catalyst can also be used in a solvent. In order to produce more economically, it is preferably carried out in a solvent-free and catalyst-free manner, and the reaction product is separated from the hydroxyaldehyde, ketone, or formula (11) represented by the following formula (10) by a purification operation such as distillation. The hydroxy vinyl ethers and hydroxy vinyl esters shown. [Chemical 25]

The catalyst is not particularly limited as to whether it is used. In the case of use, any of an inorganic acid, an organic acid, and a Lewis acid may be used.

Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, and zeolite. Examples of the organic acid include a carboxylic acid, a sulfonic acid, a cation exchange resin, and a Lewis acid. Specific examples of the carboxylic acid include formic acid, acetic acid, and trifluoroacetic acid. Examples of the sulfonic acid include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluene. Examples of the Lewis acid include Lewis acid. : Aluminum chloride, titanium tetrachloride or tin chloride.

The reaction can be performed without using a solvent. In the case of using a solvent, as long as the raw materials are allyl alcohols (12), allyl ethers (12) or allyl esters (12) and HFA or trifluoroacetone The acid ester (13) and the fluorine-containing compound represented by the formula (10) or the formula (11) as a target may be an inert solvent. Examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and ethers.

[Aliphatic hydrocarbon] Examples of the aliphatic hydrocarbon include hexane, heptane, cyclohexane, and methylcyclohexane as a cyclic aliphatic hydrocarbon.

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

[Halogenated hydrocarbon] Examples of the halogenated hydrocarbon include dichloromethane.

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

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

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

10-3-1. Method-1 Method-1 is a method shown in the following reaction formula, that is, the hydroxycarbonyl compound (10) is selectively intramolecularly reacted by an acid or a base in a solvent Cyclization to obtain a fluorinated cyclic hemiacetal (7). [Chemical 26]

This method is preferably performed in a solvent under acidic or basic conditions.

As the acid, any of an inorganic acid, an organic acid, and a Lewis acid can be used. The amount of the acid used in the reaction is preferably 0.01 mol or more and 1 mol or less, and more preferably 0.05 mol or more and 0.2 mol or less relative to 1 mol of the hydroxycarbonyl compound (10).

Examples of the base include an inorganic base and an organic base. Under the two-phase system of water-organic solvents that can remove unreacted raw materials and traces of fluorinated alcohols, it is particularly preferable to use sodium hydroxide or potassium hydroxide under alkaline conditions. The amount of the base used in the reaction is preferably 0.5 mol or more and 10 mol or less relative to 1 mol of the hydroxycarbonyl compound (10), and particularly preferably 1 mol in terms of improving productivity. Above and below 3 moles.

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

[Organic acid] Examples of the organic acid include carboxylic acid, sulfonic acid, cation exchange resin, and Lewis acid. Examples of the carboxylic acid include formic acid, acetic acid, and trifluoroacetic acid. Examples of the sulfonic acid include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluene. Examples of the Lewis acid include aluminum chloride. , Titanium tetrachloride or tin chloride.

[Inorganic base] Examples of the inorganic base include lithium chlorohydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium hydride, sodium hydride, and potassium hydride. ,ammonia.

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

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

[Solvent] The reaction can be performed without using a solvent. In the case of using a solvent, as long as it is a solvent that is inert to the hydroxycarbonyl compound (10) as a raw material and the fluorine-containing cyclic hemiacetal (7) as a product, can. Examples include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and ethers.

Examples of the aliphatic hydrocarbon include hexane, heptane, cyclohexane, and methylcyclohexane as a cyclic aliphatic hydrocarbon. Examples of the aromatic hydrocarbon include benzene, toluene, and xylene. Examples of the halogenated hydrocarbon include dichloromethane, and examples of the ether include diethyl ether, dibutyl ether, tetrahydrofuran, or ethylene glycol dimethyl ether.

10-3-2. Method-2 Method-2 is a method shown in the following reaction formula, that is, after deprotecting hydroxyvinyl ether (11) or hydroxyvinyl ester (11), in a solvent, Or the action of a base can deprive a hydrogen atom of a hydroxyl group, thereby selectively performing intramolecular cyclization, thereby obtaining a fluorine-containing cyclic hemiacetal (7). This reaction is shown below. [Chemical 27]

The hydroxy vinyl ether (11) or hydroxy vinyl ester (11) is a compound whose hydroxy group is protected, and the protective group of the hydroxy vinyl ether (11) or hydroxy vinyl ester (11) is deprotected from the hydroxy vinyl ether (11) or hydroxy vinyl After the ester (11) is converted into the hydroxycarbonyl compound (10), intramolecular cyclization is performed in the same manner as in Method-1, whereby a fluorine-containing cyclic hemiacetal (7) can be obtained. Deprotection can use the usual deprotection methods. The acid, base or solvent used is the same as Method-1.

10-3-3. Method-3 Method-3 is a method shown in the following reaction formula, that is, hydroxyvinyl ether (11) or hydroxyvinyl ester (11) in a solvent, and the action of acid or base, The hydrogen atom of the hydroxyl group is taken away to selectively perform intramolecular cyclization to obtain a fluorinated cyclic acetal intermediate (14), and then deprotected to obtain a fluorinated cyclic hemiacetal (7). This reaction is shown below. [Chemical 28]

[Intramolecular cyclization] By adding an acid catalyst to a hydroxy vinyl ether (11) or a hydroxy vinyl ester (11) in the absence of a solvent or a solvent, and heating to about the boiling point of the solvent, the formula (14) can be obtained. Fluorinated cyclic acetal intermediate.

In terms of obtaining a fluorine-containing cyclic acetal intermediate (14) in a higher yield, trifluoroacetic acid, methanesulfonic acid or sulfuric acid is particularly preferred. The amount of the acid used in the reaction is preferably 0.01 mol or more and 1 mol or less, and more preferably 0.05 mol or more, relative to 1 mol of hydroxyvinyl ether (11) or hydroxyvinyl ester (11). 0.2 mol or less.

[Acid] As the acid used in Method-3, any of an inorganic acid, an organic acid, and a Lewis acid can be used.

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

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

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

[Deprotection] The fluorinated cyclic acetal intermediate (14) is a form in which the hydroxyl group of the fluorinated cyclic hemiacetal (7) is protected with other substituents, and the fluorinated cyclic can be obtained by deprotecting the protecting group Hemiacetal (7). Deprotection can use the usual deprotection methods.

On the other hand, in the case of the fluorine-containing compound (15) in which Z of the hydroxy vinyl ether (11) has a polymerizable group, the fluorine-containing monomer (4) can be synthesized by intramolecular cyclization in the previous stage of Method-3 . This reaction is shown below. [Chemical 29] [Example]

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

1. Synthesis of fluorinated cyclic hemiacetal The fluorinated cyclic hemisphere belonging to the fluorinated monomer represented by the above formula (7) used to obtain the precursor of the fluorinated monomer (4) was synthesized by the following production method: Acetal-1 to 7.

