KR102234960B1 - Fluorinated monomer, fluorinated polymer, and composition for pattern formation using the same, and method for pattern formation thereof - Google Patents

Abstract

(식 중, R¹은 수소 원자, 불소 원자 또는 탄소수 1∼10의 알킬기이고, R²∼R⁵는 수소 원자, 탄소수 1∼10의 알킬기이고, X는 단결합 또는 2가의 기이고, Y는 탄소수 1∼3의 함불소 알킬기, 또는 카르본산 에스테르기(-COOR)이고, R은 탄소수 1∼3의 함불소 알킬기이다. 이들 기가 포함하는 7개 이하의 수소 원자가 불소 원자에 의해 치환되어 있어도 된다.)When used as a film with a photoacid generator, it is a pattern forming material that exhibits water repellency after film formation and becomes hydrophilic by acid by irradiation with light, and does not contain a perfluoroalkyl group having 4 or more carbon atoms that gives a highly sensitive and high resolution pattern. It provides a non-fluorinated polymer. The fluorinated polymer of the present invention is characterized by containing a repeating unit represented by formula (1).

(In the formula, 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, X is a single bond or a divalent group, and Y is A fluorinated alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and R is a fluorinated alkyl group having 1 to 3 carbon atoms, and up to 7 hydrogen atoms contained in these groups may be substituted with a fluorine atom. .)

Description

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

The present invention relates to a fluorinated monomer, a fluorinated polymer, and a composition for forming a pattern using the same, and a method for forming a pattern thereof. In particular, a resist material used for lithography in semiconductor manufacturing, or an electronic circuit or the like with ink in the manufacturing of electronic devices, for example, on a glass or resin substrate by printing using a conductive ink. The present invention relates to a fluorinated polymer that can be used in printed electronics to form a patterned circuit using a conductive film ink, a fluorinated monomer as a precursor thereof, a composition for pattern formation using the same, and a pattern formation method thereof.

A fluorinated polymer is known for its excellent properties due to having a fluorine atom in its chemical structure. A fluorinated polymer having water repellency, heat resistance, transparency, low refractive index, photosensitivity, and the like is used as a resist material in semiconductor manufacturing and a pattern forming material in printed electronics.

A fluorinated polymer having an acid-decomposable group used in a resist material in semiconductor manufacturing is made into a resist film by adding a photoacid generator, and acid-decomposable groups are dissociated from the fluorinated polymer by acid generated from the photoacid generator by light irradiation. As a result, the property of soluble or insoluble in the developer is changed, and pattern formation on the resist film becomes possible. In printed electronics, a fluorinated polymer is used as a material for a pattern forming film provided with a pattern that repels or does not repel ink.

In common with photolithography and printed electronics, when a fluorinated polymer having an acid-decomposable group containing fluorine is used as a pattern forming material, the formed fluorinated polymer film exhibits high water repellency before light irradiation, and fluorine after light irradiation. When the contained acid-decomposable group is dissociated, the irradiation part changes from water repellency to hydrophilicity.

In printed electronics, when a film made of a pattern forming material is irradiated with light through a patterned mask, a self-repelling pattern consisting of an unirradiated water-repellent portion to which the mask pattern is transferred and a hydrophilic portion after irradiation is formed. Then, when the ink is applied, the water-repellent portion repels the ink, thereby forming a pattern by the ink.

For example, in Patent Document 1 and Patent Document 2, as a pattern forming material for printed electronics that imparts a propellant pattern, the number of carbon atoms for forming a high-definition pattern by suppressing wet diffusion and permeation of ink. A resin having 6 or more long-chain perfluoroalkyl groups is disclosed, and by dissociation of the perfluoroalkyl groups contained in these resins by light irradiation, the lyophilic portion and liquid repellent to the ink. It is described that the pattern of the) part is formed.

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

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

For example, in Patent Document 3, as an acid-dissociable monomer, a radiation-sensitive resin composition containing a fluorine-free cyclic acetal monomer such as 2-tetrahydrofuranyl methacrylate, and a photoacid generator Disclosed is a pattern forming method used. In addition, in Patent Document 4, as a pattern forming material that has high sensitivity and high resolution and increases the residual film rate during development, a monomer having a cyclic acetal group not containing fluorine, a monomer having an acid decomposable group, and a monomer having a crosslinkable group are copolymerized. A positive photosensitive composition comprising a polymer and a radiation-sensitive acid generator is disclosed.

Patent Document 5 discloses a fluorinated polymer having a cyclic hemiacetal structure and a fluorinated monomer as a precursor. In addition, Patent Document 6 states that in a fluorinated monomer having a cyclic hemiacetal structure, the cyclic hemiacetal structure is modified with a substituent, and the water repellency, oil solubility, and acid decomposition properties in the case of a fluorinated polymer can be adjusted according to the selection of the substituent. It is disclosed.

Pamphlet of international publication WO2014/178279 Japanese Unexamined Patent Application Publication No. 2016-87602 Japanese Unexamined Patent Application Publication No. Hei 4-26850 Japanese Unexamined Patent Application Publication No. 2012-42837 Japanese Unexamined Patent Application Publication No. 2006-152255 Japanese Unexamined Patent Application Publication No. 2010-106138

In the present invention, when a film containing a photoacid generator is used in a photoresist and printed electronics, it exhibits water repellency after film formation and before light irradiation, and becomes hydrophilic by the action of an acid generated from the photoacid generator after light irradiation. It is an object to provide a fluorinated polymer that does not contain a perfluoroalkyl group having 4 or more carbon atoms, which is used in a composition for pattern formation that has a high contact angle with water before irradiation, a low contact angle after light irradiation, and imparts a high-sensitivity and high-resolution pattern. It is done. Another object of the present invention is to provide a pattern forming composition containing the fluorinated polymer as a pattern forming material, and a pattern forming method using the pattern forming composition. In addition, it is an object of the present invention to provide a fluorinated monomer and a fluorinated compound, and a method for producing the same as a precursor.

As shown in the examples of the present specification, the present inventors have a fluorinated polymer comprising the following repeating unit (1) having an acid-decomposable group having a fluorinated cyclic acetal skeleton bonded to a trifluoromethyl group at a specific position ( Hereinafter, the fluorinated polymer (1) may be called) was newly synthesized. Next, the composition for pattern formation containing the fluorinated polymer (1) of the present invention was developed on a substrate to form a film.

[Formula 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 linear alkyl group having 1 to 10 carbon atoms. Y is a fluorinated alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and R is a fluorinated alkyl group having 1 to 3 carbon atoms.)

Next, the fluorinated polymer (1) of the present invention, a fluorinated polymer containing the repeating unit (A) described in Patent Document 6 shown below, a fluorinated polymer containing the repeating unit (B) described in Patent Document 3, Alternatively, a photoacid generator, a solvent, etc. were added to a fluorinated polymer containing a repeating unit (C) known as a general-purpose resist material to prepare a composition for pattern formation, followed by spreading and forming a film on a substrate, followed by heat curing.

Then, the film containing the fluorinated polymer (1) exhibited a contact angle of about 10° higher with respect to water compared to the film containing the fluorinated polymer (A) and the fluorinated polymer (B) (Table 3 of Examples ], Examples 1 to 7 and Comparative Examples 1 to 2). In addition, when the resist sensitivity was measured, the resist film containing the fluorinated polymer (1) was added to the resist film containing the fluorinated polymer containing the repeating unit (A) or the resist film containing the repeating unit (B). In comparison, it showed high sensitivity. The resist film containing the fluorinated polymer (1) is higher than that of the resist film containing the copolymer having the repeating unit (A), the copolymer having the repeating unit (B), and the copolymer having the repeating unit (C). The sensitivity was shown (refer to resists 1 to 3 and comparative resists 1 to 3 in [Table 4] in Examples). Since the resist film containing the fluorinated polymer (1) exhibited higher sensitivity than the resist film containing the fluorinated polymer having the repeating unit (A), compared to the fluorinated polymer having the repeating unit (A). With respect to the fluoropolymer (A), it is estimated that the acid decomposition property of the fluorinated cyclic acetal structure of the fluorinated polymer (1) of the present invention is high.

[Formula 2]

Subsequently, a photomask having a 30 nm line and space pattern was prepared, and each film was irradiated with ultraviolet light through a mask. As a result, a pattern containing a fluorinated polymer belonging to the fluorinated polymer (1) of the present invention It was found that the resist pattern composed of the forming composition has high sensitivity and high resolution compared to resist patterns composed of other pattern forming compositions not within the scope of the present invention. Refer to comparative resist 1 to 3)

In this way, the inventors of the present invention show high water repellency after film formation and before light irradiation after film formation when a film containing a photoacid generator in lithography and printed electronics, and after light irradiation due to the action of the acid generated from the photoacid generator. By being hydrophilic, the contact angle with water before light irradiation is high, the contact angle after light irradiation is low, and fluorine-containing, which does not contain a perfluoroalkyl group having 4 or more carbon atoms, used in a pattern forming composition that gives a highly sensitive and highly accurate pattern. It was confirmed that a polymer was obtained.

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

[Invention 1]

A fluorinated polymer containing a repeating unit represented by formula (1).

[Formula 3]

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

[Invention 2]

The fluorinated polymer of Invention 1, ^{wherein R 2} , R ⁴ , and R ⁵ in the above formula (1) are hydrogen atoms.

[Invention 3]

Further, the fluorinated polymer of 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 of the inventions 1 to 3, an acid generator, a basic compound, and a solvent.

[Invention 5]

A film forming step of forming a film by applying the composition for forming a resist pattern of the invention 4 on a substrate,

An exposure step of irradiating exposure with electromagnetic waves or high energy rays having a wavelength of 300 nm or less through a photomask, and transferring the pattern of the photomask to the film;

A method of forming a resist pattern, comprising a developing step of obtaining a pattern by developing a film using a developer.

[Invention 6]

A composition for forming an ink pattern, comprising the fluorinated polymer of the inventions 1 to 3, an acid generator and a solvent.

[Invention 7]

A film forming step of forming a film by applying the composition for forming an ink pattern of the invention 6 on a substrate,

An exposure step of irradiating the film with light having a wavelength of 150 nm or more and 500 nm or less through a photomask to transfer the pattern of the mask to the film to obtain a pattern forming film having a liquid-repellent portion and a lyophilic portion;

A method for forming an ink pattern, comprising a pattern forming step of applying ink to the obtained pattern forming film.

[Invention 8]

A film forming step, which is a step of heating (pre-baking) a coating film obtained by applying the composition for forming an ink pattern of the invention 6 on a substrate,

Subsequently, a pattern in which light having a wavelength of 150 nm or more and 500 nm or less is scanned and exposed to the film with 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, and apply ink to the obtained pattern-forming film. A method of forming an ink pattern, including a forming process.

[Invention 9]

Fluorinated monomer represented by formula (4).

[Formula 4]

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

[Invention 10]

The fluorinated monomer of Invention 9, ^{wherein R 2} , R ⁴ , and R ⁵ in the formula (4) are hydrogen atoms.

[Invention 11]

Further, the fluorinated monomer of Invention 10, wherein Y in the formula (4) is a trifluoromethyl group.

[Invention 12]

Cyclic hemiacetal compound represented by formula (7) by cyclizing a hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or hydroxyvinyl ester represented by formula (11) A method for producing a fluorinated monomer represented by Formula (4) of Invention 9, including the step of obtaining.

[Formula 5]

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

[Invention 13]

Fluorinated cyclic hemiacetal represented by formula (7).

[Formula 6]

(In the formula, R ² to ^{R 5} are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms and Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorine-containing alkyl group or the carboxylic acid ester group are substituted by a fluorine atom. R is a fluorinated alkyl group having 1 to 3 carbon atoms.)

[Invention 14]

The fluorinated cyclic hemiacetal of the invention 13, ^{wherein R 2} , R ⁴ , and R ⁵ in the formula (7) are hydrogen atoms.

[Invention 15]

Further, in the above formula (7), Y is a trifluoromethyl group, the fluorinated cyclic hemiacetal of the invention 14.

[Invention 16]

The hydroxycarbonyl compound represented by the following formula (10) or the hydroxyvinyl ether or hydroxyvinyl ester represented by the formula (11) is cyclized, and the fluorinated ring represented by the formula (7) of the inventions 13 to 15 A method for producing fluorinated cyclic hemiacetal to obtain hemiacetal.

[Formula 7]

(In the formula, R ² to ^{R 5} are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms and Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorine-containing alkyl group or the carboxylic acid ester group are substituted by a fluorine atom. R is a C1-C3 fluorinated alkyl group, Z is a hydrogen atom or a C1-C20 linear, C3-C20 branched or cyclic alkyl group, and some or all of the hydrogen atoms in Z are It may be substituted with a halogen atom, and may contain an ether bond, a siloxane bond, a thioether bond, and a carbonyl bond.)

According to the present invention, when a film containing a photoacid generator is formed in a photoresist and printed electronics, the film exhibits water repellency after film formation and before light irradiation, and after light irradiation, fluorine is removed by the action of the acid generated from the photoacid generator. Since the acid-decomposable group contained is dissociated and the film becomes hydrophilic, the contact angle with water before light irradiation is high, the contact angle after light irradiation is low, and a perfluorocarbon number of 4 or more is used for a pattern forming composition that gives a high-sensitivity and high-resolution pattern. A fluorinated polymer containing no alkyl group was obtained. Further, a pattern formation composition containing the fluorinated polymer as a pattern formation material, and a pattern formation method using the pattern formation composition were obtained. Further, as the precursors, a fluorinated monomer and a fluorinated compound, 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 accumulating in the environment.

Hereinafter, the best mode of implementation of the present invention will be described, but the present invention is not limited to the following embodiments, and within the scope not departing from the spirit of the present invention, based on the ordinary knowledge of those skilled in the art, the following It should be understood that appropriate changes, improvements, and the like are included in the scope of the present invention.

1. Fluorinated polymer

[Fluorinated polymer (1)]

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

[Formula 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 fluorinated alkyl group having 1 to 3 carbon atoms, or a carboxylic acid ester group (-COOR) (R is a fluorinated 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 C 1 to C 10 linear or C 3 to C 10 branched alkyl group, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less hydrogen atoms are fluorine atoms. And may be substituted.

R ¹ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a fluorine atom, a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, 1,1,1,3,3,3-hexafluoro A loisopropyl group (-C(CF ₃ ) ₂ H) and a heptafluoroisopropyl group can be illustrated. From the ease of polymerization, R ¹ is preferably a hydrogen atom, a fluorine atom, or a methyl group.

[R ² ∼R ⁵ ]

R ² to ^{R 5} are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less may be substituted with a fluorine atom. .

R ² to ^{R 5} are preferably a donor alkyl group than an electron-withdrawing substituent, and a hydrogen atom or a methyl group without steric hindrance is preferable from the viewpoint of ease of synthesis.

[X]

X is a single bond or a divalent group, and up to 7 hydrogen atoms included in the divalent group may be substituted with a fluorine atom.

X is preferably a C2-C10 divalent group, a methylene group, a C2-C10 alkylene group, a C2-C10 alkenylene group, a C6-C10 divalent aryl group, or a C4-C10 2 And a valent alicyclic hydrocarbon group. The alkylene group or alkenylene group may contain an ether bond (-O-), a carbonyl group (-(C=O-), a carboxyl group (-(C=O)O-, or -O(C=O)-)) Since the liquid repellency decreases when the divalent group becomes long chain, it is preferably a single bond, an oxyethylene group (-O-CH ₂ -CH ₂ -) or an oxyacetyl group (-O-CH ₂ -CO-). .

[Y]

Y is a fluorinated alkyl group having 1 to 3 carbon atoms, or a carboxylic acid ester group having 1 to 3 carbon atoms (-COOR) (R is a fluorinated alkyl group having 1 to 3 carbon atoms). 7 or less hydrogen atoms contained in the fluorinated alkyl group or the carboxylic acid ester group may be substituted with a fluorine atom.

Y is a trifluoromethyl group, trifluoroethyl group, pentafluoroethyl group, trifluoropropyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, or heptafluoroisopropyl group can do. From the ease of synthesis, a trifluoromethyl group, a trifluoroethyl group, and a 1,1,1,3,3,3-hexafluoroisopropyl group are preferable.

In addition, in the fluorinated polymer (1) of the present invention, depending on the kind and combination of the substituents shown above, there may be cases where an asymmetric carbon atom is contained in the molecule, and enantiomers (enantiomers), dia. Stereomers (isomers having two or more subtitle carbon atoms, which are not enantiomers) may exist. However, Formula (1) represents and represents all of these stereoisomers. In addition, stereoisomers may be used alone or as a mixture.

[Fluorinated polymer (2)]

It is preferable that the fluorinated polymer (1) of the present invention is a fluorinated polymer containing the following repeating units (2) in which ^{R 2} , R ⁴ , and R ^{5 in the formula (1) are hydrogen atoms.} When forming a film on a substrate using the fluorinated polymer (1) as a pattern forming composition, for solubility in a solvent, it is preferable that ^{R 2} , R ⁴ , and R ^{5 in the above formula (1) be a hydrogen atom.} For use in the invention, preferably, it is a polymer having a fluorinated cyclic acetal structure containing a repeating unit represented by formula (2). Hereinafter, it may be called a fluorinated polymer (2).

[Formula 9]

(In the formula, R ¹ , R ³ , X, and Y are synonymous with formula (1).)

[Fluorinated Polymer (3)]

It is preferable that the fluorinated polymer (1) of the present invention is a fluorinated polymer (3) containing the following repeating units (3) in which Y in the formula (1) is a trifluoromethyl group. In addition, for solubility in a solvent, it is preferable that Y in the above formula (1) is a trifluoromethyl group, and it is preferably a polymer having a fluorinated cyclic acetal structure including a repeating unit represented by formula (3). Do. Hereinafter, it may be called a fluorinated polymer (3).

[Formula 10]

(In the formula, R ¹ , R ³ , and X have the same meaning as formula (1).)

1-1. Decomposition of Fluorinated Polymer (1) by Acid

It is known that the cyclic acetal structure is decomposed by an acid from an acid generator similarly to a general acetal. The fluorinated cyclic acetal structure of the fluorinated polymer (1) of the present invention is also inferred that the reaction shown below proceeds in the same manner.

In the reaction with an acid, the acid-decomposable group (1B) is dissociated from the fluorinated polymer (1) represented by the following formula, leaving a repeating unit represented by formula (1A), or the ring opening of a fluorinated cyclic acetal structure.環), it is estimated that there are two reaction pathways in which the repeating unit represented by formula (1C) is generated, and from the water-repellent fluorinated polymer (1), the repeating unit represented by the hydrophilic formula (1A) or the formula ( It is presumed that by generating the fluorinated polymer containing the repeating unit represented by 1C), the contact angle of the ink to the film decreases, and the function of pattern formation by the ink is expressed.

[Formula 11]

1-2. Monomers that impart other repeating units

In the fluorinated polymer (1) of the present invention, other repeating units other than the repeating unit (1) may be included. Other repeating units other than the repeating unit (1) are the solvent solubility of the fluorinated polymer (1) when the composition for pattern formation containing the fluorinated polymer (1) as a component is used as a film, or It is added in the structure of the fluorinated polymer (1) for the purpose of adjusting the hardness and the like.

The fluorinated polymer (1) containing the repeating unit (1) and other repeating units is obtained by copolymerizing a fluorinated monomer (4) giving the repeating unit (1) and a monomer giving another repeating unit.

The monomer giving other repeating units should just have a polymerizable unsaturated bond and can be copolymerized with the fluorinated monomer (4) giving the repeating unit (1), and as a monomer giving other repeating units, it gives an adhesive group. Monomers, acrylic acid esters, fluorinated acrylic acid esters, methacrylic acid esters, fluorinated methacrylic acid esters, hexafluoroisopropanol group (-C(CF ₃ ) ₂ OH, hereinafter sometimes referred to as HFIP group) ), styrenes, fluorinated styrenes, vinyl ethers, allyl ethers, fluorinated vinyl ethers, fluorinated allyl ethers, olefins, fluorinated olefins, norbornene, fluorinated norbornene , Or other monomers having a polymerizable unsaturated bond.

[Monomer having adhesion group]

When using the fluorinated polymer (1) as a resist component, by introducing an adhesive group into the chemical structure, preferable adhesion to the substrate in lithography can be obtained. As an adhesive group, a group containing a lactone structure is mentioned.

When introducing an adhesive group into the fluorinated polymer (1) of the present invention, a monomer containing a group having a monocyclic or polycyclic lactone structure copolymerizable with the fluorinated monomer (4) can be used.

The monocyclic lactone structure is a group obtained by removing one hydrogen atom from γ-butyrolactone or mevalonic lactone to form a bond, and as a polycyclic lactone structure, one hydrogen atom is removed from norbornanlactone and bonded. One can be illustrated by hand. A lactone structure is introduced into the fluorinated polymer (1) of the present invention by copolymerizing an acrylic acid ester or a methacrylic acid ester containing a lactone structure. By doing so, when using the fluorinated polymer (1) as a resist component for lithography, it is expected that not only the adhesion to the substrate will be improved, but also the affinity to the developer will be improved.

The following repeating units can be exemplified as a repeating unit that imparts adhesion to a substrate when a resist film is formed.

[Formula 12]

From the ease of availability, it is particularly preferably 5-methacryloyloxy-2,6-norbornanecarbolactone (hereinafter sometimes referred to as MNLA). In the figure above, it is represented by MNLA.

[Acrylic acid esters]

As acrylic esters, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl Acrylamide, N-methylol as an acrylate, lauryl acrylate, 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate, or an acrylate having an ethylene glycol, propylene glycol or tetramethylene glycol group, or an unsaturated amide Acrylamide or diacetoneacrylamide, or tert-butyl acrylate, 3-oxocyclohexyl acrylate, adamantyl acrylate, methyl adamantyl acrylate, ethyl adamantyl acrylate, hydroxyadamantyl acrylate , Cyclohexyl acrylate or tricyclodecanyl acrylate, or an acrylate having a ring structure such as a lactone ring or a norbornene ring, or these acrylic esters having a cyano group at the α-position.

[Fluorinated acrylic acid esters]

Examples of the fluorinated acrylic acid esters include fluorinated acrylic acid esters having a fluorinated organic group at the α-position of the acrylic moiety or the ester moiety. Both the α-position and the ester moiety may have a fluorinated organic group, or may have a cyano group in the α-position and a fluorinated alkyl group in the ester moiety.

Examples of the fluorinated organic group that the fluorinated acrylic acid esters have at the α-position include a trifluoromethyl group, a trifluoroethyl group, or a nonafluoro-n-butyl group.

As the fluorinated organic group in the ester moiety of fluorinated acrylic acid esters, a perfluoro or a fluorinated alkyl group containing a hydrogen atom, or a cyclic hydrogen atom is substituted with a fluorine atom, a trifluoromethyl group, or an HFIP group. A group including a fluorinated benzene ring, a fluorinated cyclopentane ring, a fluorinated cyclohexane ring, or a fluorinated cycloheptane ring can be illustrated.

As fluorinated acrylic acid esters, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1,1,1,3,3,3-hexafluoroiso Propylacrylate, heptafluoroisopropylacrylate, 1,1-dihydroheptafluoro-n-butylacrylate, 1,1,5-trihydrooctafluoro-n-pentylacrylate, 1,1, 2,2-tetrahydrotridecafluoro-n-octylacrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decylacrylate, 6-[3,3,3-trifluoro -2-hydroxy 2-(trifluoromethyl)propyl]bicyclo[2.2.1]heptyl-2-ylacrylate, 6-[3,3,3-trifluoro-2-hydroxy 2-( Trifluoromethyl)propyl]bicyclo[2.2.1]heptyl-2-yl 2-(trifluoromethyl)acrylate, 1,4-bis(1,1,1,3,3,3-hexafluoro Rho-2-hydroxyisopropyl)cyclohexylacrylate, or 1,4-bis(1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl)cyclohexyl-2-tri Fluoromethyl acrylate can be illustrated.

[Methacrylic acid esters]

As methacrylic acid esters, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n -Octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, or having an ethylene glycol, propylene glycol or tetramethylene glycol group Methacrylate, or methacrylamide as unsaturated amide, N-methylolacrylamide, N-methylolmethacrylamide or diacetoneacrylamide, or tert-butylmethacrylate, 3-oxocyclohexylmethacrylate, a Damantyl methacrylate, methyladamantyl methacrylate, ethyladamantyl methacrylate, hydroxyadamantyl methacrylate, cyclohexyl methacrylate or tricyclodecanyl methacrylate, or lactone ring or nor A methacrylate having a ring structure, such as a bornene ring, can be illustrated.

[Fluorinated methacrylic acid esters]

Examples of the fluorinated methacrylic acid esters include fluorinated methacrylic acid esters having a fluorinated organic group at the ester site.

Examples of such a fluorinated organic group include perfluorofluoro or a fluorinated alkyl group containing a hydrogen atom, or a fluorine-containing benzene ring in which a hydrogen atom of a cyclic structure is substituted with a fluorine atom, a trifluoromethyl group, an HFIP group, or the like. A fluorine cyclopentane ring, a fluorine-containing cyclohexane ring, or a fluorine-containing cycloheptane ring can be illustrated.

As fluorinated acrylic acid esters, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1,1,1,3,3,3-hexafluoro Loisopropylmethacrylate, heptafluoroisopropylmethacrylate, 1,1-dihydroheptafluoro-n-butylmethacrylate, 1,1,5-trihydrooctafluoro-n-pentylmethacrylate Rate, 1,1,2,2-tetrahydrotridecafluoro-n-octylmethacrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decylmethacrylate, perfluorocyclo Hexylmethylacrylate, perfluorocyclohexylmethylmethacrylate, 6-[3,3,3-trifluoro-2-hydroxy-2-(trifluoromethyl)propyl]bicyclo[2.2.1] Heptyl-2-ylmethacrylate, or 1,4-bis(1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl)cyclohexyl methacrylate can be illustrated.

[Monomer having HFIP group]

As a monomer which has an HFIP group, the monomer shown below can be illustrated.

[Formula 13]

(R ⁹ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. In addition, a part or all of the HFIP group may be protected by a protecting group.)

[Styrene, fluorinated styrene]

Styrene and hydroxystyrene can be illustrated as styrenes.

Examples of fluorinated styrenes include pentafluorostyrene, trifluoromethylstyrene, bistrifluoromethylstyrene, styrene obtained by substituting a hydrogen atom of an aromatic ring structure with a fluorine atom or trifluoromethyl group, an HFIP group, or a hydroxyl group thereof. Styrene obtained by substituting a hydrogen atom of an aromatic ring structure by an HFIP group protected by a protecting group, styrene having a halogen atom, an alkyl group, or a fluorinated alkyl group bonded to the α-position, or styrene containing a perfluorovinyl group can be illustrated .

[Vinyl ethers, allyl ethers, fluorinated vinyl ethers, fluorinated allyl ethers]

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

[Olefins, fluorinated olefins]

As olefins, ethylene, propylene, isobutene, cyclopentene, or cyclohexene can be illustrated. As fluorinated olefins, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene or hexafluoroisobutene, 1-chloro-2,3,3,4 ,4,5,5-heptafluorocyclopentene, octafluorocyclopentene or decafluorocyclohexene can be illustrated.

[Norbornene, fluorinated norbornene]

Norbornenes and fluorinated norbornenes need only have a polymerizable group, and may have not only one norbornene skeleton but also a plurality of norbornene skeletons. Norbornene or fluorinated norbornene is produced by a Diels-Alder addition reaction of an unsaturated compound and a diene compound.

Examples of such unsaturated compounds include fluorinated olefins, allyl alcohol, fluorinated allyl alcohol, homoallyl alcohol, fluorinated homoallyl alcohol, acrylic acid, α-fluoroacrylic acid, α-trifluoromethylacrylic acid, methacrylic acid, and the acrylic acid ester. , Methacrylic acid ester, fluorinated acrylic acid ester or fluorinated methacrylic acid ester, 2-(benzoyloxy)pentafluoropropane, 2-(methoxyethoxymethyloxy)pentafluoropropene, 2-(tetrahyde Roxypyranyloxy) pentafluoropropene, 2-(benzoyloxy)trifluoroethylene, or 2-(methoxymethyloxy)trifluoroethylene can be illustrated. As a diene compound, cyclopentadiene or cyclohexadiene can be illustrated.

Examples of the fluorinated norbornene compound include 3-(5-bicyclo[2.2.1]hepten-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanol. can do.

[Other monomers having polymerizable unsaturated bonds]

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

As other monomers, when the length of the organic group from the polymerization site becomes a long chain, or when it contains many heteroatoms, the influence of the organic group derived from other repeating units becomes strong, and the fluorinated alkyl group at the terminal is There is a fear that the effect of exerting liquid repellency may be reduced, and the solubility of the polymer may be lowered. Therefore, as other monomers, preferably, they are acrylic acid esters and methacrylic acid esters having less than 10 carbon atoms, and particularly preferably methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate or isobutyl methacrylate.

1-3. Content ratio of each repeating unit in fluorinated polymer (1)

The content ratio of the repeating unit represented by formula (4) with respect to the total amount of the fluorinated polymer (1) is 10 mol% or more and 100 mol% or less, and more preferably 10 mol% or more and 90 mol% or less. When the content of the repeating unit (1) in the fluorinated polymer (1) is less than 10 mol%, water repellency is not obtained in the unexposed portion of the patterned film formed by exposing the film made of the fluorinated polymer (1).

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

The repeating units derived from other monomers are for improving the solubility of the fluorinated polymer (1) in an organic solvent, adhesion to the substrate when used as a film, or hardness. If it is not necessary, it is not necessary to use, but if it is less than 10 mol%, the adhesion or rigidity with the substrate when it is formed as a film is not improved, and if it exceeds 90 mol%, the content of the repeating unit (1) decreases, and the fluorinated polymer It is difficult to obtain the effect of obtaining water repellency in the unexposed portion of the patterned film, and that the hydrophilicity of the exposed portion is obtained, obtained by exposing the film made of (1).

1-4. Molecular weight of fluorinated polymer (1)

The number average molecular weight of the fluorinated polymer (1) of the present invention is 1,000 or more and 100,000 or less, and preferably 3,000 or more and 50,000 or less. The molecular weight dispersion is 1 or more and 4 or less, preferably 1 or more and 2.5 or less. When the number average molecular weight is less than 1000, the film made of the composition for pattern formation containing the fluorinated polymer (1) as a component becomes brittle, and it becomes 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 composed of a liquid-repellent portion and a lyophilic portion, and there is a fear that the durability of the pattern may be insufficient. When the number average molecular weight is more than 100,000, the fluorinated polymer (1) becomes difficult to dissolve in a solvent, and cracks occur after film formation, and a film made of a composition for pattern formation containing the fluorinated polymer (1) as a component is used as a coating film. Difficult to form.

2. Synthesis of Fluorinated Polymer

[Synthesis of Fluorinated Polymer (1)]

Synthesis of the fluorinated polymer (1) of the present invention can be selected from generally used polymerization methods. Radical polymerization and ionic polymerization are preferred, and coordination anionic polymerization, living anionic polymerization, and cation polymerization may be selected as the case may be. The reactor used for the polymerization reaction is not particularly limited. Moreover, in polymerization, you may use a polymerization solvent. Hereinafter, radical polymerization will be described.

Radical polymerization is a batch type, semi-continuous polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization in the presence of a radical polymerization initiator or a radical initiator. It can be performed by the operation of either an equation or a continuous type.

<Radical polymerization initiator>

Examples of the radical polymerization initiator include azo compounds, peroxide compounds, and redox compounds.

As an azo compound, azobisisobutyronitrile can be illustrated. As peroxide compounds, t-butylperoxypivalate, di-t-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, disinnamyl peroxide, di-n-propyl peroxide Carbonate, t-butylperoxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, or ammonium persulfate can be exemplified.

<Polymerization solvent>

As the polymerization solvent, it is preferable that radical polymerization is not inhibited, and an ester solvent, a ketone solvent, a hydrocarbon solvent, or an alcohol solvent is exemplified. In addition, water, ether, cyclic ether, freon, or aromatic solvents may be used.

As the polymerization solvent, ethyl acetate or n-butyl acetate as an ester solvent, acetone or methyl isobutyl ketone as a ketone solvent, toluene or cyclohexane as a hydrocarbon solvent, methanol as an alcohol solvent, isopropyl alcohol or ethylene glycol monomethyl Ether can be illustrated.

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

<Polymerization conditions>

The polymerization temperature may be appropriately selected according to the kind of the radical polymerization initiator or the radical polymerization initiator. It is preferable to appropriately select the kind of radical polymerization initiator or radical polymerization initiator so that the polymerization temperature is 20°C or more and 200°C or less, and preferably 30°C or more and 140°C or less. The molecular weight of the fluorinated polymer (1) can be controlled by selecting a radical polymerization initiator or a radical polymerization initiator, and adjusting polymerization conditions.