1-1-1. Synthesis of fluorine-containing cyclic hemiacetal-1 (Part 1) A reactor equipped with a stirrer was charged with allyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., 11.6 g (0.2 mol), and the reaction was carried out. The reactor was hermetically closed. 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 temperature in the reactor was raised to 150 ° C, and the stirring was continued for 40 hours. Reaction After completion, remove the contents and transfer to a separatory funnel. Add 50 ml of 3.5% by weight hydrochloric acid. After stirring for 2 hours, separate into an organic layer and an aqueous layer. Add 4% by weight sodium hydroxide water to the organic layer. After 50 ml of 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 a fluorinated cyclic hemiacetal represented by the following formula at a yield of 50%- 1 22.4 g. This reaction is shown below. <Results of NMR (nuclear magnetic resonance) analysis> The results of nuclear magnetic resonance analysis (hereinafter, sometimes referred to as NMR) are disclosed below. ¹ H-NMR (solvent: deuterochloroform, standard substance: TMS (Tetramethyl silane, tetramethylsilane)): 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: deuterochloroform, standard material: C ₆ D ₆ ): δ (ppm) -77.5 (3F, s), -79.5 (3F, s)

1-1-2. Synthesis of fluorinated 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. The reactor was hermetically sealed. Next, after degassing the inside of the reactor with a vacuum pump, while stirring the contents with a stirrer, 66.4 g (0.40 mol) of HFA was introduced. Then, the temperature in the reactor was raised to 120 ° C, and stirring was continued for 20 minutes. After the reaction is completed, remove the contents and transfer to a separatory funnel. Add 50 ml of 4% by weight sodium hydroxide water and stir for 1 hour. Separate the organic layer, and press at 3.0 kPa and 60 ° C to 62 ° C. Distillation under reduced pressure was performed to obtain 28 g of fluorine-containing cyclic hemiacetal-1 represented by the following formula at a yield of 63%. The following shows this reaction.

1-2. Synthesis of fluorine-containing cyclic hemiacetal-2 A reactor equipped with a stirrer was charged with β-methylallyl alcohol (manufactured by Tokyo Chemical Industry 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 temperature in the reactor was raised to 40 ° C, and the stirring was continued for 2 hours. After the reaction was completed Remove the contents and transfer to a separatory funnel. Add 50 ml of 3.5 mass% hydrochloric acid. After stirring for 2 hours, separate the organic layer from the aqueous layer. Add 50 ml of 4 mass% sodium hydroxide water 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 68 ° C to 69 ° C to obtain 43.7 g of a fluorine-containing cyclic hemiacetal-2 represented by the following formula at a yield of 92%. The following shows this reaction. <Results of NMR analysis> ¹ H-NMR (solvent: deuterochloroform, standard 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) isomers 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: deuterochloroform, standard material: C ₆ D ₆ ): δ (ppm) -77.5 (3F, m), -79.5 (3F, m)

1-3. Synthesis of fluorine-containing cyclic hemiacetal-3 In addition to using 2-methyl-3-buten-2-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the fluorine-containing cyclic hemiacetal-2 Except for the β-methylallyl alcohol used in the synthesis, in the same procedure as the synthesis of the fluorine-containing cyclic hemiacetal-2, a reaction shown in the following formula was performed to obtain a fluorine-containing cyclic hemiacetate at a yield of 87%. Acetal-3. This reaction is shown below. [Chemical 33]

1-4. Synthesis of fluorine-containing cyclic hemiacetal-4 Instead of using crotyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the β-methylallyl used in the synthesis of the above-mentioned fluorine-containing cyclic hemiacetal-2 Except for alcohols, a reaction represented by the following formula was performed in the same procedure as in the synthesis of a fluorinated cyclic hemiacetal-2 to obtain a fluorinated cyclic hemiacetal-4 in a yield of 75%. This reaction is shown below. [Chem 34]

1-5. Synthesis of fluorine-containing cyclic hemiacetal-5 In addition to using 3-methyl-2-buten-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the fluorine-containing cyclic hemiacetal-2 Except for the β-methylallyl alcohol used in the synthesis, a reaction shown in the following formula was performed in the same procedure as the synthesis of the fluorinated cyclic hemiacetal-2 to obtain a fluorinated cyclic half in a yield of 65%. Acetal-5. This reaction is shown below. [Chemical 35]

1-6. Synthesis of fluorine-containing cyclic hemiacetal-6 In a 100 ml glass flask equipped with a stirrer, the β-methylallyl alcohol β-methylallyl alcohol was protected with a third butyldimethylsilyl group according to a conventional method. -Methylallyl-tert-butyldimethylsilyl ether 1.86 g (0.01 mol), and trifluoropyruvic acid 1,1,1,3,3,3-hexafluoroisopropyl ester 2.92 g (0.01 mol). Then, the temperature in the reactor was raised to 50 ° C., and the stirring was continued for 18 hours. After the reaction was completed, the contents were taken out and transferred to a separating funnel. 10 ml of 3.5% by mass hydrochloric acid was added, and after stirring for 2 hours, the organic layer and the aqueous layer were separated. To the organic layer was added 10 ml of a sodium hydroxide solution having a concentration of 4% by mass, and after stirring for 1 hour, the organic layer was separated and separated by silica gel column chromatography. 19.0 g of a fluorine-containing cyclic hemiacetal-6 represented by the following formula was obtained in a yield of 52%. This reaction is shown below. [Chemical 36] <NMR analysis results> ¹ H-NMR (solvent: deuterochloroform, standard 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) isomers 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: deuterochloroform, standard material: C ₆ D ₆ ): δ (ppm ) -77.1 (6F, m), -78.5 (3F, m)

[Synthesis of trifluoropyruvic acid 1,1,1,3,3,3-hexafluoroisopropyl ester] The following shows trifluoropyruvic acid 1,1 used in the synthesis of the above-mentioned fluorine-containing cyclic hemiacetal-6. Synthesis sequence of 1,1,3,3,3-hexafluoroisopropyl ester.

To a 10 ml glass flask with a stirrer was added 17.0 g (0.1 mol) of ethyl trifluoropyruvate (Central Glass Co., Ltd., trade name: E-TFPA), and 10% by mass of sodium hydroxide water 50 was added thereto. ml and stir for 2 hours. After concentrating under reduced pressure and distilling off ethanol, 55 ml of 10% by mass hydrochloric acid was added for neutralization, and 30 ml of dichloromethane was added. The trifluoropyruvic acid produced was extracted in a dichloromethane layer. The methylene chloride layer was separated, and after removing water with a desiccant, 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. HFIP ( Central Glass Co., Ltd.) 16.8 g (0.1 mol), and further stirred for 2 hours. To the reaction solution, 30 ml of hydrochloric acid having a concentration of 3.5% by mass was added, 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 trifluoropyruvic acid 1,1,1,3,3,3-hexafluoroisopropyl ester at a yield of 55%. This reaction is shown below. [Chemical 37] <NMR analysis results> ¹ H-NMR (solvent: deuterochloroform, standard material: TMS): δ (ppm) 5.65 (1H, m) ¹⁹ F-NMR (solvent: deuterochloroform, standard material: C ₆ D ₆ ): δ (ppm) -76.6 (6F, s), -83.1 (3F, s)

1-7. Synthesis of fluorine-containing cyclic hemiacetal-7 In addition to the use of 2,3,2-trifluoroethyl trifluoropyruvate, which was synthesized separately, instead of the above-mentioned synthesis of fluorine-containing cyclic hemiacetal Except for trifluoropyruvic acid 1,1,1,3,3,3-hexafluoroisopropyl ester, the reaction shown in the following formula was carried out in the same order as the synthesis of the fluorinated cyclic hemiacetal-6. Yield 61%. Fluorinated cyclic hemiacetal-7 was obtained. This reaction is shown below. [Chemical 38]

[Synthesis of 2,2,2-trifluoroethyl trifluoropyruvate] The following shows the trifluoropyruvate 2,2,2-trifluoroethyl used in the synthesis of the above-mentioned fluorinated cyclic hemiacetal-7. The synthesis order.