In addition, as a method of removing the polymerization solvent such as an organic solvent or water from a solution or dispersion containing the fluorinated polymer (1) after polymerization, a known method can be used, and reprecipitation, filtration, or heat distillation under reduced pressure. Can be mentioned.

When using the fluorinated polymer (1) of the present invention as a resist component, the solubility of the developer solution of the fluorinated polymer (1) varies depending on the molecular weight of the fluorinated polymer (1), and patterning conditions in lithography may change. have. When the molecular weight of the fluorinated polymer (1) is high, the dissolution rate in the developing solution is slow, and when the molecular weight is low, the dissolution rate tends to increase. The molecular weight of the fluorinated polymer (1) can be controlled by adjusting these polymerization conditions.

3. Composition for forming resist pattern

The composition for forming a resist pattern of the present invention is formed by adding an acid generator, a basic compound, and a solvent to any of the fluorinated polymers (1) to (3), and can be used for lithography. Hereinafter, the composition for forming a resist pattern may be simply referred to as a resist.

The fluorinated polymers (1) to (3) of the present invention are particularly suitably used as a component of a photosensitizing positive resist. The resist of the present invention is to provide a resist containing fluorinated polymers (1) to (3), particularly a photosensitizing positive resist material.

The resist of the present invention contains (A) any of the fluorinated polymers (1) to (3) of the present invention, (B) a photoacid generator, (C) a basic compound, and (D) a solvent as its components. desirable. Moreover, you may add (E) surfactant as needed.

3-1. (B) photoacid generator

The photoacid generator used for the resist of the present invention is not particularly limited, and any one used as an acid generator for a chemically amplified resist can be selected and used, and onium sulfonate or sulfonic acid ester may be mentioned. For example, iodonium sulfonate, sulfonium sulfonate, N-imide sulfonate, N-oxime sulfonate, o-nitrobenzyl sulfonate, or trismethanesulfonate of pyrogarol can be exemplified. .

Acids generated from these photoacid generators by exposure in lithography are alkanesulfonic acid, arylsulfonic acid, or partially or completely fluorinated arylsulfonic acid or alkanesulfonic acid. Among these photoacid generators, a photoacid generator that generates partially or completely fluorinated alkanesulfonic acid is preferred. For example, triphenylsulfonium trifluoromethanesulfonate, or triphenylsulfonium perfluoro-n-butanesulfonate can be illustrated.

3-2. (C) basic compound

A basic compound can be blended into the resist containing any of the fluorinated polymers (1) to (3) of the present invention. The basic compound has an effect of slowing the diffusion rate when the acid generated from the photoacid generator diffuses into the resist film. The blending of the basic compound is expected to improve the shape of the resist pattern by adjusting the acid diffusion distance, and to improve the stability of imparting a resist pattern with the desired accuracy even if the time left until exposure after the formation of the resist film is long. .

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

The blending amount of the basic compound in the resist of the present invention is 0.001 to 2 parts by mass per 100 parts by mass of the fluorinated polymer (1), and preferably 0.01 to 1 parts by mass per 100 parts by mass of the fluorinated polymer (1). . 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, the resolution and sensitivity may decrease.

3-3. (D) solvent

In addition to (A) any of the fluorinated polymers (1) to (3) of the present invention, (B) a photoacid generator, and (C) a basic compound, a solvent (D) is added to the resist of the present invention. The solvent may be a uniform solution by dissolving a resist component containing (A) any of the fluorinated polymers (1) to (3) of the present invention, (B) a photoacid generator, and (C) a basic compound. , It can be used by selecting from conventional solvents for resists. Moreover, you may mix and use two or more types of solvents.

Examples of such solvents include ketones, alcohols, polyhydric alcohols, esters, aromatic solvents, ethers, fluorine solvents, or terpene petroleum naphtha solvents or paraffinic solvents that are high boiling point solvents for the purpose of improving coating properties. .

For example, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isobutyl ketone, methyl isopentyl ketone or 2-heptanone as ketones, isopropanol as alcohols, butanol, isobutanol, n-pentanol, iso Pentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptane Ol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol or oleyl alcohol, ethylene as a polyhydric alcohol Glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoacetate Propyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME), and derivatives of these polyhydric alcohols, methyl lactate as esters, ethyl lactate (EL), methyl acetate, Ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate or ethyl ethoxypropionate, toluene or xylene as aromatic solvents, diethyl ether as ethers, dioxane, anisole or diisopropyl ether, or fluorine-based Hexafluoroisopropyl alcohol as a solvent can be illustrated.

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 blended in the resist of the present invention is not particularly limited, but the solid content concentration in the resist is preferably 3% by mass or more and 25% by mass or less, and more preferably 5% by mass or more and 15% by mass or less. By adjusting the solid content concentration of the resist, it is possible to adjust the film thickness of the formed resin film.

In addition, it should be noted that the fluorinated polymers (1) to (3) of the present invention are excellent in solubility in a wide range of solvents, and are soluble in alcoholic solvents having 5 to 20 carbon atoms among the above alcoholic solvents. . As such alcohols, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexane Ol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecane Ol or oleyl alcohol can be illustrated.

3-4. (E) surfactant

In the resist of the present invention, a surfactant may be added as necessary. Examples of the surfactant include a fluorine-based surfactant, a silicone-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 formed into a solution with an alcohol-based solvent or the like having 5 to 20 carbon atoms that cannot dissolve a general resist material. 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, has an appropriate degree of water repellency, and has developer affinity.

The resist of the present invention has a moderate degree of water repellency in water before exposure and shows rapid solubility in a developer after exposure, so not only dry exposure, but also a medium having a higher refractive index than air, such as water, between the resist and the lens. It is estimated that pattern formation of excellent resolution without roughness is possible in liquid immersion exposure to be filled and exposed. In photolithography by immersion exposure, a top coat film, which is a protective film of a resist, may or may not be used, but it is assumed that the resist of the present invention can be applied to immersion exposure by adjusting the composition and formulation.

As a medium for immersion exposure, in addition to water, a fluorine-based solvent, a silicone-based solvent, a hydrocarbon-based solvent, a sulfur-containing solvent, etc. can be mentioned, and the resist containing the fluorinated polymer (1) of the present invention is likely to be applicable to these media as well. have.

4. Method of forming resist pattern

In the method of forming a resist pattern of the present invention, a film forming step of forming a film by applying the resist of the present invention on a substrate, an electromagnetic wave or high energy ray having a wavelength of 300 nm or less through a photomask is irradiated and exposed, and the photomask is It includes an exposure process of transferring a pattern to a film, and a developing process of obtaining a pattern by developing a film using a developer. In addition, in this invention, a high-energy ray represents an electron beam or a soft X-ray.

The resist pattern formation method of the present invention is a pattern formation method by lithography using a resist containing any of fluorinated polymers (1) to (3), and (A) a resist film is formed by applying a resist on a substrate. (B) After heating the resist film, an exposure step in which the resist film is exposed by irradiating electromagnetic waves or high energy rays with a wavelength of 300 nm or less through a patterned photomask, and (C) the exposed resist film is alkali It is developed with a developer to obtain a resist pattern in which a pattern of a photomask is transferred onto a substrate.

For example, in the film forming step (A), a resist containing any of the fluorinated polymers (1) to (3) of the present invention is applied by spin coating on a silicon wafer as a substrate, and a silicon wafer is formed. A resist film is formed on the substrate by prebaking on a hot plate at 60 to 200°C for 10 seconds to 10 minutes, preferably 80°C to 150°C for 30 seconds or more and for 2 minutes or less. Subsequently, in the exposure step (B), a patterned photomask is set in an exposure apparatus, and high energy rays such as ultraviolet rays, excimer lasers, and X-rays or electron beams are exposed to 1 mJ/cm 2 or more and 200 mJ/cm 2 or less. , Preferably 10 mJ/cm 2 or more and 100 mJ/cm 2 or less, after irradiation to the resist film through a photomask, on a hot plate 60° C. or more and 150° C. or less, 10 seconds or more and 5 minutes or less, preferably 80° C. or more At 130° C. or less, 30 seconds or more and 3 minutes or less, post-exposure bake (PEB) is performed as necessary. Subsequently, in the development step (C), a developer using an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 0.1% by mass or more and 5% by mass or less, preferably 2% by mass or more and 3% by mass or less is used, 10 seconds or more and 3 minutes or less, preferably 30 seconds or more and 2 minutes or less, by contacting the resist film with a conventional method such as a dip method, a paddle method, or a spray method, and developing, a desired resist pattern is obtained.

As the substrate, in addition to a silicon wafer, it is possible to use a metal or glass substrate. Further, an organic or inorganic film may be provided on the substrate. For example, there may be an antireflection film, an underlayer of a multilayer resist, or a resist pattern may be formed.

In addition, in the lithography of the resist of the present invention, the wavelength of the electromagnetic wave used for exposure is not limited, but UV light (wavelength 248 nm) by KrF excimer laser, UV light (wavelength 193 nm) by ArF excimer laser, extreme ( Extreme ultraviolet lithography (EUV) and X-ray can be selected, and in particular, UV light by an ArF excimer laser is preferably employed.

The resist of the present invention has an appropriate degree of water repellency in water before exposure, shows rapid solubility in a developer solution after exposure, and can form a pattern with excellent resolution without roughness.

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

5. Composition for ink pattern formation

The composition for ink pattern formation of the present invention is formed by adding an acid generator and a solvent to any of the fluorinated polymers (1) to (3), and can be used for ink pattern formation in print electronics. Hereinafter, a pattern made of ink may be referred to as an ink pattern.

The composition for ink pattern formation of the present invention contains, as a component, any of the fluorinated polymers (1) to (3), (A) an acid generator, and (B) a solvent. It is preferable to include the other (C) sensitizers, (D) sensitizers, and (E) polymerizable compounds, and if necessary, a surfactant, a storage stabilizer, an adhesion aid, or a heat resistance improving agent may be included.

(A) The acid generator is a compound that generates an acid by irradiation with light during exposure in a film formed from the composition for forming an ink pattern. (B) The solvent is a substance for dissolving or dispersing a component of the composition for forming an ink pattern. (C) The target is a substance for preventing the diffusion of acid from the acid generator during exposure to make the pattern obtained with high definition. (D) The sensitizer is a substance for increasing exposure sensitivity. (E) The polymerizable compound is a substance for hardening the pattern-forming film obtained after exposure. Hereinafter, each component is described.

5-1. (A) acid generator

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

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

[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 an aryl group having 6 to 20 carbon atoms. Some or all of the hydrogen atoms in these groups may be substituted by halogen atoms or substituents. Preferably, it is a C1-C12 linear or C3-C12 branched alkyl group. As a substituent, an alicyclic group containing a interchangeable alicyclic group, such as a C1-C10 alkoxy group and a 7,7-dimethyl-2-oxonorbornyl group, is mentioned.

As a C1-C12 fluoroalkyl group, a trifluoromethyl group, a pentafluoroethyl group, or a heptylfluoropropyl group can be illustrated. Examples of the substituent that the alicyclic hydrocarbon having 4 to 12 carbon atoms may have include an alkyl group or an alkoxy group having 1 to 5 carbon atoms.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, a tolyl group, or 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 an oxime sulfonate compound, (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2) -Ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino- 5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, or (5-octylsulfonyloxyimino)-(4-methoxyphenyl)acetonitrile can be illustrated.

[Onium salt]

Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, alkylsulfonium salt, benzylsulfonium salt, dibenzylsulfonium salt, substituted benzylsulfonium salt, benzothiazolium salt or tetrahydrothiophenium salt.

<Diphenyliodonium salt>

Diphenyliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfo Nate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodo Nium tetrafluoroborate, bis(4-t-butylphenyl)iodoniumtetrafluoroborate, bis(4-t-butylphenyl)iodoniumhexafluoroarsenate, bis(4-t-butylphenyl) ) Iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodoniumtrifluoroacetate, bis(4-t-butylphenyl)iodonium-p-toluenesulfonate, or bis( 4-t-butylphenyl) iodonium camphorsulfonic acid can be illustrated.

<Triphenylsulfonium salt>

As triphenylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfo Nate or triphenylsulfonium butyl tris (2,6-difluorophenyl) borate can be illustrated.

<Alkylsulfonium salt>

As the alkylsulfonium salt, 4-acetoxyphenyldimethylsulfoniumhexafluoroantimonate, 4-acetoxyphenyldimethylsulfoniumhexafluoroarsenate, dimethyl-4-(benzyloxycarbonyloxy)phenylsulfoniumhexafluoro Roantimonate, dimethyl-4-(benzoyloxy)phenylsulfoniumhexafluoroantimonate, dimethyl-4-(benzoyloxy)phenylsulfoniumhexafluoroarsenate, or dimethyl-3-chloro-4- Acetoxyphenylsulfoniumhexafluoroantimonate can be illustrated.

<Benzylsulfonium salt>

Examples of benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfoniumhexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfoniumhexafluorophosphate, and 4-acetoxyphenylbenzylmethylsulfoniumhexafluoroantimo Nate, benzyl-4-methoxyphenylmethylsulfoniumhexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfoniumhexafluoroantimonate, benzyl-3-chloro-4-hydroxy Phenylmethylsulfoniumhexafluoroarsenate, or 4-methoxybenzyl-4-hydroxyphenylmethylsulfoniumhexafluorophosphate can be illustrated.

<Dibenzylsulfonium salt>

Dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, and 4-acetoxyphenyldibenzylsulfoniumhexafluoroanti Monate, dibenzyl-4-methoxyphenylsulfoniumhexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfoniumhexafluoroarsenate, dibenzyl-3-methyl-4- Hydroxy-5-t-butylphenylsulfoniumhexafluoroantimonate, or benzyl-4-methoxybenzyl-4-hydroxyphenylsulfoniumhexafluorophosphate can be illustrated.

<Substituted benzylsulfonium salt>

As substituted benzylsulfonium salts, p-chlorobenzyl-4-hydroxyphenylmethylsulfoniumhexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfoniumhexafluoroantimonate, p-chlorobenzyl- 4-hydroxyphenylmethylsulfoniumhexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfoniumhexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethyl Sulfonium hexafluoro antimonate, or o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoro antimonate can be illustrated.

<Benzothiazolium salt>

Examples of benzothiazolium salts include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazoliumhexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, and 3-(p-methoxybenzyl)benzo. Thiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, or 3-benzyl-5-chlorobenzothiazolium hexafluoroantimonate can be illustrated.

<Tetrahydrothiophenium salt>

As the tetrahydrothiophenium salt, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydro Thiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-(4-n-butoxynaphthalene -1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate, 1-(4-n-butoxynaphthalene-1 -Yl)tetrahydrothiophenium-2-(5-t-butoxycarbonyloxybicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, Or 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium-2-(6-t-butoxycarbonyloxybicyclo[2.2.1]heptan-2-yl)-1, 1,2,2-tetrafluoroethanesulfonate can be illustrated.

<Sulfonimide compound>

Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, and N-(2). -Trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyl Oxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy) Diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, 4-methylphenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N- (4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5 -Ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethanesulfur Fonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2, 3-dicarboximide, N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(camphorsulfonyloxy)-7-oxabicyclo[ 2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3- Dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)-7-oxabi Cyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3- Dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-fluorophenyl Sulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2 .1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide , N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane -5,6-oxy-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide , N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthyldicarboxyyi Mid, N-(campersulfonyloxy)naphthyldicarboximide, N-(4-methylphenylsulfonyloxy)naphthyldicarboximide, N-(phenylsulfonyloxy)naphthyldicarboximide, N-(2-trifluoro Romethylphenylsulfonyloxy)naphthyldicarboximide, N-(4-fluorophenylsulfonyloxy)naphthyldicarboximide, N-(pentafluoroethylsulfonyloxy)naphthyldicarboximide, N-(heptafluoro Propylsulfonyloxy)naphthyldicarboximide, N-(nonafluorobutylsulfonyloxy)naphthyldicarboximide, N-(ethylsulfonyloxy)naphthyldicarboximide, N-(propylsulfonyloxy)naphthyldicarboxyyi Mid, N-(butylsulfonyloxy)naphthyldicarboximide, N-(pentylsulfonyloxy)naphthyldicarboximide, N-(hexylsulfonyloxy)naphthyldicarboximide, N-(heptylsulfonyloxy)naph Tyldicarboximide, N-(octylsulfonyloxy)naphthyldicarboximide, or N-(nonylsulfonyloxy)naphthyldicarboximide can be illustrated.

<Halogen-containing compound>

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound.

<Diazomethane compound>

As a diazomethane compound, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-tolylsulfonyl)diazomethane , Bis(2,4-xylylsulfonyl)diazomethane, bis(p-chlorophenylsulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl(1,1 -Dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, or phenylsulfonyl(benzoyl)diazomethane can be illustrated.

<Sulfone compound>

Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, and diaryldisulfone compounds.

<Sulfonic acid ester compound>

Examples of the sulfonic acid ester compound include an alkyl sulfonic acid ester, a haloalkyl sulfonic acid ester, an aryl sulfonic acid ester, or an iminosulfonate.

<Carboxylate ester compound>

Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

<(A) Acid generator contained in the composition for ink pattern formation of the present invention>

These (A) acid generators may be used alone or in combination of two or more. Since the effect of improving the exposure sensitivity of the film made of the composition for forming an ink pattern is large, it is preferably an oxime sulfonate compound, an onium salt, and a sulfonic acid ester compound, and particularly preferably an oxime sulfonate compound.

[Containing of (A) Acid Generator in Ink Pattern Forming Composition]

The content of the acid generator (A) in the composition for forming an ink pattern of the present invention is expressed by mass% based on the fluorinated polymer (1) of the present invention, preferably 0.1% or more and 10% or less, more preferably Is 1% or more and 5% or less. By setting the content of the (A) acid generator in the above-described range, a high exposure sensitivity of the composition for forming an ink pattern is obtained, and a more highly fine pattern forming film by a liquid-repellent portion and a lyophilic portion is obtained.

5-2. (B) solvent

As the (B) solvent used as a component in the composition for forming an ink pattern of the present invention, it is sufficient to dissolve or disperse each component of the composition for forming an ink pattern, and alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl And organic solvents such as ether acetates, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aliphatic hydrocarbons, aromatic hydrocarbons, ketones or esters. Below, each (B) solvent is shown.

[Alcohol]

Examples of alcohols include long-chain alkyl alcohols, aromatic alcohols, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ethers.

<Long-chain alkyl alcohols>

As long-chain alkyl alcohols, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, or 1,8-octanediol can be illustrated.

<Aromatic alcohols>

As aromatic alcohols, benzyl alcohol can be illustrated. Examples of 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>

As propylene glycol monoalkyl ethers, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, or propylene glycol monobutyl ether can be illustrated.

<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.

Since the composition for forming an ink pattern of the present invention is easy to dissolve and is easy to form a film, among these alcohols, preferably, benzyl alcohol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, or propylene glycol mono It is ethyl ether.

[Ethers]

Examples of ethers include tetrahydrofuran, hexylmethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, or 1,4-dioxane.

[Diethylene glycol alkyl ethers]

Examples of diethylene glycol alkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, or diethylene glycol ethyl methyl ether.

[Ethylene glycol alkyl ether acetates]

Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, 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 acetate.

[Propylene glycol monoalkyl ether propionates]

As propylene glycol monoalkyl ether propionates, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, or propylene glycol monobutyl ether propionate can be exemplified. have.

[Aliphatic hydrocarbons]

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

[Aromatic hydrocarbons]

Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, or dichlorobenzene.

[Ketones]

Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, or 4-hydroxy-4-methyl-2-pentanone.

[Esters]

As esters, methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxy Methyl oxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionic acid, 3-hydroxy Butyl oxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid propyl , Butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, or ethyl 2-ethoxypropionate.

These (B) solvents may be used alone or in combination of two or more.

[Content of the solvent (B) in the composition for forming an ink pattern]

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

5-3. (C) ??

(C) The target used in the composition for ink pattern formation of the present invention is to function as an acid diffusion inhibitor that prevents diffusion of acid from the acid generator (A) at the time of exposure in the case of a film. And a photodegradable base that generates a weak acid by photosensitive. As a photodegradable base, it is preferably an onium salt compound.

The photodegradable base generates an acid in the exposed portion, while exhibiting a high acid trapping function by anion in the unexposed portion, (A) replenishes the acid from the acid generator, and from the exposed portion to the unexposed portion. It deactivates the acid that diffuses. The acid is deactivated only in the unexposed part. In the pattern formation film after exposure of the pattern forming composition of the present invention, the boundary between the liquid-repellent portion and the lyophilic portion becomes clear, the contrast of the pattern after ink application is improved, and a stationary pattern is obtained. (C) You may use it individually or in combination of 2 or more types.

[Containment of (C) ??in the composition for ink pattern formation]

The content of (C)? In the composition for ink pattern formation is preferably 0.001 parts by mass to 5 parts by mass, more preferably 0.005 parts by mass to 3 parts by mass per 100 parts by mass of the fluorinated polymer (1). It's wealth. (C) By making the content of the ??in the above-described range, the boundary between the liquid-repellent portion and the lyophilic portion in the pattern-forming film after exposure of the composition for forming an ink pattern of the present invention becomes clear, and the contrast of the pattern after ink application Is improved, and a still pattern is obtained.

5-4. (D) sensitizer

The sensitizer (D) used for the composition for forming an ink pattern of the present invention is added when it is desired to further improve the exposure sensitivity of the composition for forming an ink pattern. (D) It is preferable that a sensitizer is a compound which absorbs light rays or radiation and becomes excited. (D) The sensitizer is in an excited state, so that (A) when it comes into contact with the acid generator, it causes electron transfer, energy transfer, or heat generation, whereby (A) the acid generator is decomposed to produce an acid. It gets easier. (D) The sensitizer may have an absorption wavelength in a region of 350 nm to 450 nm, and polynuclear aromatics, xanthenes, xanthones, cyanines, merocyanines, rhodacyanus, oxonols, thiazines, Acridines, acridones, anthraquinones, squaliums, styryls, base styryls, or coumarins.

Below, each (D) sensitizer is shown.

[Polynuclear aromatics]

Examples of polynuclear aromatics include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, or 9,10-dipropyloxyanthracene. can do.

[Xanthenes]

Examples of xanthenes include fluorocein, eosin, erythrosine, rhodamine B, and rose bengal.

[Xanthones]

Examples of xanthones include xanthone, thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, or isopropyl thioxanthone.

[Cyanines]

As cyanines, thiacarbocyanine and oxacarbocyanine can be illustrated.

[Merocyanines]

Examples of merocyanines include merocyanine and carbomerocyanine.

[Tiagins]

As thiazines, thionine, methylene blue, and toluidine blue can be illustrated.

[Acridines]

Examples of acridine include acridine orange, chloroflavin, and acriflavin.

[Acridones]

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

[Anthraquinones]

As anthraquinones, anthraquinone can be illustrated.

[Squaliums]

As squalium, squalium can be illustrated.

[Base styryls]

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

[Coumarins]

As coumarins, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, or 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[l]benzopyrano[ 6,7,8-ij]kinoridin-11-non can be illustrated.

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

[(D) sensitizer contained in the composition for forming an ink pattern of the present invention]

As the sensitizer (D) used in the composition for forming an ink pattern of the present invention, since it has a large effect of improving exposure sensitivity, preferably polynuclear aromatics, acridones, styryls, base styryls, coumarins, or They are xanthones, particularly preferably xanthones. Among the xanthones, diethyl thioxanthone and isopropyl thioxanthone are preferable.

[Content of the sensitizer (D) in the composition for forming an ink pattern]

The content of the (D) sensitizer is preferably 0.1 to 8 parts by mass, and more preferably 1 to 4 parts by mass per 100 parts by mass of the fluorinated polymer (1). (D) By making the content of the sensitizer within the above-described range, the exposure sensitivity of the composition for forming an ink pattern is improved, and the boundary between the liquid-repellent portion and the lyophilic portion in the pattern-forming film after exposure of the pattern-forming composition of the present invention is It becomes clear, the contrast of the ink pattern after ink application is improved, and a still pattern is obtained.

5-5. (E) polymerizable compound

The (E) polymerizable compound used as a component in the composition for forming an ink pattern of the present invention is contained in the composition for forming an ink pattern in order to make the resulting pattern forming film more rigid. (E) The polymerizable compound is a compound having an ethylenically unsaturated bond other than the fluorinated polymer (1). Examples of such (E) polymerizable compounds include monofunctional or bifunctional or higher acrylic acid esters and methacrylic acid esters from the fact that the polymerizability is good and the pattern forming film obtained from the composition for forming an ink pattern becomes harder. have.

Below, each (E) polymerizable compound is shown.

[Monofunctional acrylic acid ester and methacrylic acid ester]

<Monofunctional acrylic acid ester>

As monofunctional acrylic acid ester, 2-hydroxyethyl acrylate, diethylene glycol monoethyl ether acrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, or (2-methacryloyloxyethyl) )(2-hydroxypropyl)phthalate can be illustrated.

<Monofunctional methacrylic acid ester>

Examples of the monofunctional methacrylic acid ester include 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether methacrylate, or ω-carboxypolycaprolactone monoacrylate.

Monofunctional acrylic acid esters and methacrylic acid esters can be obtained commercially, for example, from Dong-A Synthetic Co., Ltd. under the brand name Aaronics (registered trademark), product numbers M-101, M-111, M-114, and M -5300, brand names KAYARAD, product numbers TC-110S, TC-120S from Nihon Kayaku Co., Ltd., and brand names Viscoat 158 and 2311 Viscoat from Osaka Organic Chemical Industry Co., Ltd. are on the market.

[Bifunctional acrylic acid ester and methacrylic acid ester]

As a bifunctional acrylic acid ester, ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol diacrylate, or 1,9-nonanediol diacrylate Rate can be illustrated.

As a bifunctional methacrylic acid ester, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, or 1 , 9-nonanediol dimethacrylate can be illustrated.

Bifunctional acrylic acid ester and methacrylic acid ester can be obtained commercially, for example, from Dong-A Synthetic Co., Ltd. under the brand name Aaronix (registered trademark), product number M-210, M-240, M-6200, Nihongaya Brand name KAYARAD, product number HDDA, HX-220, R-604 from Ku Co., Ltd., brand name Viscoat from Osaka Organic Chemical Co., Ltd., product number 260, 312, 335HP, brand name Light acrylate 1,9-NDA from Kyoeisha Chemical Is commercially available.

[Acrylic acid ester and methacrylic acid ester of trifunctional or higher function]

Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate as trifunctional or higher acrylic acid esters and methacrylic acid esters Rate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide Modified dipentaerythritol hexaacrylate, tri(2-acryloyloxyethyl) phosphate, tri(2-methacryloyloxyethyl) phosphate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, Tris (acryloxyethyl) isocyanurate, or a compound having a linear alkylene group and an alicyclic structure, and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule, and three, four or five A polyfunctional urethane acrylate compound obtained by reacting with a compound having a dog's (meth)acryloyloxy group can be illustrated.

Trifunctional or higher acrylic acid esters and methacrylic acid esters can be obtained commercially, for example, from Dong-A Synthetic Co., Ltd. under the brand name Aaronics (registered trademark), product numbers M-309, M-315, M-400, M-405. , M-450, M-7100, M-8030, M-8060, TO-1450, brand name KAYARAD, part number TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 from Nihon Kayaku Co., Ltd. DPEA-12, brand name Viscoat, product number 295, 300, 360, GPT, 3PA, 400 from Osaka Organic Chemical Co., Ltd., and light acrylate 1,9-NDA brand name from Kyoeisha Chemical Co., Ltd. are commercially available. Polyfunctional urethane acrylate compounds are commercially available from Daiichi Pharmaceutical Co., Ltd. under the brand name New Frontier (registered trademark), product number R-1150, and Nihon Kayaku Co., Ltd. under the brand name KAYARAD, product number DPHA-40H, and the like.

As the (E) polymerizable compound used in the composition for ink pattern formation of the present invention, since it has a greater effect of making the resulting pattern forming film harder, preferably ω-carboxypolycaprolactone monoacrylate, 1,9- Nonandiol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate and dipentaerythritol It is a mixture with pentaacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, or a polyfunctional urethane acrylate-based compound. Particularly preferably, a trifunctional or higher (meth)acrylic acid ester is preferred, and it is a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

[Content of (E) polymerizable compound in the 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, particularly preferably, based on 100 parts by mass of the fluorinated polymer (1). Is 5 parts by mass to 100 parts by mass. (E) By setting the amount of the polymerizable compound to be within the above-described range, the pattern forming film obtained from the composition for forming an ink pattern can be made harder.

6. How to form an ink pattern

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

[Ink pattern formation method (A)]

In the method (A) of forming an ink pattern of the present invention, a film forming step of forming a film by applying the composition for forming an ink pattern on a substrate, and light having a wavelength of 150 nm or more and 500 nm or less are applied to the film through a photomask. It includes an exposure step of obtaining a pattern forming film having a liquid-repellent portion and a lyophilic portion by irradiation exposure, transferring the pattern of the photomask to the film, and an ink pattern forming step of applying ink to the obtained pattern forming film to obtain a pattern by ink. .

[Ink pattern formation method (B)]

In the method (B) of forming an ink pattern of the present invention, a film forming step of heating a coating film obtained by applying the composition for forming an ink pattern on a substrate, and subsequently, light having a wavelength of 150 nm or more and 500 nm or less by a drawing device. And a drawing step of obtaining a pattern forming film having a liquid repellent portion and a lyophilic portion by scanning exposure to the film to draw a pattern on the film, and an ink pattern forming step of applying ink to the obtained pattern forming film.

6-1. Film formation process, exposure or drawing process, and ink pattern formation process of the ink pattern formation method

Below, the film forming process common to the ink pattern formation method (A) and (B) of the present invention, the exposure process in the ink pattern formation method (A), and the drawing process in (B), and ink It shows about the ink pattern formation process common to the pattern formation method (A) and (B).

6-2. Production process

The film forming step is a step of heating (pre-baking) the obtained coating film by applying the composition for forming an ink pattern of the present invention to a substrate.

[Board]

As the substrate used in the film forming step, a semiconductor substrate such as a resin substrate, a glass substrate, quartz, or silicon, which has been conventionally used for an electronic circuit, can be mentioned. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyether sulfone, polycarbonate, or polyimide.

Before applying the composition for forming an ink pattern to the substrate, pretreatment such as cleaning, roughening, and application of minute uneven surfaces may be performed as necessary.

[Application method]

The method of applying the ink pattern forming composition to the substrate is not particularly limited, and application using a brush or brush, dipping method, spray method, roll coating method, rotation coating method (spin coating method), slit die coating method, bar coating Method, flexo printing, offset printing, inkjet printing, or dispensing method. In the method for forming a pattern of the present invention, preferably, a spin coating method is preferred.

[Film thickness]

The thickness of the coating film formed in the above step may 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-baked]

Although it also varies depending on the composition of the composition for forming an ink pattern to be used, 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. It is from 1 minute to 10 minutes.

6-3. Exposure process and drawing process

[Exposure process]

In the exposure step in the ink pattern forming method (A), the film obtained in the film forming step is exposed to light having a wavelength of 150 nm or more and 500 nm or less through a photomask, and the pattern of the photomask is transferred to the film. , A step of obtaining a pattern forming film having a liquid repellent portion and a lyophilic portion. In the exposure, exposure is performed through a photomask having a predetermined pattern so that an exposed portion of a pattern similar to that of a desired pattern is formed.

[Drawing process]

In the drawing step in the ink pattern forming method (B), the film obtained in the film forming step is scanned and exposed to light having a wavelength of 150 nm or more and 500 nm or less by a drawing device, and the pattern is drawn on the film, and the liquid-repellent portion It is a process of obtaining a pattern formation film which has a lyophilic part and. For example, it is carried out by scanning a predetermined pattern using a direct drawing type exposure apparatus.

[Used light]

For exposure and drawing, visible light, ultraviolet light, X-ray, or radiation, which is a flow of charged particles, can be used. It is preferably an ultraviolet ray having a wavelength of 150 nm or more and 500 nm or less, and particularly preferably an ultraviolet ray of 365 nm by an ultraviolet light emitting diode.

By exposure and drawing, the acid-dissociable group of the fluorinated polymer (1) is desorbed and volatilized due to the effect of the acid generated from the acid generator (A) in the film. As a result, the film thickness of the exposed part becomes thinner than the film thickness of the unexposed part, and a concave pattern is formed. At that time, since the acid-dissociable group has a fluorine-containing atom, the unexposed portion exhibits liquid repellency, and the exposed portion becomes lyophilic. Accordingly, the film formed on the substrate becomes a pattern forming film having a liquid-repellent unexposed portion and a lyophilic exposed portion which is a concave pattern.

[heating]

It is preferable to heat the pattern formation film after exposure. By heating the pattern forming film after exposure, it is possible to further volatilize the component by the acid-dissociable group dissociated from the fluorinated polymer (1) in the exposed portion, and a more stationary pattern consisting of exposed concave portions and unexposed convex portions Is obtained.