In a 100 ml glass flask with a stirrer, 16.2 g (0.1 mol) of CDI (carbonyldiimidazole) was added to a dichloromethane solution of trifluoropyruvic acid as shown in the previous synthesis example, and the mixture was stirred at room temperature for 1 hour. Then, 10.0 g (0.1 mol) of 2,2,2-trifluoroethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred for 2 hours. To the reaction solution, 30 ml of hydrochloric acid having a concentration of 3.5% by mass was added, 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 trifluoropyruvate 2,2,2-trifluoroethyl ester in a yield of 50%. This reaction is shown below. [Chemical 39]

2. Synthesis of fluorine-containing monomer The fluorine-containing cyclic hemiacetal-1, 2, 6, 7 of the above formula (7) was used to synthesize a fluorine-containing monomer (4).

2-1. Synthesis of fluorinated monomer-1 In a 300 ml glass flask equipped with a stirrer, fluorinated cyclic hemiacetal-1 22.4 g (0.1 mol), triethylamine 15.1 g (0.15 mol) were added as To a polymerization inhibitor, methoxyphenol (1000 ppm), 16.9 g (0.11 mol) of methacrylic anhydride 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 stirred. After liquid separation, 20 ml of 1% by weight sodium hydroxide water was added and stirred for 1 hour, followed by liquid separation. After washing the organic layer twice with 30 ml of pure water, distillation under reduced pressure was performed at 1.1 kPa and a temperature of 70 ° C to 72 ° C to obtain a fluorine-containing monomer-1 at a yield of 85%. This reaction is shown below. [Chemical 40] <NMR analysis results> ¹ H-NMR (solvent: deuterochloroform, standard 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: deuterochloroform, standard material: C ₆ D ₆ ): δ (ppm) -77.5 (3F, s) , -79.5 (3F, s)

2-2. Synthesis of fluorinated monomer-2 except that fluorinated cyclic hemiacetal-2 is used instead of the fluorinated cyclic hemiacetal-1 used in the synthesis of the above-mentioned fluorinated monomer-1. The fluorinated monomer-1 was synthesized in the same order, and the reaction shown in the following formula was performed to obtain a fluorinated monomer-2 in a yield of 93%. This reaction is shown below. [Chemical 41] <NMR Analysis Results> The results of nuclear magnetic resonance analysis are shown below. ¹ H-NMR (solvent: deuterochloroform, standard substance: TMS): δ (ppm) 1.19 (3H, s) (isomer A), 1.23 (3H, s) (isomer B), no difference after that The peaks of the structures are separated and assigned to the mixture. 1.92 (3H, s), 2.32-2.59 (2H, m), 2.72-2.89 (2H, m), 5.65 (1H, q), 6.14 (1H, q), 6.17 (1H, dd) ¹⁹ F-NMR ( Solvent: deuterochloroform, standard material: C ₆ D ₆ ): δ (ppm) -77.3 (3F, s), -79.0 (3F, s)

2-3. Synthesis of fluorinated monomer-3 In addition to using 2-fluoropropenyl chloride instead of the methacrylic anhydride used in the synthesis of the above-mentioned fluorinated monomer-2, the synthesis with fluorinated monomer-2 In the same order, a reaction represented by the following formula was performed to obtain fluoromonomer-3 in a yield of 70%. This reaction is shown below. [Chemical 42] <Results of NMR analysis> ¹ H-NMR (solvent: deuterochloroform, standard substance: TMS): δ (ppm) 1.17 (3H, s) (isomer A), 1.22 (3H, s) (isomer B) After that, no peak separation of the isomers occurred, which belonged to the mixture. 1.92 (3H, s), 2.32-2.59 (2H, m), 2.72-2.89 (2H, m), 6.12 (1H, q), 6.45 (1H, q), 6.68 (1H, d) ¹⁹ F-NMR ( Solvent: deuterochloroform, standard material: C ₆ D ₆ ): δ (ppm) -10.3 (1F, S), -77.3 (3F, s), -79.0 (3F, s)

2-4. Synthesis of fluorinated monomer-4 In addition to using 2-methacryloxyethylenyl chloride instead of the methacrylic anhydride used in the synthesis of the above-mentioned fluorinated monomer-2, The synthesis of isomer-2 was carried out in the same order, and a reaction represented by the following formula was performed to obtain a fluorine-containing monomer-4 at a yield of 80%. This reaction is shown below. [Chemical 43] <NMR analysis results> ¹ H-NMR (solvent: deuterochloroform, standard material: 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: deuterochloroform, standard substance: C ₆ D ₆ ): δ (ppm) -77.7 (3F, s), -79.6 (3F, s)

2-5. Synthesis of fluorinated monomer-5 In a 300 ml glass flask with a stirrer, fluorinated cyclic hemiacetal-2 was added 22.4 g (0.1 mol), triethylamine 15.1 g (0.15 mol), and potassium iodide 0.8 g (0.05 mol), dimethylformamide 20 ml, methoxyphenol (1000 ppm) as a polymerization inhibitor, and 16.3 g (0.11 mol) of chloroethyl methacrylate were 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 stirred, and after liquid separation, 50 ml of 5% by weight hydrochloric acid water was added and stirred for 30 minutes, followed by liquid separation. After washing the organic layer twice with 50 ml of pure water, distillation under reduced pressure was performed at 1.0 kPa and a temperature of 89 ° C to 91 ° C to obtain a fluorine-containing monomer-5 at a yield of 45%. This reaction is shown below. [Chemical 44] <NMR analysis results> ¹ H-NMR (solvent: deuterochloroform, standard material: 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: deuterochloroform , Reference material: C ₆ D ₆ ): δ (ppm) -77.0 (3F, s), -79.3 (3F, s)

2-6. Synthesis of fluorine-containing monomer-6 In addition to using fluorine-containing cyclic hemiacetal-6 instead of the fluorine-containing cyclic hemiacetal-2 used in the synthesis of the above-mentioned fluorine-containing cyclic monomer-2, In the same procedure as the synthesis of the fluorinated monomer-2, a reaction represented by the following formula was performed to obtain a fluorinated monomer-6 in a yield of 78%. This reaction is shown below.