As a method of heating the pattern forming film, for example, a method of heating the film-forming substrate using a hot plate, a batch type oven or a conveyor type oven, a method of hot air drying using a dryer, etc., a method of vacuum baking. Can be mentioned. The heating conditions vary depending on the composition of the composition, the thickness of the obtained coating film, and the like, but it is preferably 3 minutes or more and 30 minutes or less at 60°C or more and 150°C or less.

6-4. Ink pattern formation process

The formation of the ink pattern is achieved by applying ink to the obtained pattern forming film to obtain a pattern by ink.

The difference in the contact angle between the propellant portion and the liquid-repellent portion of the pattern forming film before and after exposure to water and hexadecane, which are ink solvents, is preferably 30° or more, and more preferably 50° or more. Since the contact angle difference is within the above-described range, even when ink is applied to the convex liquid-repellent portion, the ink is splashed and the ink is easily moved to the concave portion, which is the lyophilic portion, and is composed of the exposed concave portion and the unexposed convex portion. A still ink pattern is obtained.

[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 the ink.

6-5. Application to electronic circuits and electronic devices

In the method for forming an ink pattern of the present invention, an electronic device can be manufactured by forming an electric circuit made of a conductive ink pattern on a substrate. The electronic circuit is a wiring made of a conductive ink pattern formed on a substrate. Electronic devices are devices having an electronic circuit, and include portable information devices such as liquid crystal displays and mobile phones, digital cameras, organic displays, organic EL lights, and various sensors or wearable devices.

7. Fluorinated monomer

The fluorinated polymers (1) to (3) of the present invention are synthesized by homopolymerizing or copolymerizing the fluorinated monomer (4) of the present invention shown below.

[Fluorinated monomer (4)]

The fluorinated monomer of the present invention is a fluorinated monomer represented by the following formula (4) and has a fluorinated cyclic acetal structure, and the fluorinated polymer (1) is a fluorinated monomer (4) alone or by copolymerization. Is obtained. Hereinafter, it may be called a fluorinated monomer (4).

[Formula 14]

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a C 1 to C 10 linear or C 3 to C 10 branched alkyl group, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms. ^{R 2} to R ⁵ are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine. X is a single bond or a divalent group, and up to 7 hydrogen atoms including the divalent group may be substituted with a fluorine atom Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a car It is a main acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorinated alkyl group or the carboxylic acid ester group may be substituted with a fluorine atom, R is a fluorinated alkyl group having 1 to 3 carbon atoms. )

[Fluorine-containing monomer (5)]

The fluorinated monomer (4) of the present invention is preferably a fluorinated monomer (5) in which ^{R 2} , R ⁴ , and R ^{5 in the formula (4) are hydrogen atoms.}

When the fluorinated polymer (1) obtained by polymerizing the fluorinated monomer (4) as a component of the resist or ink pattern forming composition of the present invention is formed on a substrate, for solubility in a solvent, the formula (4) ) In R ² , R ⁴ , and R ⁵ are preferably a hydrogen atom, and preferably a fluorinated monomer having a fluorinated cyclic acetal structure represented by the following formula (5). Hereinafter, it may be called a fluorinated monomer (5).

[Formula 15]

(R ¹ , R ³ , X, and Y in Formula (5) have the same meaning as Formula (4).)

[Fluorinated Monomer (6)]

The fluorinated monomer (5) of the present invention is further preferably a fluorinated monomer (6) below, in which Y in the formula (5) is a trifluoromethyl group. When forming a film on a substrate using the above-described fluorinated polymer (2) obtained by homopolymerizing or copolymerizing the fluorinated monomer (5) as a composition for forming a resist or ink pattern, for solubility in a solvent, the formula (5) It is preferable that Y in) is a trifluoromethyl group, and is a fluorinated monomer having a fluorinated cyclic acetal structure preferably represented by the following formula (6). Hereinafter, it may be called a fluorinated monomer (6).

[Formula 16]

(R ¹ , R ³ , and X in Formula (6) have the same meaning as Formula (4).)

As the fluorinated monomer (4) of the present invention, a specific example is exemplified below, but is not limited thereto.

[Formula 17]

8. Method for producing fluorinated monomer (4)

It shows about the manufacturing method of the fluorinated monomer (4) of this invention. In the method for producing a fluorinated monomer of the present invention, a hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or a hydroxyvinyl ester represented by the formula (11) is cyclized, and the formula (7) A step of obtaining a cyclic hemiacetal compound represented by) is included.

[Formula 18]

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a C 1 to C 10 linear or C 3 to C 10 branched alkyl group, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms. ^{R 2} to R ⁵ are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine. X is a single bond or a divalent group, and up to 7 hydrogen atoms including the divalent group may be substituted with a fluorine atom Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a car It is a main acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorine-containing alkyl group or the carboxylic acid ester group may be substituted with a fluorine atom, R is a fluorine-containing alkyl group having 1 to 3 carbon atoms, and Z is hydrogen An atom or a C 1-20 linear, C 3-20 branched or cyclic alkyl group, and some or all of the hydrogen atoms in Z may be substituted with halogen atoms, ether bonds, siloxane bonds, thioether bonds And may contain a carbonyl bond, the same as below.)

8-1. Acylation or alkylation of fluorinated cyclic hemiacetal compounds

The fluorinated monomer (4) of the present invention introduces a polymerizable group into the fluorinated cyclic hemiacetal compound represented by formula (7) (hereinafter, sometimes referred to as fluorinated cyclic hemiacetal compound (7)), Synthesis is possible by obtaining a fluorine monomer (4). This reaction is shown below.

[Formula 19]

(R ¹ , R ² ∼R ⁵ , X, Y are the same as the above formula, and A is a hydrogen atom, a halogen atom, an acroyl group, or a metachromyl group.)

This reaction is possible by acylation 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, in the acryloyl compound shown in the above reaction formula, It is a reaction for synthesizing the fluorinated monomer (4) by reacting with an acylating agent in which X is a single bond or an alkylating agent in which X is a divalent organic group.

8-1-1. Acylation of Fluorinated Cyclic Hemiacetal Compounds

[Acylating agent]

Examples of the acylating agent include carboxylic acid chloride or carboxylic anhydride. Examples of the acylating agent include acrylic acid chloride, methacrylic acid chloride, acrylic acid anhydride, methacrylic acid anhydride, 2-fluoroacrylic acid chloride, or 2-methacrylic acid chloride.

The amount of the acylating agent used is preferably 0.5 mol or more and 10 mol or less, and particularly preferably 1 mol or more and 3 mol or less, since the acylation yield increases with respect to 1 mol of the fluorinated cyclic hemiacetal compound (7). The reaction with the acylating agent can be carried out in the presence of a base, and the reaction can be carried out without a solvent or in a solvent.

[base]

Examples of the base include inorganic bases and organic bases. The amount of the base used for the reaction is preferably 0.05 or more and 10 mol or less, and particularly 1 mol or more and 3 mol or less with respect to 1 mol of the fluorinated cyclic hemiacetal compound (7) because the yield increases.

<Inorganic base>

Examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate or potassium hydrogen carbonate.

<Organic base>

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

[menstruum]

Examples of the solvent include a hydrocarbon-based solvent, an ether-based solvent, or a chlorine-based solvent. If necessary, you may use it with water.

<Hydrocarbon solvent>

As a hydrocarbon solvent, hexane, heptane, cyclohexane, methylcyclohexane, toluene, or xylene can be illustrated.

<Ether solvent>

Examples of the ether solvent include diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, or ethylene glycol dimethyl ether.

<Chlorine solvent>

Examples of the chlorine-based solvent include methylene chloride, chloroform, or 1,2-dichloroethylene.

8-1-2. Alkylation of fluorinated cyclic hemiacetal compounds

Introduction of a polymerizable group is also possible by alkylation of the hydroxyl group of the fluorinated cyclic hemiacetal compound (7). In the reaction, a catalyst may be used to accelerate the reaction rate.

[Alkylating agent]

Examples of the alkylating agent include halogenated alkyls and sulfonic acid esters.

The reaction with the alkylating agent can be carried out in the presence of a base, and the reaction can be carried out without a solvent or in a solvent. The amount of the alkylating agent used is preferably 0.5 mol or more and 10 mol or less per 1 mol of the fluorinated cyclic hemiacetal compound (7), and particularly 1 mol or more and 3 mol or less because the yield increases.

<alkyl halide>

Examples of the halogenated alkyl include chloroethyl acrylate, chloroethyl methacrylate, bromoethyl acrylate, and bromoethyl methacrylate.

<Sulfonic acid ester>

Examples of sulfonic acid esters include acrylate-2-methylsulfonyloxyethyl, methacrylate-2-methylsulfonyloxyethyl, acrylate-2-p-toluenesulfonyloxyethyl, and methacrylate-2-p-toluenesulfonyloxyethyl. Can be illustrated.

[base]

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

<Inorganic base>

Examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride, and ammonia.

<Organic base>

As the organometallic salt, an organolithium salt, a Grignard reagent, or an alkali metal salt can be illustrated.

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

Examples of the Grignard reagent include methyl magnesium bromide.

As the alkali metal salt, sodium methoxide, sodium ethoxide, or potassium t-butoxide can be exemplified.

[menstruum]

As the solvent, a solvent generally said to be good for a nucleophilic substitution reaction is preferable, and aprotic polar solvents and proton polar solvents are exemplified. It may be a two-layer system of these solvents and water.

Examples of the aprotic polar solvent include N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, or N-methylpyrrolidone.

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

[catalyst]

In order to accelerate the reaction rate of the alkylation reaction, iodide or bromide may be added as a catalyst. When adding a catalyst, the addition amount is preferably 0.001 to 1 mol, particularly 0.005 to 0.5 mol, per 1 mol of the hemiacetal compound (7).

<Iodine>

Examples of iodide include sodium iodide, lithium iodide, or tetrabutylammonium iodide.

<Bromide>

Examples of bromide include sodium bromide, lithium bromide, or tetrabutylammonium bromide.

9. Fluorinated annular hemiacetal

[Fluorinated phantom hemiacetal (7)]

The fluorinated polymer (1) of the present invention is obtained by polymerizing a fluorinated monomer (4). The fluorinated monomer is a fluorinated monomer and has a fluorinated cyclic acetal structure. The fluorinated cyclic hemiacetal (7) is a compound as a precursor of the fluorinated monomer (4).

[Formula 20]

(In the formula, R ² to ^{R 5} are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms and Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorine-containing alkyl group or the carboxylic acid ester group are substituted by a fluorine atom. R is a fluorinated alkyl group having 1 to 3 carbon atoms.)

[Fluorinated phantom hemiacetal (8)]

The fluorinated hemiacetal (7) of the present invention is preferably the following fluorinated hemiacetal (8) in which R ² , R ⁴ , and R ⁵ in the formula (7) are hydrogen atoms.

The fluorinated polymer (2) of the present invention is obtained by polymerizing the fluorinated monomer (5). The fluorinated monomer is a fluorinated monomer and has a fluorinated cyclic acetal structure. Moreover, the following fluorinated cyclic hemiacetal (8) is a compound as a precursor of the fluorinated monomer (5).

[Formula 21]

^{(R 3} and X in Formula (8) have the same meaning as Formula (7).)

[Fluorinated phantom hemiacetal (9)]

The fluorinated hemiacetal (7) of the present invention is further preferably a fluorinated 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 a fluorinated monomer (6), and has a fluorinated cyclic acetal structure. The following fluorinated cyclic hemiacetal (9) is a compound as a precursor of the fluorinated monomer (6).

[Formula 22]

^{(R 3} in Formula (9) has the same meaning as Formula (7).)

10. Synthesis of fluorinated cyclic hemiacetal (7)

The manufacturing method of the fluorinated cyclic hemiacetal (7) of the present invention will be described.

By cyclizing the hydroxycarbonyl compound represented by the following formula (10) or the hydroxyvinyl ether or hydroxyvinyl ester represented by the formula (11) to obtain the cyclic hemiacetal compound of the invention 12 represented by the formula (7) It is a method for producing a cyclic hemiacetal compound to be obtained.

[Formula 23]

(In the formula, R ² to ^{R 5} are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms and Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorine-containing alkyl group or the carboxylic acid ester group are substituted by a fluorine atom. R is a C1-C3 fluorinated alkyl group, Z is a hydrogen atom or a C1-C20 linear, C3-C20 branched or cyclic alkyl group, and some or all of the hydrogen atoms in Z are It may be substituted with a halogen atom, and may contain an ether bond, a siloxane bond, a thioether bond, and a carbonyl bond.)

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

10-1. 1st process

The first step is a carbonyl-ene reaction of allyl alcohols, allyl ethers or allyl esters with hexafluoroacetone (hereinafter sometimes referred to as HFA) or trifluoropyruvate ester, as shown in formula (10). It is a step of obtaining the hydroxyvinyl ester represented or the hydroxyvinyl ether represented by formula (11).

Below, by the carbonyl-ene reaction of allyl alcohols, allyl ethers or allyl esters represented by formula (12) and trifluorocarbonyl compound represented by formula (13), represented by formula (10) G represents a reaction for obtaining a hydroxyvinylcarbonyl compound or a hydroxyvinyl ether or hydroxyester represented by formula (11). Hereinafter referred to as hydroxycarbonyl compounds (10), hydroxyvinyl ethers (11) allyl alcohols (12), allyl ethers (12), allyl esters (12), and trifluorocarbonyl compounds (13). There are cases.

[Formula 24]

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a C 1 to C 10 linear or C 3 to C 10 branched alkyl group, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms. ^{R 2} to R ⁵ are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine. Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorine-containing alkyl group or the carboxylic acid ester group are formed by a fluorine atom. R is a C1-C3 fluorinated alkyl group, Z is a hydrogen atom, or a C1-C20 linear, C3-C20 branched or cyclic alkyl group, and part of the hydrogen atoms in Z or All may be substituted with a halogen atom, and an ether bond, a siloxane bond, a thioether bond, and a carbonyl bond may be included.)

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 protected hydroxyl group are mixed with HFA in which Y is a trifluoromethyl group, and the like It is possible to selectively synthesize hydroxyvinyl ester (10) or hydroxyvinyl ether (11) by heating as necessary under closed pressurization. In addition, even when a trifluoropyruvate ester is used instead of HFA, the reaction proceeds efficiently.

This reaction is an ene reaction of an allyl moiety of allyl alcohols (12), allyl ethers (12) or allyl esters (12) with a fluorinated carbonyl compound (13), and allyl alcohols (12), allyl ethers ( 12) Or the higher the electron density of the olefin portion on the allyl esters (12) side, the easier the reaction proceeds, and the reaction can be selectively proceeded with fewer side reactions. ^{R 2 to R 5} in allyl alcohols (12), allyl ethers (12), or allyl esters (12) are preferably hydrogen atoms, and some of them are preferably substituted by electron donating groups. A methyl group is preferred.

The amount of HFA or trifluoropyruvate ester used per 1 mol in allyl alcohols (12), allyl ethers (12) or allyl esters (12) is preferably 0.5 mol or more and 10 mol or less, and particularly 1 mol or more and 3 Mole or less is preferable.

[Allyl alcohol]

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

[Allyl ethers]

As the allyl ethers (12) or allyl esters (12) in which Z is other than a hydrogen atom, it is preferable to introduce a protecting group into the hydroxyl group of the allyl alcohols (12) described above, and the types of the protecting group include silyl groups, acetals, and acyls. , Benzyls, or carbamates. In order to improve the electron density of the olefin moiety and to accelerate the reaction, the protecting group is preferably acetal, silyl, carbamate or benzyl.

<Silyl air flow>

Examples of silyl groups include trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, or t-butyldiphenylsilyl group.

<Acetals>

Examples of acetals include tetrahydropyranyl group, ethoxyethyl group, butoxyethyl group, methoxymethyl group, methylthiomethyl group, benzyloxymethyl group, or methoxyethoxymethyl group.

<Acyls>

Examples of acyls include formyl group, acetyl group, trifluoroacetyl group, propionyl group, benzoyl group, pivaloyl group, acrylyl group, or methacrylyl group.

<Benzyls>

As benzyls, a benzyl group and a p-methoxybenzyl group can be illustrated.

<Carbamates>

Examples of carbamates include t-butoxycarbonyl group and benzyloxycarbonyl group.

10-2. 1st process

The reaction in the first step proceeds even without a catalyst or a solvent, but in order to accelerate the reaction, it is also possible to use an acid catalyst in a solvent. In order to manufacture more cheaply, it is carried out in a solvent-free, no-catalyst, and from the reaction product, a hydroxycarbonyl compound represented by the following formula (10), or a hydroxyvinyl ether represented by the formula (11), hydroxyvinyl It is preferable to isolate esters by a purification operation such as distillation.

[Formula 25]

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

Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, or zeolite. Examples of the organic acid include carboxylic acid, sulfonic acid, cation exchange resin, and Lewis acid. Specifically, formic acid, acetic acid or trifluoroacetic acid as the carboxylic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid as the sulfonic acid, and aluminum chloride, titanium tetrachloride, or tin chloride as the Lewis acid can be illustrated. .

The reaction proceeds even without using a solvent, but when used, allyl alcohols (12), allyl ethers (12) or allyl esters (12) as raw materials, HFA or trifluoropyruvate ester (13), and the target product are formula A solvent that is inert to the fluorine-containing compound represented by (10) or formula (11) may be sufficient. Examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons or ethers.

[Aliphatic hydrocarbons]

Examples of the aliphatic hydrocarbon include hexane, heptane, cyclohexane, and methylcyclohexane, which is a cyclic aliphatic hydrocarbon.

[Aromatic hydrocarbons]

As an aromatic hydrocarbon, benzene, toluene, or xylene can be illustrated.

[Halogenated hydrocarbons]

Methylene chloride can be illustrated as the halogenated hydrocarbon.

[Ethers]

Examples of ethers include diethyl ether, dibutyl ether, tetrahydrofuran, or ethylene glycol dimethyl ether.

10-3. 2nd process

The second step is a step of cyclizing a hydroxycarbonyl compound (10), hydroxyvinyl ether or hydroxyvinyl ester (11) in a molecule to obtain a cyclic hemiacetal compound (7).

Although it varies in various ways depending on the kind and substituent of the product in the first step, it is mainly possible by the three methods described above (Methods 1 to 3).

10-3-1. Method-1

Method-1 is a hydroxycarbonyl compound (10) in a solvent, as shown in the following reaction formula, selectively undergoes intramolecular cyclization by the action of an acid or a base, and fluorinated cyclic hemiacetal (7) How to get it.

[Formula 26]

It is preferable to carry out this method in a solvent under acidic conditions or basic conditions.

As the acid, either inorganic acid, organic acid, or Lewis acid can be used. The amount of acid used for the reaction is preferably 0.01 mol or more and 1 mol or less, and particularly preferably 0.05 mol or more and 0.2 mol or less, based on 1 mol of the hydroxycarbonyl compound (10).

Examples of the base include inorganic bases and organic bases. In a two-layer system of a water-organic solvent, in which it is possible to remove unreacted raw materials and trace amounts of fluorinated alcohols, it is particularly preferable to use sodium hydroxide or potassium hydroxide under basic conditions. The amount of the base used in the reaction is preferably 0.5 mol or more and 10 mol or less, and particularly 1 mol or more and 3 mol or less, so that the yield increases, with respect to 1 mol of the hydroxycarbonyl compound (10).

[Inorganic acid]

Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, or zeolite.

[Organic acid]

Examples of the organic acid include carboxylic acid, sulfonic acid, cation exchange resin, and Lewis acid. Examples of the carboxylic acid include formic acid, acetic acid or trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid as the sulfonic acid, and aluminum chloride, titanium tetrachloride, or tin chloride as the Lewis acid.

[Inorganic base]

Examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride, and ammonia.

[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, or n-butyllithium. Examples of the Grignard reagent include methyl magnesium bromide. Examples of the organic alkali metal salt include sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[menstruum]

The reaction proceeds even without using a solvent, but when used, a solvent inert to the hydroxycarbonyl compound (10) as a raw material and the fluorinated cyclic hemiacetal (7) as a product may be used. Examples include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and ethers.

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

10-3-2. Method-2

Method-2, as shown in the following reaction formula, after deprotecting the hydroxyvinyl ether (11) or the hydroxyvinyl ester (11), in a solvent, by the action of an acid or a base, the hydrogen atom of the hydroxyl group is removed. This is a method for obtaining a fluorinated cyclic hemiacetal (7) by selectively performing intramolecular cyclization by extraction. This reaction is shown below.

[Formula 27]

Hydroxyvinyl ether (11) or hydroxyvinyl ester (11) is a compound in which a hydroxyl group is protected, and hydroxyvinyl ether (11), or hydroxyvinyl ester (11) deprotects a protecting group, and After conversion from vinyl ether (11) or hydroxyvinyl ester (11) to hydroxycarbonyl compound (10), intramolecular cyclization is carried out in the same manner as in Method 1 to obtain fluorinated cyclic hemiacetal (7). I can. For deprotection, it is possible to use a general deprotection method. The acid, base, or solvent to be used is the same as in Method-1.

10-3-3. Method-3

Method-3, as shown in the following reaction formula, by extracting the hydrogen atom of the hydroxyl group by the action of hydroxyvinyl ether (11) or hydroxyvinyl ester (11) in a solvent, an acid or a base, selectively This is a method of obtaining a fluorinated cyclic hemiacetal (7) by performing intramolecular cyclization to obtain a fluorinated cyclic acetal intermediate (14), followed by deprotection. This reaction is shown below.

[Formula 28]

[My Molecular Currency]

By heating the hydroxyvinyl ether (11) or the hydroxyvinyl ester (11) to the boiling point of the solvent by adding an acid catalyst without a solvent or in a solvent, a fluorinated cyclic acetal intermediate represented by formula (14) can be obtained. have.

Since the fluorinated cyclic acetal intermediate (14) can be obtained in a high yield, trifluoroacetic acid, methanesulfonic acid or sulfuric acid is particularly preferred. The amount of acid used for the reaction is preferably 0.01 mol or more and 1 mol or less, and particularly preferably 0.05 mol or more and 0.2 mol or less, based on 1 mol of hydroxyvinyl ether (11) or hydroxyvinyl ester (11).

[mountain]

As the acid used in Method-3, any of inorganic acids, organic acids, and Lewis acids can be used.

<Inorganic acid>

Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, or zeolite.

<Organic acid>

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

Examples of the carboxylic acid include formic acid, acetic acid or trifluoroacetic acid, and examples of the sulfonic acid include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, or p-toluenesulfonic acid. As the Lewis acid, aluminum chloride, titanium tetrachloride, or tin chloride can be exemplified.

[Deprotection]

The fluorinated cyclic acetal intermediate (14) is a form in which the hydroxyl group of the fluorinated cyclic hemiacetal (7) is protected by another substituent, and by deprotecting the protecting group, it becomes possible to obtain the fluorinated cyclic hemiacetal (7). For deprotection, a general deprotection method can be used.

On the other hand, in the case of the fluorinated compound (15) in which Z of the hydroxyvinyl ether (11) has a polymerizable group, the fluorinated monomer (4) can be synthesized by intramolecular cyclization in the front end of Method-3. Do. This reaction is shown below.

[Formula 29]

Example

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

1. Synthesis of fluorinated cyclic hemiacetal

As a precursor for obtaining the fluorinated monomer (4), fluorinated cyclic hemiacetals-1 to 7 belonging to the fluorinated monomer represented by the above formula (7) were synthesized by the following production method.

1-1-1. Synthesis of fluorinated cyclic hemiacetal-1 (Part 1)

Into a reactor equipped with a stirrer, allyl alcohol (manufactured by Tokyo Kasei Corporation, 11.6 g (0.2 mol) was introduced and the reactor was sealed. Next, after degassing the inside of the reactor with a vacuum pump, the contents were stirred with a stirrer while stirring the contents with a stirrer. And HFA 66.4 g (0.40 mol) was introduced Next, after the temperature in the reactor was raised to 150° C., stirring was continued for 40 hours After completion of the reaction, the contents were taken out and transferred to a separatory funnel, and hydrochloric acid having a concentration of 3.5 mass% After 50 ml was added and stirred for 2 hours, the organic layer and the aqueous layer were separated 50 ml of sodium hydroxide water having a concentration of 4% by mass was added to the organic layer, and after stirring for 1 hour, the organic layer was separated, pressure 3.0 kPa, temperature 60 It distilled under reduced pressure under the conditions of C to 62 C to obtain 22.4 g of fluorinated cyclic hemiacetal-1 represented by the following formula in a yield of 50%.

[Formula 30]

<NMR analysis result>

The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. ¹ H-NMR (solvent: heavy chloroform, reference substance: TMS); δ (ppm) 2.32-2.59 (2H, m), 2.65-2.78 (2H, m), 4.11 (1H, br), 6.20 (1H, d)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: 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)

Into a reactor equipped with a stirrer, 11.6 g (0.2 mol) of allyl alcohol and methanesulfonic acid (0.2 g (0.0002 mol) were introduced, and the reactor was sealed. While stirring, HFA 66.4 g (0.40 mol) was introduced, and then the inside of the reactor was heated up to 120° C. Then, stirring was continued for 20 hours After completion of the reaction, the contents were removed and transferred to a separatory funnel, and a concentration of 4% by mass was added. After adding 50 ml of sodium hydroxide water and stirring for 1 hour, the organic layer was separated, distilled under reduced pressure under the conditions of a pressure of 3.0 kPa and a temperature of 60°C to 62°C, and 28 as fluorinated cyclic hemiacetal-1 represented by the following formula g was obtained in a yield of 63%, and this reaction is shown below.

[Chemical Formula 31]

1-2. Synthesis of fluorinated cyclic hemiacetal-2

Into a reactor equipped with a stirrer, β-metalyl alcohol (manufactured by Tokyo Kasei Co., Ltd., 14.4 g (0.2 mol) was introduced, and the reactor was sealed. Next, after degassing the inside of the reactor with a vacuum pump, the contents were carried out with a stirrer. While stirring, HFA 66.4 g (0.40 mol) was introduced Next, after heating the inside of the reactor at 40° C., stirring was continued for 2 hours After completion of the reaction, the contents were taken out and transferred to a separatory funnel, and the concentration was 3.5% by mass. 50 ml of hydrochloric acid was added, and after stirring for 2 hours, the organic layer and the aqueous layer were separated, 50 ml of sodium hydroxide solution having a concentration of 4% by mass was added to the organic layer, and after stirring for 1 hour, the organic layer was separated and a pressure of 3.0 kPa, It distilled under reduced pressure under conditions of a temperature of 68°C to 69°C to obtain 43.7 g in a yield of 92% as fluorinated cyclic hemiacetal-2 represented by the following formula.

[Formula 32]

<NMR analysis result>

¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ(ppm)

Isomer 1: 1.14 (3H, d), 1.93-2.05 (1H, m), 2.40 (2H, dd), 3.80 (1H, d), 5.19 (1H, d)

Isomer 2: 1.10 (3H, d), 2.18 (1H, dd), 2.2-2.5 (1H, m), 2.55 (1H, dd), 3.25 (1H, d), 5.55 (1H, d)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-77.5(3F, m), -79.5(3F, m)

1-3. Synthesis of fluorinated cyclic hemiacetal-3

Except for using 2-methyl-3-butene-2-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in place of the β-metalyl alcohol used in the above-described fluorinated cyclic hemiacetal-2 synthesis, fluorinated cyclic hemiacetal- In the same procedure as in the synthesis of 2, the reaction represented by the following formula was performed to obtain fluorinated cyclic hemiacetal-3 in a yield of 87%. This reaction is shown below.

[Formula 33]

1-4. Synthesis of fluorinated cyclic hemiacetal-4

In the same procedure as for the synthesis of fluorinated cyclic hemiacetal-2, except that crotyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in place of the β-metalyl alcohol used in the above-described fluorinated cyclic hemiacetal-2 synthesis. , Reaction represented by the following formula was performed, and fluorinated cyclic hemiacetal-4 was obtained in a yield of 75%. This reaction is shown below.

[Formula 34]

1-5. Synthesis of fluorinated cyclic hemiacetal-5

Except for using 3-methyl-2-butene-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in place of the β-metalyl alcohol used in the above-described fluorinated cyclic hemiacetal-2 synthesis, fluorinated cyclic hemiacetal- In the same procedure as in the synthesis of 2, the reaction represented by the following formula was performed to obtain fluorinated cyclic hemiacetal-5 in a yield of 65%. This reaction is shown below.

[Formula 35]

1-6. Synthesis of fluorinated cyclic hemiacetal-6

1.86 g (0.01 mol) of β-metalyl alcohol protected with t-butyldimethylsilyl in a 100 ml glass flask equipped with a stirrer in advance and synthesized separately 2.92 g (0.01 mol) of 1,1,1,3,3,3-hexafluoroisopropyl trifluoropyruvate were mixed. Subsequently, after raising the temperature in the reactor by 50° C., stirring was continued for 18 hours. After completion of the reaction, the contents were taken out and transferred to a separatory funnel, 10 ml of hydrochloric acid having a concentration of 3.5% by mass was added, followed by stirring for 2 hours, and the organic layer and the aqueous layer were separated. 10 ml of sodium hydroxide solution having a concentration of 4% by mass was added to the organic layer, and after stirring for 1 hour, the organic layer was separated and separated by silica gel column chromatography. Fluorinated cyclic hemiacetal-6 represented by the following formula, 19.0 g, was obtained in a yield of 52%. This reaction is shown below.

[Chemical Formula 36]

<NMR analysis result>

¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ(ppm)

Isomer 1: 1.17 (3H, d), 1.97-2.11 (1H, m), 2.45 (2H, dd), 3.81 (1H, d), 5.25 (1H, d), 5.68 (1H, m)

Isomer 2: 1.11 (3H, d), 2.22 (1H, dd), 2.25-2.53 (1H, m), 2.65 (1H, dd), 3.30 (1H, d), 5.60 (1H, d), 5.68 (1H , m)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-77.1(6F, m), -78.5(3F, m)

[Synthesis of trifluoropyruvate 1,1,1,3,3,3-hexafluoroisopropyl]

The procedure for synthesizing trifluoropyruvate 1,1,1,3,3,3-hexafluoroisopropyl used in the synthesis of the fluorinated cyclic hemiacetal-6 is shown below.

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

[Chemical Formula 37]

<NMR analysis result>

¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 5.65 (1H, m)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-76.6(6F, s), -83.1(3F, s)

1-7. Synthesis of fluorinated cyclic hemiacetal-7

In place of the trifluoropyruvate 1,1,1,3,3,3-hexafluoroisopropyl used in the synthesis of the above-described fluorinated cyclic hemiacetal-6, trifluoropyruvate 2,2,2 separately synthesized Except having used -trifluoroethyl, the reaction represented by the following formula was performed in the same procedure as the synthesis of fluorinated cyclic hemiacetal-6, and fluorinated cyclic hemiacetal-7 was obtained in a yield of 61%. This reaction is shown below.

[Formula 38]

[Synthesis of 2,2,2-trifluoroethyl trifluoropyruvate]

The procedure for synthesizing 2,2,2-trifluoroethyl trifluoropyruvate used in the synthesis of the fluorinated cyclic hemiacetal-7 is shown below.

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

[Chemical Formula 39]

2. Synthesis of Fluorinated Monomer

A fluorinated monomer (4) was synthesized using the above formula (7) fluorinated cyclic hemiacetal-1, 2, 6, and 7.

2-1. Synthesis of Fluorinated Monomer-1

To a 300 ml glass flask equipped with a stirrer, 22.4 g (0.1 mol) of fluorinated cyclic hemiacetal-1, 15.1 g (0.15 mol) of triethylamine, and methoxyphenol (1000 ppm) as a polymerization inhibitor were added, and an internal temperature of 30°C. Below, 16.9 g (0.11 mol) of methacrylic anhydride was dripped. After stirring for 2 hours, 40 ml of diisopropyl ether and 30 ml of pure water were added, and after stirring and separation, 20 ml of 1% by weight sodium hydroxide solution was added and stirred for 1 hour, followed by separation. The organic layer was washed twice with 30 ml of pure water, and then distilled under reduced pressure under conditions of 1.1 kPa and a temperature of 70°C to 72°C to obtain a fluorinated monomer-1 in a yield of 85%. This reaction is shown below.

[Formula 40]

<NMR analysis result>

¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ(ppm) 1.92(3H, s), 2.32-2.59(2H, m), 2.72-2.89(2H, m), 5.65(1H, q), 6.12(1H, q), 6.68(1H, d)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-77.5(3F, s), -79.5(3F, s)

2-2. Synthesis of Fluorinated Monomer-2

In the same procedure as the synthesis of fluorinated monomer-1, except for using fluorinated cyclic hemiacetal-2 instead of fluorinated cyclic hemiacetal-1 used in the synthesis of the above-described fluorinated monomer-1, in the following formula: The reaction shown was carried out to obtain a fluorinated monomer-2 in a yield of 93%. This reaction is shown below.