[Chemical 45] <NMR analysis results> ¹ H-NMR (solvent: deuterochloroform, standard material: 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: deuterochloroform, standard substance: C ₆ D ₆ ): δ (ppm) -77.5 (6F, m), -79.5 (3F, m)

2-7. Synthesis of fluoromonomer-7 except that fluorinated cyclic hemiacetal-7 is used instead of the fluorinated cyclic hemiacetal-2 used in the synthesis of the above-mentioned fluorinated monomer-2. The fluoromonomer-7 was synthesized in the same order, and the reaction represented by the following formula was performed to obtain fluoromonomer-7 in a yield of 74%. This reaction is shown below. [Chemical 46] <Results of NMR analysis> ¹ H-NMR (solvent: deuterochloroform, standard substance: TMS): δ (ppm) 1.22 (3H, s), 1.89 (3H, s), 2.24-2.50 (2H, m), 2.68- 2.87 (2H, m), 4.86 (2H, m), 5.65 (1H, q), 6.13 (1H, q), 6.18 (1H, dd) ¹⁹ F-NMR (solvent: deuterochloroform, standard substance: C ₆ D ₆ ): δ (ppm) -77.9 (3F, m), -78.5 (3F, m)

2-8. Synthesis of fluorinated monomer-8 In addition to using 2-fluoropropenyl chloride instead of the methacrylic anhydride used in the synthesis of the above-mentioned fluorinated monomer-6, the synthesis with fluorinated monomer-6 In the same order, a reaction represented by the following formula was performed to obtain a fluorine-containing monomer-8 in a yield of 68%. This reaction is shown below. [Chemical 47] <Results of NMR analysis> ¹ H-NMR (solvent: deuterochloroform, standard substance: TMS): δ (ppm) 1.17 (3H, s), 2.27-2.52 (2H, m), 2.62-2.82 (2H, m), 5.64 (1H, q), 5.93 (1H, m), 6.42 (1H, q), 6.68 (1H, dd) ¹⁹ F-NMR (solvent: deuterochloroform, standard material: C ₆ D ₆ ): δ (ppm) -10.1 (1F, S), -77.9 (6F, m), -79.0 (3F, m)

2-9. Synthesis of fluorinated monomer-9 In addition to using 2-fluoropropenyl chloride instead of the methacrylic anhydride used in the synthesis of the above-mentioned fluorinated monomer-7, the synthesis with fluorinated monomer-7 In the same order, a reaction represented by the following formula was performed to obtain a fluorine-containing monomer-9 in a yield of 65%. This reaction is shown below. [Chemical 48] <Results of NMR analysis> ¹ H-NMR (solvent: deuterochloroform, standard substance: TMS): δ (ppm) 1.17 (3H, s), 2.27-2.52 (2H, m), 2.62-2.82 (2H, m), 4.93 (2H, m), 5.64 (1H, q), 6.42 (1H, q), 6.68 (1H, dd) ¹⁹ F-NMR (solvent: deuterochloroform, standard material: C ₆ D ₆ ): δ (ppm) -10.4 (1F, S), -77.1 (6F, m), -79.3 (3F, m)

3. Synthesis of comparative monomers For comparison with the fluorinated monomers -1 to 7 of the present invention, the comparative monomers 1-3 which do not belong to the fluorinated monomer represented by formula (6) were synthesized.

3-1. Synthesis of Comparative Monomer-1 A 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, and 0.1 g of p-toluenesulfonic acid was added and stirred for 1 hour. Add 3 ml of triethylamine to stop the reaction. The obtained reaction mixture was washed with 50 ml of water, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off, distillation under reduced pressure was performed at a temperature of 0.4 kPa and a temperature of 66 ° C to 67 ° C to obtain 50 g of a comparative monomer. This reaction is shown below. [Chemical 49]

3-2. Synthesis of Comparative Monomer-2 A 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 butyllithium (1.6 M hexane solution) was added under a nitrogen atmosphere at 5 ° C, and the mixture was stirred at 5 ° C for 1 hour. Next, 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 water-based post-treatment, it was purified by silica gel column chromatography to obtain 25.3 g of triol as a synthetic intermediate. A mixture of 24 g of a 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, it was neutralized with dilute hydrochloric acid, and the organic layer was separated. The crude product obtained by usual post-treatments such as washing, drying, and concentration was subjected to distillation under reduced pressure to obtain 20 g of hemiacetal. The mixture of 3.2 g of 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. The insoluble matter was separated by filtration, concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain Comparative monomer-2 3 g. This reaction is shown below. [Chemical 50] (Mel stands for methyl iodide)

3-3. Synthesis of Comparative Monomer-3 In a 300 ml glass flask with a stirrer, vinyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., the same below) 33.6 g (0.3 mol) and HFIP 52.9 g ( After 0.315 mol), 0.74 g (7.5 mmol) of sulfuric acid was slowly added, and the mixture was stirred at a reaction temperature of 40 ° C. for 6 hours to perform a reaction represented by the following formula. This reaction is shown below. [Chemical 51] After the reaction solution was cooled 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, left to stand and separated, and an organic layer was taken. The collected organic layer was subjected to distillation under reduced pressure to obtain 39 g of a comparative monomer-3 at a yield of 47%. The boiling point of the obtained comparative monomer-3 was 62 ° C at a pressure of 4.0 kPa.

4. Polymer synthesis uses fluoromonomers -1-9, comparative monomers 1-3, and hexafluoroisopropyl methacrylate (Central Glass Co., Ltd., trade name HFIP-) as comparative monomer 4. M). Synthesis of fluoropolymers 1-12 and comparative polymers-1-7. The fluoropolymers 1 to 12 belong to the fluoropolymer (4). The 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).

In addition, for the fluoropolymers 1 to 9 and the comparative polymers 1-4, in order to clearly show the effect of the monomer and the difference in performance, a self-polymer was synthesized and its performance was compared. For fluoropolymers -10-12 and comparative polymers-5-7, comonomers were fixed to 5-methacryloxy-2,6-norkanyl lactone (MNLA) for The performance of the fluorine-containing monomer of the present invention and the comparative monomer as a material for resist was compared.

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

4-1. Synthesis of fluoropolymer-1 In a 300 ml glass flask with a stirrer, 29.2 g (0.1 mol) of fluoromonomer-1 as a solvent was added at room temperature. g, a methyl ethyl ketone solution having a concentration of 33% by mass. After adding 0.8 g (0.005 mol) of 2,2'-azobis (isobutyronitrile) (hereinafter sometimes referred to as AIBN, manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, degassing while stirring, The inside of the flask was replaced with nitrogen, and the temperature was raised to 80 ° C, followed by reaction for 6 hours. The content after the reaction was added dropwise to 500 g of n-heptane to obtain a white precipitate. The precipitate was separated by filtration, and dried under reduced pressure at a temperature of 60 ° C. to obtain 25.6 g of a fluorinated polymer-1 containing a repeating unit based on a fluorinated monomer-1 as a white solid at a yield of 88%. [Chemical 52] <GPC measurement result> Mw = 22,000, Mw / Mn = 2.0

4-2. Synthesis of fluoropolymer-2 In addition to using fluoromonomer-2 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-1, The synthesis was performed in the same order, and a fluoropolymer-2 containing the following repeating units was synthesized. The fluoropolymer-2 was obtained in a yield of 87%. [Chem 53] <GPC measurement result> Mw = 23,100, Mw / Mn = 2.1

4-3. Synthesis of fluoropolymer-3 In addition to using fluoromonomer-3 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-1, The fluoropolymer-3 containing the following repeating units was synthesized in the same order as the synthesis, and the fluoropolymer-3 was obtained in a yield of 93%. [Chemical 54] <GPC measurement result> Mw = 21,200, Mw / Mn = 2.3

4-4. Synthesis of fluoropolymer-4 In addition to using fluoromonomer-4 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-1, The synthesis was performed in the same order, and a fluoropolymer-4 containing the following repeating units was synthesized. The fluoropolymer-4 was obtained in a yield of 92%. [Chem 55] <GPC measurement result> Mw = 22,500, Mw / Mn = 2.1

4-5. Synthesis of fluoropolymer-5 In addition to using fluoromonomer-5 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-1, The synthesis was performed in the same order, and a fluoropolymer-5 containing the following repeating units was synthesized, and the fluoropolymer-5 was obtained at a yield of 90%. [Chemical 56] <GPC measurement result> Mw = 24,200, Mw / Mn = 2.3

4-6. Synthesis of fluoropolymer-6 In addition to using fluoromonomer-6 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-1, The synthesis was performed in the same order, and a fluoropolymer-6 containing the following repeating units was synthesized, and the fluoropolymer-6 was obtained in a yield of 72%. [Chemical 57] <GPC measurement result> Mw = 20,700, Mw / Mn = 2.5

4-7. Synthesis of fluoropolymer-7 In addition to using fluoromonomer-7 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-1, The fluoropolymer-7 containing the following repeating units was synthesized in the same order as the synthesis, and the fluoropolymer-7 was obtained in a yield of 78%. [Chem 58] <GPC measurement result> Mw = 20,100, Mw / Mn = 2.2

4-8. Synthesis of fluoropolymer-8 In addition to using fluoromonomer-8 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-1, The synthesis was performed in the same order, and a fluoropolymer-8 containing the following repeating units was synthesized, and the fluoropolymer-8 was obtained at a yield of 90%. [Chemical 59] <GPC measurement result> Mw = 19,700, Mw / Mn = 2.3

4-9. Synthesis of fluoropolymer-9 In addition to using fluoromonomer-9 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-1, The fluoropolymer-9 containing the following repeating units was synthesized in the same order as the synthesis, and the fluoropolymer-9 was obtained in a yield of 89%. [Chemical 60] <GPC measurement result> Mw = 20,900, Mw / Mn = 2.1

4-10. Synthesis of fluoropolymer-10 In a glass flask, fluorinated monomer-1 (29.2 g (0.1 mol)) was charged at room temperature (about 20 ° C) to provide adhesion when made into a resist 11.1 g (0.05 mol) of 5-methacryloxy-2,6-norkanyl lactone (MNLA) and n-dodecyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.67 g 82.8 g of 2-butanone was added to dissolve it. 1.7 g of 2,2'-azobis (isobutyronitrile) (hereinafter sometimes referred to as AIBN, manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was added, and after degassing while stirring, the inside of the flask was deaerated. After replacing with nitrogen, the temperature was raised to 75 ° C, and the reaction was allowed to proceed for 16 hours. The content after the reaction was added dropwise to 620.0 g of n-heptane to obtain a white precipitate. The precipitate was separated by filtration, and dried under reduced pressure at a temperature of 60 ° C to obtain a white solid containing 85% of a repeating unit derived from the fluorinated monomer-1 and a repeating unit derived from MNLA as a white solid. Fluoropolymer-8 34 g. [Chem 61] <NMR measurement result> The composition ratio of each repeating unit in the fluoropolymer-10 was measured by NMR. The measurement results are expressed in mol% as repeating units derived from fluorinated monomer-10: repeating units derived from MNLA = 67: 33. <GPC measurement result> Mw = 8,500, Mw / Mn = 1.7

4-11. Synthesis of fluoropolymer-11 In addition to using fluoromonomer-2 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-10, The fluoropolymer-11 was synthesized in the same order as the synthesis, and a fluoropolymer-11 containing the following repeating units was obtained in a yield of 86%. [Chem 62] <NMR measurement result> The composition ratio of each repeating unit in the fluoropolymer-11 was measured by NMR. The measurement results are expressed in mol% as repeating units derived from fluorinated monomer-11: repeating units derived from MNLA = 65: 35. <GPC measurement result> Mw = 8,700, Mw / Mn = 1.6

4-12. Synthesis of fluoropolymer-12 In addition to using fluoromonomer-6 instead of fluoromonomer-1 used in the above-mentioned synthesis of fluoropolymer-10, The fluoropolymer-12 was synthesized in the same order as the synthesis, and a fluoropolymer-12 containing the following repeating units was obtained in a yield of 73%. [Chem 63] <NMR measurement result> The composition ratio of each repeating unit in the fluoropolymer-12 was measured by NMR. The measurement results are expressed in mol% as repeating units derived from fluoromonomer-12: repeating units derived from MNLA = 64: 36. <GPC measurement results> Mw = 7,700, Mw / Mn = 1.7

5. Synthesis of Comparative Polymers In order to compare the fluoropolymers 1 to 10 of the present invention, the comparative polymers -1 to 7 which do not belong to the fluoropolymer (4) were synthesized.

5-1. Synthesis of Comparative Polymer-1 In addition to the use of Comparative Monomer-1 instead of the Fluoromonomer-1 used in the synthesis of the above-mentioned Fluoropolymer-1, it was synthesized with Fluoropolymer-1 In the same order, Comparative Polymer-1 containing the following repeating units was synthesized. [Chemical 64] <GPC measurement result> Mw = 20,100, Mw / Mn = 2.2

5-2. Synthesis of Comparative Polymer-2 In addition to the use of Comparative Monomer-2 instead of the Fluoromonomer-1 used in the above-mentioned synthesis of Fluoropolymer-1, it was synthesized with Fluoropolymer-1 In the same order, Comparative Polymer-2 containing the following repeating units was synthesized. [Chem 65] <GPC measurement result> Mw = 23,400, Mw / Mn = 2.1

5-3. Synthesis of Comparative Polymer-3 In addition to the use of Comparative Monomer-3 instead of the Fluoromonomer-1 used in the synthesis of the Fluoropolymer-1 above, the synthesis with Fluoropolymer-1 In the same order, Comparative Polymer-3 containing the following repeating units was synthesized. [Chemical 66] <GPC measurement result> The GPC measurement result was Mw = 22,800 and Mw / Mn = 2.1.