[Formula 41]

<NMR analysis result>

The results of nuclear magnetic resonance analysis are shown below.

¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 1.19 (3H, s) (Isomer A), 1.23 (3H, s) (Isomer B), after which the isomer peaks were not separated and attributed as a mixture. 1.92(3H, s), 2.32-2.59(2H, m), 2.72-2.89(2H, m), 5.65(1H, q), 6.14(1H, q), 6.17(1H, dd)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-77.3(3F, s), -79.0(3F, s)

2-3. Synthesis of Fluorinated Monomer-3

Except for using 2-fluoroacrylic acid chloride in place of the methacrylic anhydride used in the synthesis of the above-described fluorinated monomer-2, the reaction represented by the following formula was carried out in the same procedure as the synthesis of the fluorinated monomer-2. , Fluorinated monomer-3 was obtained in a yield of 70%. This reaction is shown below.

[Formula 42]

<NMR analysis result>

¹ H-NMR (solvent: deuterium chloroform, reference substance: TMS); δ (ppm) 1.17 (3H, s) (Isomer A), 1.22 (3H, s) (Isomer B), after which the peaks of the isomers were not separated and attributed as a mixture. 1.92(3H, s), 2.32-2.59(2H, m), 2.72-2.89(2H, m), 6.12(1H, q), 6.45(1H, q), 6.68(1H, d)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-10.3(1F, S), -77.3 (3F, s), -79.0(3F, s)

2-4. Synthesis of Fluorinated Monomer-4

Reaction represented by the following formula in the same procedure as the synthesis of fluorinated monomer-2, except that 2-methacrylic anhydride was used in place of the methacrylic anhydride used in the synthesis of the above-described fluorinated monomer-2. And fluorinated monomer-4 was obtained in a yield of 80%. This reaction is shown below.

[Formula 43]

<NMR analysis result>

¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 1.21 (3H, s), 1.90 (3H, s), 2.30-2.55 (2H, m), 2.74-2.86 (2H, m), 4.43 (2H, s), 5.60 (1H, q), 6.09(1H, q), 6.15(1H, dd)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-77.7(3F, s), -79.6(3F, s)

2-5. Synthesis of Fluorinated Monomer-5

To a 300 ml glass flask with a stirrer, fluorinated cyclic hemiacetal-2 22.4 g (0.1 mol), triethylamine 15.1 g (0.15 mol), potassium iodide 0.8 g (0.05 mol), dimethylformamide 20 ml, polymerization inhibitor As methoxyphenol (1000 ppm) was added, and 16.3 g (0.11 mol) of chloroethyl methacrylate was added dropwise at an internal temperature of 30°C or less. After stirring for 2 hours, 40 ml of diisopropyl ether and 30 ml of pure water were added, and after stirring and separation, 50 ml of 5% by weight hydrochloric acid was added and stirred for 30 minutes, followed by liquid separation. The organic layer was washed twice with 50 ml of pure water, and then distilled under reduced pressure under the conditions of 1.0 kPa and a temperature of 89°C to 91°C to obtain a fluorinated monomer-5 in a yield of 45%. This reaction is shown below.

[Formula 44]

<NMR analysis result>

¹ H-NMR (solvent: deuterium chloroform, reference substance: TMS); δ (ppm) 1.23 (3H, s), 1.92 (3H, s), 2.22-2.50 (2H, m), 2.70-2.81 (2H, m), 3.85 (2H, m), 4.03 (2H, m), 5.63(1H, q), 6.15(1H, q), 6.22(1H, dd)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-77.0(3F, s), -79.3(3F, s)

2-6. Synthesis of Fluorinated Monomer-6

Except for using fluorinated cyclic hemiacetal-6 instead of fluorinated cyclic hemiacetal-2 used in the synthesis of the above-described fluorinated cyclic monomer-2, in the same procedure as the synthesis of fluorinated cyclic monomer-2, the following formula The reaction shown in was performed to obtain a fluorinated monomer-6 in a yield of 78%. This reaction is shown below.

[Formula 45]

<NMR analysis result>

¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 1.16 (3H, s), 1.95 (3H, s), 2.27-2.54 (2H, m), 2.65-2.80 (2H, m), 5.61 (1H, q), 5.83 (1H, m), 6.12(1H, q), 6.18(1H, dd)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-77.5(6F, m), -79.5(3F, m)

2-7. Synthesis of Fluorinated Monomer-7

Except for using fluorinated cyclic hemiacetal-7 instead of fluorinated cyclic hemiacetal-2 used in the synthesis of the above-described fluorinated monomer-2, in the same procedure as for the synthesis of fluorinated monomer-2, The reaction shown was carried out to obtain a fluorinated monomer-7 in a yield of 74%. This reaction is shown below.

[Formula 46]

<NMR analysis result>

¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ (ppm) 1.22 (3H, s), 1.89 (3H, s), 2.24-2.50 (2H, m), 2.68-2.87 (2H, m), 4.86 (2H, m), 5.65 (1H, q), 6.13(1H, q), 6.18(1H, dd)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-77.9(3F, m), -78.5(3F, m)

2-8. Synthesis of Fluorinated Monomer-8

Except for using 2-fluoroacrylic acid chloride in place of the methacrylic anhydride used in the synthesis of the above-described fluorinated monomer-6, the reaction represented by the following formula was carried out in the same procedure as the synthesis of the fluorinated monomer-6. , Fluorinated monomer-8 was obtained in a yield of 68%. This reaction is shown below.

[Chemical Formula 47]

<NMR analysis result>

¹ H-NMR (solvent: deuterium chloroform, reference substance: TMS); δ(ppm) 1.17(3H, s), 2.27-2.52(2H, m), 2.62-2.82(2H, m), 5.64(1H, q), 5.93(1H, m), 6.42(1H, q), 6.68 (1H, dd)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-10.1(1F, S), -77.9(6F, m), -79.0(3F, m)

2-9. Synthesis of Fluorinated Monomer-9

Except for using 2-fluoroacrylic acid chloride instead of the methacrylic anhydride used in the synthesis of the above-described fluorinated monomer-7, the reaction represented by the following formula was carried out in the same procedure as the synthesis of the fluorinated monomer-7. , Fluorinated monomer-9 was obtained in a yield of 65%. This reaction is shown below.

[Formula 48]

<NMR analysis result>

¹ H-NMR (solvent: deuterated chloroform, reference substance: TMS); δ(ppm) 1.17(3H, s), 2.27-2.52(2H, m), 2.62-2.82(2H, m), 4.93(2H, m), 5.64(1H, q), 6.42(1H, q), 6.68 (1H, dd)

¹⁹ F-NMR (solvent: heavy chloroform, reference substance: C ₆ D ₆ ); δ(ppm)-10.4(1F, S), -77.1(6F, m), -79.3(3F, m)

3. Synthesis of comparative monomers

In order to compare with the fluorinated monomers-1 to 9 of the present invention, comparative monomers 1-3 that do not belong to the fluorinated monomers represented by formula (6) were synthesized.

3-1. Synthesis of Comparative Monomer-1

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

In a 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 paratoluenesulfonic acid was added, followed by stirring for 1 hour. The reaction was stopped by adding 3 ml of triethylamine. The obtained reaction mixture was washed with 50 ml of water, dried over anhydrous magnesium sulfate, and the solvent was distilled off, followed by distillation under reduced pressure under conditions of 0.4 kPa and a temperature of 66°C to 67°C to obtain 50 g of comparative monomer-1. This reaction is shown below.

[Formula 49]

3-2. Synthesis of Comparative Monomer-2

Comparative monomer-2 was synthesized using the method described in Patent Document 5.

To a mixture of 16.8 g of HFIP and 120 g of tetrahydrofuran, 129 ml of butyllithium (1.6 M hexane solution) was added at 5°C under a nitrogen atmosphere, followed by stirring at 5°C for 1 hour. Next, 14.2 g of 2-oxopropyl methacrylate was added at 5°C. After stirring for 10 hours, diluted hydrochloric acid was added to stop the reaction and neutralized. After normal aqueous post-treatment, purification was performed 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 the usual post-treatment of washing, drying and concentration was distilled under reduced pressure to obtain 20 g of hemiacetal.

A 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 filtered off and concentrated under reduced pressure, followed by purification by silica gel column chromatography to obtain 3 g of a comparative monomer-2. This reaction is shown below.

[Formula 50]

(MeI represents methyl iodide)

3-3. Synthesis of Comparative Monomer-3

To a 300 ml glass flask equipped with a stirrer, 33.6 g (0.3 mol) of vinyl methacrylate (manufactured by Tokyo Kasei Co., Ltd., the same below), and 52.9 g (0.315 mol) of HFIP were added, and then 0.74 g (7.5 mmol) of sulfuric acid was gradually added. Further, the mixture was stirred at a reaction temperature of 40° C. for 6 hours, and a reaction represented by the following formula was performed. This reaction is shown below.

[Formula 51]

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

4. Synthesis of polymer

Using fluorinated monomers-1 to 9, comparative monomers-1 to 3, and hexafluoroisopropyl methacrylate (manufactured by Santral Glass Co., Ltd., brand name HFIP-M) as comparative monomer 4, fluorinated polymers-1 to 12 and Comparative Polymers-1 to 7 were synthesized. The fluorinated polymers-1 to 12 belong to the fluorinated polymer (1). Comparative monomers -1 to 7 are for comparison with the fluorinated polymers -1 to 12 of the present invention, and do not belong to the fluorinated polymer (1).

In addition, in the fluorinated polymers-1 to 9 and the comparative polymers-1 to 4, magnetic polymers were synthesized so that the difference in the effect and performance of the monomers was clearly indicated, and the performances thereof were compared. In the fluorinated polymers-10 to 12 and the comparative polymers-5 to 7, a copolymerization monomer is fixed to 5-methacryloyloxy-2,6-norbornanecarbolactone (MNLA), and the fluorinated monomer of the present invention It was carried out in order to compare the performance of the and the comparative monomers as a resist material.

[Analysis of polymer]

<NMR>

The composition of the repeating unit in the polymer was determined by the measured values of ¹ H-NMR and ^{19 F-NMR by NMR.}

<Molecular weight>

The number average molecular weight Mn and the molecular weight dispersion (ratio of the number average molecular weight Mn and the mass average molecular weight Mw = Mw/Mn) of the polymer are high-speed gel permeation chromatography (hereinafter sometimes referred to as GPC. Toso Corporation make, type HLC) -8320GPC) was used, and Tosoh Corporation ALPHA-M column and ALPHA-2500 column were connected in series one by one, and measured using tetrahydrofuran as a developing solvent. As a detector, a refractive index difference measurement detector was used.

4-1. Synthesis of Fluorinated Polymer-1

Into a 300 ml glass flask equipped with a stirrer, at room temperature, 29.2 g (0.1 mol) of a fluorinated monomer-1 and 60 g of 2-butanone as a solvent were added to obtain a butanone solution having a concentration of 33% by mass. As a polymerization initiator, 2,2'-azobis (isobutyronitrile) (hereinafter sometimes referred to as AIBN, manufactured by Wako Pure Chemical Industries, Ltd.) 0.8 g (0.005 mol) was added, and after degassing while stirring, the inside of the flask was It was substituted with nitrogen gas, and after raising the temperature to 80 degreeC, it was made to react for 6 hours. The content after completion of the reaction was added dropwise to 500 g of n-heptane to obtain a white precipitate. This precipitate was filtered off, 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 in a yield of 88%.

[Formula 52]

<GPC measurement result>

Mw=22,000, Mw/Mn=2.0

4-2. Synthesis of Fluorinated Polymer-2

In place of the fluorinated monomer-1 used in the synthesis of the fluorinated polymer-1 described above, except that the fluorinated monomer-2 was used, in the same procedure as the synthesis of the fluorinated polymer-1, the following repeating units were included. The fluorinated polymer-2 was synthesized to obtain a fluorinated polymer-2 in a yield of 87%.

[Chemical Formula 53]

<GPC measurement result>

Mw=23,100, Mw/Mn=2.1

4-3. Synthesis of Fluorinated Polymer-3

In place of the fluorinated monomer-1 used in the synthesis of the fluorinated polymer-1 described above, except for using the fluorinated monomer-3, in the same procedure as the synthesis of the fluorinated polymer-1, the following repeating units are included. The fluorinated polymer-3 was synthesized to obtain a fluorinated polymer-3 in a yield of 93%.

[Chemical Formula 54]

<GPC measurement result>

Mw=21,200, Mw/Mn=2.3

4-4. Synthesis of Fluorinated Polymer-4

In the same procedure as for the synthesis of fluorinated polymer-1, the following repeating units were included, except that fluorinated monomer-4 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1. The fluoropolymer-4 was synthesized to obtain a fluorinated polymer-4 in a yield of 92%.

[Chemical Formula 55]

<GPC measurement result>

Mw=22,500, Mw/Mn=2.1

4-5. Synthesis of Fluorinated Polymer-5

In the same procedure as for the synthesis of fluorinated polymer-1, the following repeating units were included, except that the fluorinated monomer-5 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1. The fluoropolymer-5 was synthesized to obtain a fluorinated polymer-5 in a yield of 90%.

[Chemical Formula 56]

<GPC measurement result>

Mw=24,200, Mw/Mn=2.3

4-6. Synthesis of Fluorinated Polymer-6

Except for using the fluorinated cyclic monomer-6 instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1, the following repeating units are included in the same procedure as the synthesis of the fluorinated polymer-1. The fluorinated polymer-6 was synthesized to obtain a fluorinated polymer-6 in a yield of 72%.

[Chemical Formula 57]

<GPC measurement result>

Mw=20,700, Mw/Mn=2.5

4-7. Synthesis of Fluorinated Polymer-7

In the same procedure as for the synthesis of fluorinated polymer-1, the following repeating units were included, except that the fluorinated monomer-7 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1. The fluoropolymer-7 was synthesized to obtain a fluorinated polymer-7 in a yield of 78%.

[Chemical Formula 58]

<GPC measurement result>

Mw=20,100, Mw/Mn=2.2

4-8. Synthesis of Fluorinated Polymer-8

In the same procedure as the synthesis of fluorinated polymer-1, the following repeating units were included, except that fluorinated monomer-8 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1. The fluoropolymer-8 was synthesized to obtain a fluorinated polymer-8 in a yield of 90%.

[Chemical Formula 59]

<GPC measurement result>

Mw=19,700, Mw/Mn=2.3

4-9. Synthesis of Fluorinated Polymer-9

In the same procedure as for the synthesis of fluorinated polymer-1, the following repeating units were included, except that fluorinated monomer-9 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1. The fluoropolymer-9 was synthesized to obtain a fluorinated polymer-9 in a yield of 89%.

[Chemical Formula 60]

<GPC measurement result>

Mw=20,900, Mw/Mn=2.1

4-10. Synthesis of Fluorinated Polymer-10

In a glass flask, 29.2 g (0.1 mol) of fluorinated monomer-1 at room temperature (about 20° C.), 5-methacryloyloxy-2,6-norbornane giving a repeating unit of adhesion when used as a resist 11.1 g (0.05 mol) of carbolactone (MNLA) and 0.67 g of n-dodecyl mercaptan (manufactured by Tokyo Chemical Co., Ltd.) were introduced, and 82.8 g of 2-butanone was added to dissolve. As a polymerization initiator, 1.7 g of 2,2'-azobis (isobutyronitrile) (hereinafter sometimes referred to as AIBN, manufactured by Wako Junyaku Co., Ltd.) was added and degassed while stirring, and then the flask was replaced with nitrogen gas. Then, the temperature was raised to 75° C. and then reacted for 16 hours. The content after completion of the reaction was added dropwise to 620.0 g of n-heptane to obtain a white precipitate. This precipitate was filtered off, dried under reduced pressure at a temperature of 60° C., and 34 g of a fluorinated polymer-10 containing a repeating unit derived from fluorinated monomer-1 and a repeating unit derived from MNLA shown below as a white solid Was obtained in a yield of 85%.

[Chemical Formula 61]

<NMR measurement result>

The composition ratio of each repeating unit in the fluorinated polymer-10 was measured by NMR. The measurement result was expressed in mol%, and the repeating unit by fluorinated monomer-1: the repeating unit by MNLA was 67:33.

<GPC measurement result>

Mw=8,500, Mw/Mn=1.7

4-11. Synthesis of Fluorinated Polymer-11

In place of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-10, except for using the fluorinated monomer-2, the fluorinated polymer-11 was synthesized in the same procedure as the synthesis of the fluorinated polymer-10. , A fluorinated polymer-11 containing the following repeating units was obtained in a yield of 86%.