5-4. Synthesis of Comparative Polymer-4 In addition to the use of Comparative Monomer-4 instead of the Fluoromonomer-1 used in the synthesis of the Fluoropolymer-1 described above, the synthesis with Fluoropolymer-1 In the same order, Comparative Polymer-4 containing the following repeating units was synthesized. [Chemical 67] <GPC measurement result> Mw = 20,100, Mw / Mn = 2.1

5-5. Synthesis of Comparative Polymer-5 In addition to using Comparative Monomer-1 instead of the Fluoromonomer-1 used in the synthesis of the Fluoropolymer-8 described above, the synthesis with the Fluoromonomer-8 In the same order, a comparative polymer-5 containing the following repeating units was synthesized, and a comparative polymer-5 was obtained in a yield of 89%. [Chemical 68] <NMR measurement result> The composition ratio of each repeating unit in Polymer-5 was compared by NMR measurement. The measurement results are expressed in mol% as repeating units derived from Comparative Monomer-1: repeating units derived from MNLA = 67: 33. <GPC measurement results> Mw = 8, 300, Mw / Mn = 1.7

5-6. Synthesis of Comparative Polymer-6 In addition to the use of Comparative Monomer-2 instead of the Fluoromonomer-1 used in the synthesis of the Fluoropolymer-8, the synthesis with the Fluoromonomer-8 In the same order, a comparative polymer-6 containing the following repeating units was synthesized, and a comparative polymer-6 was obtained in a yield of 83%. [Chemical 69] <NMR measurement result> The composition ratio of each repeating unit in Polymer-6 was compared by NMR measurement. The measurement results are expressed in mol% as repeating units derived from Comparative Monomer-2: repeating units derived from MNLA = 65: 35. <GPC measurement results> Mw = 8, 900, Mw / Mn = 1.6

5-7. Synthesis of Comparative Polymer-7 In addition to using Comparative Monomer-4 instead of the Fluoromonomer-1 used in the synthesis of the Fluoropolymer-8 described above, the synthesis with the Fluoromonomer-8 In the same order, a comparative polymer-7 containing the following repeating units was synthesized, and a comparative polymer-7 was obtained at a yield of 81%. [Chem 70] <NMR measurement result> The composition ratio of each repeating unit in Polymer-7 was compared by NMR measurement. The measurement results are expressed in mol% as repeating units derived from Comparative Monomer-3: repeating units derived from MNLA = 66: 34. <GPC measurement results> Mw = 8, 100, Mw / Mn = 1.6

5-8. Repeating units of fluoropolymer-1 to 10 and comparative polymer-1 to 7 The repeating units contained in fluoropolymer-1 to 10 and comparative polymer 1 to 7 are shown below. [Chemical 71]

5-9. Composition, molecular weight, and yield of fluoropolymer-1 to 10 and comparative polymer-1 to 7 Table 1 shows the composition of fluoropolymer-1 to 10 and comparative polymer-1 to 7 (repeat Ratio of units), weight average molecular weight, molecular weight distribution, and yield.

[Table 1]

5-10. Fluoropolymer-1 to 9, Glass transition point and 5% weight reduction of Comparative polymer-1 to 4 Fluoropolymer-1 to 9, Comparative polymer-1 to 4 glass transition point and 5% weight reduction rate. [Method for measuring glass transition point and 5% weight reduction rate] The thermal properties of fluoropolymers 1 to 9 and comparative polymers 1-4 were measured. The glass transition point (hereinafter sometimes referred to as Tg) was measured using a differential scanning calorimeter (hereinafter sometimes referred to as DSC) and a differential thermal-thermogravimetric measurement device (hereinafter sometimes referred to as DTA) manufactured by Hitachi-hightech Co., Ltd. And 5% weight reduction rate (hereinafter sometimes referred to as Td5) under thermogravimetric measurement.

[Measurement Results] Table 2 shows the measurement results of Tg and Td5 of the fluoropolymers 1 to 9 and the comparative polymers 1-4. Known in pattern forming materials used in lithography and printed electronics, the higher Tg and Td5 tend to have the following tendency: the mask pattern is transferred more faithfully, and the line edge roughness of the resulting pattern or Line Width Roughness is better.

[Table 2]

The fluoropolymers 1-9 and comparative polymers 1-2 having a cyclic acetal structure have a Tg higher than that of the chain-like comparative polymers 3 and 4 by approximately 25 ° C. The fluoropolymers 1 to 3, 8, and 9 showed higher Tg compared to the comparative polymer 1 having the same skeleton without fluorine atoms.

6. Pattern-forming composition for printed electronics 6-1. Preparation of pattern-forming composition for printed electronics The use of fluorinated polymers-1 to 9 and comparative polymers containing repeating units shown below- 1 to 4 to prepare the pattern forming compositions 1 to 9 of the present invention, and the comparative compositions 1 to 4 for comparison. [Chemical 72]

N-hydroxynaphthalene dimethylideneimine-trifluoromethanesulfonate was added as (A) acid generator to fluoropolymer-1 to 9 and comparative polymer-1 to 4, and (D) 2-Isopropyl-9-oxosulfur sensitizer, 2-phenylbenzimidazole as (C) quencher, and diethylene glycol methyl ether as (B) organic solvent, for pattern formation Compositions 1 to 9 and Comparative Compositions 1-4. The composition ratios of the pattern forming compositions-1 to 9 and the comparative compositions-1 to 4 are expressed in terms of parts by mass as a polymer: (A) acid generator: (D) sensitizer: (C) quencher : (B) The organic solvent is prepared in a manner of 100: 2: 1: 0.05: 300.

6-2. Film formation of patterning composition for printed electronics technology Pattern composition -1 to 9 prepared by spin coater coating on glass substrate, comparative composition 1-4, in Dry on a hot plate heated to 100 ° C for 2 minutes to form a film with a thickness of 0.5 μm. Then, the film was irradiated with a high-pressure mercury lamp. Furthermore, the photomask was irradiated with ultraviolet light using a high-pressure mercury lamp, the pattern of the photomask was transferred to a film, and then it was heated and dried at a temperature of 100 ° C. for 5 minutes using a hot plate. In this way, a glass substrate obtained by forming a pattern (a hydrophilic pattern) including a hydrophilic portion and a water-repellent portion was obtained.

6-3. Measurement of the contact angle before and after exposure of the film including the composition for pattern formation and the formation of a pattern using an aqueous ink [Measurement of the contact angle] A water droplet was placed on the film on the glass substrate, and a contact angle meter (Kyowa (Interface Science Co., Ltd.), the static contact angle of the ultraviolet light unirradiated portion and the irradiated portion were measured by the droplet method, and the dynamic receding contact angle of the ultraviolet light unirradiated portion was measured by the expansion and contraction method. In the present invention, the so-called static contact angle refers to the angle formed when the water droplet is placed on the film surface and drops, and the so-called dynamic receding contact angle refers to the contact angle when the droplet is attracted by a needle or the like, and the so-called dynamic The forward contact angle refers to the contact angle when a water droplet is ejected by a needle or the like, and the water droplet expands.

In patterning materials used in lithography and printed electronics, the patterning film is preferably a high static contact angle of the unirradiated portion, the mask pattern is more faithfully transferred, and the edge roughness or line of the obtained pattern is Wide roughness is better to obtain high resolution patterns. In addition, when the static contact angle of the irradiated portion is low and the difference in contact angle between the unirradiated portion and the irradiated portion is large, it is easy to cut the pattern.

When the dynamic receding contact angle of the non-irradiated part of the pattern-forming film is high, the mask pattern is transferred more faithfully, and the line pattern has a better line edge roughness or line width roughness, and a pattern with high resolution is obtained. In order to obtain a high-resolution pattern, it is preferable that in the unirradiated portion, both the dynamic forward contact angle and the dynamic backward contact angle are high, and the hysteresis (dynamic forward contact angle-dynamic backward contact angle) is small.

[Ink pattern] On the affinity pattern on the obtained glass substrate, an automatic minimum contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number MCA-2) was used, and water was added dropwise through a borosilicate glass capillary (Microcapillary) The ink was 50 pl, and the pattern was observed under a microscope after 5 seconds. In addition, it is good if the water-based ink is patterned along the affinity pattern, and it is a fail if it overflows from the pattern, and it is a pass if any of them cannot be distinguished.

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

[table 3]

[Contact Angle] The composition for forming a pattern containing a trifluoromethyl group in Examples 1 to 9 had a large contact angle in the unirradiated portion of ultraviolet light, and showed good water repellency.

The contact angle of the non-irradiated portion of the film formed from the comparative composition-1 with the comparative polymer-1 containing no fluorine atom from Comparative Example 1 was 73 °, and the receding contact angle was 58 °. The contact angle of the ultraviolet irradiated portion of the film formed from the comparative composition-2 using the comparative polymer-2 containing a fluorine atom from Comparative Example 2 was 94 degrees, and from the composition for pattern formation from Examples 1 to 9- The films formed from 1 to 9 had poor water repellency. The comparative composition-4 of the comparative example 4 used the comparative polymer-4 which has hexafluoroisopropyl group which does not have acid dissociation property, and the contact angle of the ultraviolet-ray irradiation part was large, and did not show hydrophilicity.

[Ink Pattern] In the affinity pattern formed by using each of the pattern forming compositions 1 to 9 using fluoropolymers 1 to 9 in Examples 1 to 9, the contact angle of the unirradiated portion and the contact of the irradiated portion The difference between the angles is more than 40 °, and the receding contact angle is high, so the water-based ink in the water-repellent part flows quickly to the hydrophilic part.

On the other hand, in the affinity pattern formed by using the comparative composition-2 with the comparative polymer-2, the difference between the unirradiated portion and the illuminated portion of the affinity pattern is about 30 °, and the receding contact angle is relatively low. At 80 °, the residual water-based ink in the water-repellent part can be seen. In Comparative Example 1, Comparative Polymer-1 did not contain a fluorine atom. The water repellency of the water repellent part was insufficient, water wettability existed, and the water-based ink remained. On the other hand, Comparative Example 4 used a comparative polymer-4 having hexafluoroisopropyl group without acid dissociation, and did not form a water repellent. Pattern to form a film of water-based ink on the surface of the film.

7. Resist 7.1 Preparation of resist Using a fluoropolymer-10 to 12 and a comparative polymer-5 to 7 containing the following repeating units as shown below, a resist was prepared as a resist solution- 1 to 3 and comparative resists 1-3. [Chemical 73]

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

[Film formation of a resist film] An anti-reflection film solution (manufactured by Nissan Chemical Industries, Ltd., product number ARC29A) was coated on a silicon wafer, and then dried at 200 ° C for 60 seconds to set a film thickness of 78 nm. Anti-reflection film. Then, each of the above resist solutions was filtered through a 0.2 μm membrane filter, and then applied to an anti-reflection film using a spin coater at 1,500 rpm and dried on a hot plate at 100 ° C. for 90 seconds to form Resist film.

7.2 Evaluation of the solubility of the developing solution of the resist and the resolution of the resist pattern The evaluation of the solubility of the developing solution of the resist and the resolution of the resist pattern and the measurement of the contact angle were performed for each resist film. 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, and the solubility to the developer was tested. The alkaline developer is used in a 2.38 mass% tetramethylammonium hydroxide aqueous solution (hereinafter sometimes referred to as TMAH) as a standard used in lithography. The solubility of the resist film is determined by measuring the film thickness of the resist film after immersion using a light interference-type film thickness meter. The case where the resist film completely disappeared was rated as "soluble", and the case where the film thickness of the resist film did not change was rated as "insoluble".

[Sensitivity and resolution of resist pattern] A photomask having a pattern with a line and a gap of 30 nm in the width of the wiring and the distance between adjacent wirings is prepared. The silicon wafer on which the resist film was formed was pre-baked at 100 ° C for 60 seconds, and then an argon fluoride excimer laser was used to oscillate at a wavelength of 193 nm. The system is irradiated with ultraviolet light to expose the resist film. While rotating the silicon wafer, drop pure water for 2 minutes. Thereafter, it was subjected to post-exposure baking at 120 ° C for 60 seconds, and thereafter developed using TMAH as an alkaline developer, and then immersed in pure water for 30 seconds, and then dried by an air knife. . Then, baking was performed at 100 ° C. for 45 seconds, and thus a silicon wafer having a resist pattern was obtained. <Sensitivity> In the above-mentioned operation, the optimum exposure amount Eop (mj / cm ² ) when a pattern of lines and gaps of 30 nm was formed once was obtained as a standard for sensitivity. <Resolution> The patterned silicon wafer was cut, and the resist pattern on the wafer with the pattern of 30 nm lines and gaps transferred thereon was observed with a microscope. Those who could not confirm the line edge roughness were rated The resolution is "excellent", although it can be confirmed but is small, it is rated as "good", and the line edge roughness is marked as "failed".

[Measurement method of contact angle] The contact angle of a water droplet was measured on a resist film on the obtained silicon wafer using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). For a resist film with a higher contact angle, the mask pattern is transferred more faithfully, and the resulting pattern has better line edge roughness or line width roughness, and a pattern with high resolution is obtained. In addition, in the liquid immersion exposure lithography, water does not immerse in the film, and the occurrence of watermark defects is less.

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

[Table 4]

[Evaluation of the solubility of the developing solution] As shown in Table 4, the resists 1-3 and the comparative resists 1-3 were insoluble in the alkaline developing solution in the unexposed state, and became available after exposure. Soluble. Therefore, all the resists shown in the test were used as photosensitive resins and had a dissolution contrast with TMAH as an alkaline developer.

[Evaluation of the sensitivity and resolution of the resist pattern] <Sensitivity> As for the sensitivity, the optimum exposure amount of the resists 1-3 was compared with the optimum exposure amount of the resists 1-3, and both were low values. Compared with the cyclic acetal structure of the structure of Comparative Example Resist-2, the value is relatively low. Further, the optimum exposure amount of the comparative resist-1 having a cyclic acetal structure having no fluorine atom is a low value, and the optimum exposure amount of the comparative resist-3 having a non-cyclic acetal structure is a minimum value. <Resolution> As shown in Table 4, when using Resist-1 to 3 and Comparing Resist-2, a desired pattern with a line and gap pattern of 30 nm was formed and a good resolution was displayed. It is judged as "good". On the other hand, when comparing the case of the resist-1, the line edge roughness was confirmed, and it was judged as "failed." In the case of comparing the resist-3, it was confirmed that the minute line edge roughness was inferior to the resists 1-3 and the comparative resist-2, and thus it was judged as "passing".

[Measurement result of contact angle] The water receding contact angles of the resists 1 to 3 are higher than those of the comparative resists 1 and 2. The comparative resist 2 contained a polymer having a fluorinated cyclic acetal structure, but it was inferior to the resists 1 to 3.

Claims (16)

A fluoropolymer containing 10 to 90 mol% of repeating units represented by formula (1), and the number average molecular weight of the above fluoropolymer is 1,000 to 100,000;

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and 7 of the hydrogen atoms bonded to the carbon atom in the alkyl group Less than 1 can be substituted with fluorine atoms; R ² ~ R ⁵ are hydrogen atoms, straight-chain C 1-10 or branched C 3-10 alkyl groups, bonded to carbon atoms in the alkyl group Less than 7 of the hydrogen atoms can be replaced by fluorine atoms; X is a single bond or a divalent group, and 7 or less hydrogen atoms contained in the divalent group can be replaced by fluorine atoms; Y is a carbon number of 1 ~ 3 The fluorine-containing alkyl group or carboxylic acid ester group (-COOR), the fluorine-containing alkyl group or carboxylic acid ester group contains 7 or less hydrogen atoms can be replaced by fluorine atoms; R is a fluorocarbon containing 1 to 3 carbon atoms base). The fluoropolymer according to claim 1, wherein R ² , R ⁴ and R ⁵ in the above formula (1) are hydrogen atoms. The fluorine-containing polymer according to claim 2, wherein Y in the above formula (1) is trifluoromethyl. A composition for forming a resist pattern, which contains the fluoropolymer according to any one of claims 1 to 3, an acid generator, a basic compound, and a solvent. A method for forming a resist pattern, comprising: a film forming step, which is to apply a resist pattern forming composition as described in claim 4 on a substrate to form a film; an exposure step, which is to irradiate an exposure wavelength through a photomask Electromagnetic waves or high-energy rays below 300nm, transfer the pattern of the photomask to the film; and the development step, which is to develop the film using a developing solution to obtain the pattern. An ink pattern forming composition comprising the fluoropolymer according to any one of claims 1 to 3, an acid generator, and a solvent. A method for forming an ink pattern, comprising: a film forming step, which is to apply the ink pattern forming composition according to claim 6 on a substrate to form a film; an exposure step, which is to irradiate the film with an exposure wavelength through a photomask For light of 150 nm or more and 500 nm or less, transfer the pattern of the photomask to the film to obtain a pattern forming film having a liquid-repellent portion and a lyophilic portion; and an ink pattern forming step, which is to coat the obtained pattern forming film Ink. An ink pattern forming method, comprising: a film forming step, which applies the ink pattern forming composition according to claim 6 on a substrate and heating the obtained coating film; a drawing step, which is followed by The drawing device scans the film to expose light with a wavelength of 150 nm or more and 500 nm or less, and draws a pattern on the film to obtain a pattern forming film having a liquid-repellent portion and a lyophilic portion; and an ink pattern forming step, which is based on the obtained pattern formation Ink is coated on the film. A fluorine-containing monomer, which is represented by formula (4);

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and 7 of the hydrogen atoms bonded to the carbon atom in the alkyl group Less than 1 can be substituted with fluorine atoms; R ² ~ R ⁵ are hydrogen atoms, straight-chain C 1-10 or branched C 3-10 alkyl groups, bonded to carbon atoms in the alkyl group Less than 7 of the hydrogen atoms can be replaced by fluorine atoms; X is a single bond or a divalent group, and 7 or less hydrogen atoms contained in the divalent group can be replaced by fluorine atoms; Y is a carbon number of 1 ~ 3 The fluorine-containing alkyl group or carboxylic acid ester group (-COOR), the fluorine-containing alkyl group or carboxylic acid ester group contains 7 or less hydrogen atoms can be replaced by fluorine atoms; R is a fluorocarbon containing 1 to 3 carbon atoms base). The fluorine-containing monomer according to claim 9, wherein R ² , R ⁴ and R ⁵ in the above formula (4) are hydrogen atoms. The fluorine-containing monomer according to claim 10, wherein Y in the above formula (4) is trifluoromethyl. A method for producing a fluorinated monomer represented by formula (4) of claim 9, which comprises cyclizing a hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether represented by the formula (11), And the step of obtaining the cyclic hemiacetal compound represented by formula (7);

(In the formula, R ¹ is a hydrogen atom, a fluorine atom or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and one of the hydrogen atoms bonded to the carbon atom in the alkyl group 7 or less can be substituted with fluorine atoms; R ² ~ R ⁵ are hydrogen atoms, straight-chain carbon atoms 1-10 or branched alkyl groups 3-10 carbon atoms, bonded to carbon atoms in the alkyl group 7 or less of the hydrogen atoms in the junction can be substituted with fluorine atoms; X is a single bond or a divalent group, and 7 or less hydrogen atoms contained in the divalent group can be substituted with fluorine atoms; Y is the carbon number 1 ~ 3 fluorine-containing alkyl or carboxylate group (-COOR), the fluorine-containing alkyl or carboxylate group contains 7 or less hydrogen atoms can be replaced by fluorine atoms; R is C 1 ~ 3 Fluoroalkyl; Z is a linear chain with 1 to 20 carbon atoms, a branched chain or cyclic alkyl with 3 to 20 carbon atoms. Part or all of the hydrogen atoms in Z may be substituted with halogen atoms, and may also contain (Ether bond, siloxane bond, sulfide bond, carbonyl bond). A fluorine-containing cyclic hemiacetal, which is represented by formula (7);

(In the formula, R ² to R ⁵ are hydrogen atoms, straight-chain C 1-10 or branched alkyl groups with 3 to 10 carbon atoms, and 7 of the hydrogen atoms bonded to carbon atoms in the alkyl group 1 or less can be substituted with fluorine atoms; Y is a fluorine-containing alkyl or carboxylate group with 1 to 3 carbon atoms (-COOR). 7 or less hydrogen atoms contained in a fluorine-containing alkyl or carboxylate group can Substituted by a fluorine atom; R is a fluoroalkyl group having 1 to 3 carbon atoms). The fluorine-containing cyclic hemiacetal according to claim 13, wherein R ² , R ⁴ and R ⁵ in the above formula (7) are hydrogen atoms. The fluorine-containing cyclic hemiacetal according to claim 14, wherein Y in the above formula (7) is trifluoromethyl. A method for producing a fluorine-containing cyclic hemiacetal compound which cyclizes the hydroxycarbonyl compound represented by the following formula (10) or the hydroxyvinyl ether or hydroxyvinyl ester represented by the formula (11), and obtains it as requested The fluorine-containing cyclic hemiacetal compound represented by the formula (7) in any one of items 13 to 15;

(In the formula, R ² to R ⁵ are hydrogen atoms, straight-chain C 1-10 or branched alkyl groups with 3 to 10 carbon atoms, and 7 of the hydrogen atoms bonded to carbon atoms in the alkyl group 1 or less can be substituted with fluorine atoms; Y is a fluorine-containing alkyl or carboxylate group with 1 to 3 carbon atoms (-COOR). 7 or less hydrogen atoms contained in a fluorine-containing alkyl or carboxylate group can Substituted by fluorine atoms; R is a fluorinated alkyl group having 1 to 3 carbon atoms; Z is a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms and a branched or cyclic alkyl group having 3 to 20 carbon atoms Part or all of the atoms may be substituted with halogen atoms, and may also contain ether bonds, siloxane bonds, thioether bonds, carbonyl bonds).