[Formula 62]

<NMR measurement result>

The composition ratio of each repeating unit in the fluorinated polymer-11 was measured by NMR. The measurement result was expressed in mol%, and the repeating unit by fluorinated monomer-2: the repeating unit by MNLA = 65:35.

<GPC measurement result>

Mw=8,700, Mw/Mn=1.6

4-12. Synthesis of Fluorinated Polymer-12

In place of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-10, except for using the fluorinated monomer-6, the fluorinated polymer-12 was synthesized by the same procedure as the synthesis of the fluorinated monomer-10. , A fluorinated polymer-12 containing the following repeating units was obtained in a yield of 73%.

[Chemical Formula 63]

<NMR measurement result>

The composition ratio of each repeating unit in the fluorinated polymer-12 was measured by NMR. The measurement result was expressed in mol%, and the repeating unit by fluorinated monomer-6: the repeating unit by MNLA = 64:36.

<GPC measurement result>

Mw=7,700, Mw/Mn=1.7

5. Synthesis of Comparative Polymer

In order to compare with the fluorinated polymers-1 to 12 of the present invention, comparative polymers 1 to 7 not belonging to the fluorinated polymer (1) were synthesized.

5-1. Synthesis of Comparative Polymer-1

A comparative polymer containing the following repeating units in the same procedure as the synthesis of fluorinated polymer-1, except that comparative monomer-1 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1. -1 was synthesized.

[Formula 64]

<GPC measurement result>

Mw=20,100, Mw/Mn=2.2

5-2. Synthesis of Comparative Polymer-2

A comparative polymer containing the following repeating units in the same procedure as the synthesis of fluorinated polymer-1, except that comparative monomer-2 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1. -2 was synthesized.

[Formula 65]

<GPC measurement result>

Mw=23,400, Mw/Mn=2.1

5-3. Synthesis of Comparative Polymer-3

A comparative polymer containing the following repeating units in the same procedure as the synthesis of fluorinated polymer-1, except that comparative monomer-3 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1. -3 was synthesized.

[Formula 66]

<GPC measurement result>

The GPC measurement result was Mw=22,800 and Mw/Mn=2.1.

5-4. Synthesis of Comparative Polymer-4

A comparative polymer containing the following repeating units in the same procedure as the synthesis of fluorinated polymer-1, except that comparative monomer-4 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-1. -4 was synthesized.

[Chemical Formula 67]

<GPC measurement result>

Mw=20,100, Mw/Mn=2.1

5-5. Synthesis of Comparative Polymer-5

Comparison including the following repeating units in the same procedure as the synthesis of fluorinated monomer-10, except that comparative monomer-1 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-10. Polymer-5 was synthesized to obtain a comparative polymer-5 in a yield of 89%.

[Chemical Formula 68]

<NMR measurement result>

In Comparative Polymer-5, the composition ratio of each repeating unit was measured by NMR. The measurement result was expressed in mol%, and the repeating unit by comparative monomer-1: the repeating unit by MNLA was 67:33.

<GPC measurement result>

Mw=8,300, Mw/Mn=1.7

5-6. Synthesis of Comparative Polymer-6

Comparison including the following repeating units in the same procedure as the synthesis of fluorinated monomer-10, except that comparative monomer-2 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-10. Polymer-6 was synthesized to obtain a comparative polymer-6 in a yield of 83%.

[Chemical Formula 69]

<NMR measurement result>

In Comparative Polymer-6, the composition ratio of each repeating unit was measured by NMR. The measurement result was expressed in mol%, and the repeating unit by comparative monomer-2: the repeating unit by MNLA was 65:35.

<GPC measurement result>

Mw=8,900, Mw/Mn=1.6

5-7. Synthesis of Comparative Polymer-7

Comparison including the following repeating units in the same procedure as the synthesis of fluorinated monomer-10, except that comparative monomer-3 was used instead of the fluorinated monomer-1 used in the synthesis of the above-described fluorinated polymer-10. Polymer-7 was synthesized to obtain a comparative polymer-7 in a yield of 81%.

[Formula 70]

<NMR measurement result>

In Comparative Polymer-7, the composition ratio of each repeating unit was measured by NMR. The measurement result was expressed in mol%, and the repeating unit of comparative monomer-3: the repeating unit of MNLA=66:34.

<GPC measurement result>

Mw=8,100, Mw/Mn=1.6

5-8. Repeating units of fluorinated polymers -1 to 12 and comparative polymers -1 to 7

Hereinafter, the repeating units contained in the fluorinated polymers 1 to 12 and the comparative polymers 1 to 7 are shown.

[Formula 71]

5-9. Composition, molecular weight and yield of fluorinated polymers-1 to 12 and comparative polymers-1 to 7

In Table 1, the composition (ratio of repeating units), weight average molecular weight, molecular weight distribution, and yield of fluorinated polymers -1 to 12 and comparative polymers -1 to 7 are shown.

5-10. Glass transition point and 5% weight reduction of fluorinated polymers-1 to 9 and comparative polymers 1 to 4

The glass transition points and 5% weight loss ratio of the fluorinated polymers-1 to 9 and comparative polymers-1 to 4 were measured by the following method.

[Measurement method of glass transition point and 5% weight loss]

The thermal properties of the fluorinated polymers-1 to 9 and the comparative polymers-1 to 4 were measured. Glass transition point (hereinafter referred to as Tg) using a differential scanning calorimeter (hereinafter sometimes referred to as DSC) and a differential thermogravimetric simultaneous measuring device (hereinafter referred to as DTA) manufactured by Hitachi Hi-Tech Sciences Co., Ltd. ) And a 5% weight reduction rate (hereinafter, sometimes referred to as Td5) in thermal gravimetric measurement were measured.

[Measurement result]

In Table 2, the measurement results of Tg and Td5 of fluorinated polymers-1 to 9 and comparative polymers-1 to 4 are shown. In the pattern forming material for lithography and printed electronics, it is known that the higher the Tg and Td5, the more faithfully the mask pattern is transferred, and the line edge roughness or line with roughness of the obtained pattern tends to be good. have.

The fluorinated polymers-1 to 9 and the comparative polymers 1 to 2 having a cyclic acetal structure had Tg higher than that of the chain comparative polymers 3 and 4 by about 25°C. The fluorinated polymers 1 to 3, 8, and 9 exhibited higher Tg compared to Comparative Polymer 1 having no fluorine atom in the same skeleton.

6. Composition for pattern formation for printed electronics

6-1. Preparation of composition for pattern formation for printed electronics

Using the fluorinated polymers-1 to 9 and the comparative polymers 1 to 4 containing the repeating units shown below, the composition for forming a pattern of the present invention-1 to 9 and the comparative compositions 1 to 4 for comparison Prepared.

[Formula 72]

For fluorinated polymers-1 to 9 and comparative polymers-1 to 4, (A) N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester as an acid generator, (D) 2-isopropyl as a sensitizer Thioxanthone, (C) 2-phenylbenzoimidazole as a target, (B) diethylene glycol methyl ethyl ether as an organic solvent was added, and the composition for pattern formation-1 to 9 and the comparative composition 1 to 4 were prepared. Prepared. Each composition ratio of the composition for pattern formation -1 to 9 and the comparative composition -1 to 4 is expressed in parts by mass, and polymer: (A) acid generator: (D) sensitizer: (C) ?? target: (B) organic It was formulated so that the solvent was 1 00:2:1:0.05:300.

6-2. Film formation of composition for pattern formation for printed electronics

On the glass substrate, the prepared composition for pattern formation -1 to 9 and the comparative composition -1 to 4 were applied with a spinner, and dried on a hot plate heated to 100°C for 2 minutes to form a film having a thickness of 0.5 μm. Then, a high-pressure mercury lamp was irradiated to the membrane. Further, through a photomask, ultraviolet light was irradiated using a high-pressure mercury lamp to transfer the pattern of the photomask to the film, and then, heated and dried at a temperature of 100°C for 5 minutes using a hot plate. In this way, a glass substrate formed by forming a pattern made of a hydrophilic portion and a water-repellent portion (a hydrophilic pattern) was obtained.

6-3. Measurement of a contact angle before and after exposure of a film made of a pattern forming composition, and formation of a pattern with aqueous ink

[Measurement of contact angle]

A water drop is placed on the film on the glass substrate, and the static contact angle of the non-ultraviolet light irradiation part and the irradiation part by the droplet method is measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The dynamic retreat angle of the irradiation part was measured. In the present invention, the static contact angle refers to the angle formed with the film surface when the water droplet is placed on the film surface and deposited, and the dynamic retreat angle is when the water droplet is sucked by a needle or the like and the water droplet contracts. It refers to the contact angle, and the dynamic advancing angle refers to the contact angle when the droplet is expanded by discharging the droplet with a needle or the like.

In the pattern forming material for lithography and printed electronics, the pattern forming film preferably has a higher static contact angle of the unirradiated portion, the mask pattern is transferred more faithfully, and the line edge roughness or line with roughness of the pattern obtained. It is good, and a high-resolution pattern is obtained. In addition, when the static contact angle of the irradiated portion is low and the difference between the contact angle of the unirradiated portion and the irradiated portion is larger, the pattern is easier to cut.

The higher the dynamic retreat angle of the unirradiated portion of the pattern forming film, the more faithfully the mask pattern is transferred, and the line edge roughness and line with roughness of the obtained pattern are better, and a high-resolution pattern is obtained. In order to obtain a high-resolution pattern, it is preferable that both the dynamic advancing angle and the dynamic retreating angle are high and the hysteresis (dynamic advancing angle-dynamic retreating angle) is small in the unirradiated portion.

[Ink pattern]

50 pl of aqueous ink was dripped with a borosilicate glass capillary (microcapillary) using an automatic micro contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., part number MCA-2) to the obtained propellant pattern on the glass substrate, and after 5 seconds The pattern was observed under a microscope. In addition, if the water-based ink can be patterned along the propellant pattern, it is good, it is impossible if it overflows from the pattern, and it is assumed that it cannot be distinguished from either.

[Measurement result]

In Table 3, the measurement results of the static contact angle and the dynamic contact angle of the above-described pattern formation compositions-1 to 9 and Comparative Examples 1 to 4 are shown. In Table 3, Examples 1 to 9 correspond to the measured values of the composition 1 to 9 for pattern formation, and Comparative Examples 1 to 4 correspond to the measured values of the compositions 1 to 4 for pattern formation.

[Contact angle]

The composition for pattern formation containing the trifluoromethyl group of Examples 1 to 9 had a large contact angle of the non-ultraviolet light irradiation portion and exhibited good water repellency.

The contact angle of the unirradiated portion of the film formed from Comparative Composition-1 using Comparative Polymer-1 containing no fluorine atom in Comparative Example 1 was 73° and the retreat contact angle was 58°. The contact angle of the non-ultraviolet portion of the film formed from Comparative Composition-2 using Comparative Polymer-2 containing a fluorine atom of Comparative Example 2 was 94 degrees, and formed from compositions 1 to 9 for pattern formation of Examples 1 to 9 The membrane was inferior in water repellency. Comparative composition-4 of Comparative Example 4 used Comparative Polymer-4 having a hexafluoroisopropyl group without acid dissociation, and the contact angle of the ultraviolet light irradiation portion was large and hydrophilicity was not exhibited.

[Ink pattern]

In the non-irradiated pattern of each pattern-forming composition 1 to 9 using the fluorinated polymers 1 to 9 of Examples 1 to 9, the difference between the contact angle of the unirradiated portion and the contact angle of the irradiated portion is 40° or more, and retreat. Since the contact angle was high, the water-based ink in the water repellent portion quickly flowed to the hydrophilic portion.

On the other hand, in the propellant pattern of Comparative Composition-2 using Comparative Polymer-2, the difference between the non-irradiated part and the irradiated part of the propellant pattern is about 30°, and the retraction contact angle is low at 80°, so that the water-based ink remains at the water-repellent site. Looked like this. In Comparative Example 1, Comparative Polymer-1 does not contain a fluorine atom. On the other hand, Comparative Example 4 uses Comparative Polymer-4 having a hexafluoroisopropyl group that does not have acid dissociation properties, so that the hydrophobic pattern is not formed. , A film of water-based ink has formed on the surface of the film.

7. Resist

7.1 Resist Preparation

Resists-1 to 3 and comparative resists-1 to 3 as resist solutions were prepared using fluorinated polymers-10 to 12 and comparative polymers-5 to 7 containing the following repeating units shown below.

[Chemical Formula 73]

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

[Resist film formation]

After applying the antireflection film solution (manufactured by Nissan Chemical Industries, Ltd., part number ARC29A) on a silicon wafer, it was dried at 200°C for 60 seconds to prepare an antireflection film having a thickness of 78 nm. Subsequently, each of the above resist solutions was filtered through a 0.2 µm membrane filter, and then applied on the antireflection film at a rotational speed of 1,500 rpm using a spinner, and dried on a hot plate at 100° C. for 90 seconds to form a resist film. I did.

7.2 Evaluation of the solubility of the resist developer and the resolution of the resist pattern

For each resist film, the solubility of the developer of the resist and the resolution of the resist pattern were evaluated, and the contact angle was measured. The measurement method is shown below.

[Developer solubility]

The silicon wafer on which the resist film was formed was immersed in an alkali developer at room temperature for 60 seconds to test the solubility in the developer. As the alkaline developer, an aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) having a concentration of 2.38% by mass used as a standard in lithography was used. The solubility of the resist film was determined by measuring the film thickness of the resist film after immersion with an optical interference type film thickness meter. The case where the resist film was completely disappeared was referred to as "available", and the case where no change in the film thickness of the resist film was observed was referred to as "insoluble".

[Sensitivity and resolution of resist pattern]

A photomask having a line-and-space pattern in which the width of the wiring and the interval between adjacent wirings are each 30 nm was prepared.

The silicon wafer on which the resist film was formed was prebaked at 100° C. for 60 seconds, and then irradiated with ultraviolet light so that the pattern of the photomask was transferred through the photomask at an oscillation wavelength of 193 nm using an argon fluoride excimer laser, The resist film was exposed. While rotating the silicon wafer, pure water was dripped for 2 minutes. Thereafter, post-exposure bake was performed at 120°C for 60 seconds, then developed using TMAH as an alkaline developer, and then immersed in pure water for 30 seconds, and then dried with an air knife. Subsequently, post-baking to be dried at 100°C for 45 seconds was performed, and thus a silicon wafer having a resist pattern formed thereon was obtained.

<sensitivity>

In the above operation, the optimum exposure amount Eop (mj/cm 2) when a 30 nm line and space pattern is formed once was determined and used as a standard for sensitivity.

<resolution>

The silicon wafer to which the obtained pattern was transferred was cut, and the resist pattern on the wafer to which the 30 nm line and space pattern of the photomask was transferred was observed under a microscope. Although it can be confirmed, the resolution was referred to as "good" for a small one, and the resolution "not possible" for a marked line edge roughness.

[Measurement method of contact angle]

With respect to the obtained resist film on a silicon wafer, the contact angle of water droplets was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).

In the resist film having a high contact angle, the mask pattern is transferred more faithfully, and the line edge roughness and line with roughness of the obtained pattern are good, and a high-resolution pattern is obtained. In addition, in liquid immersion exposure lithography, there is no intrusion of water into the film, so that the occurrence of watermark defects is small.

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

[Evaluation of developer solubility]

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

[Evaluation of sensitivity and resolution of resist pattern]

<sensitivity>

Regarding the sensitivity, the optimum exposure amounts of the comparative resists-1 to 3 were all lower than the optimum exposure amounts of the resists-1 to 3. The structure of Comparative Example Resist-2 was lower than that of the cyclic acetal structure. In addition, the optimum exposure amount of Comparative Resist-1, which is a cyclic acetal structure having no fluorine atom, was a low value, and the optimum exposure amount of Comparative Resist-3, which is a non-cyclic acetal structure, was the lowest.

<resolution>

As shown in Table 4, when resists-1 to 3 and comparative resist-2 were used, a pattern having a desired 30 nm line and space pattern was formed, exhibiting good resolution, and was judged as "good". On the other hand, in the case of the comparative resist-1, the line edge roughness was confirmed, and it was determined as "impossible". In the case of the comparative resist-3, a minute line edge roughness was observed, and since it was inferior when compared with the resists-1 to 3 and the comparative resist-2, it was determined as "A".

[Measurement result of contact angle]

The water receding contact angles of the resists 1-3 were all higher than those of the comparative resists 1-2. Comparative resist 2 contained a polymer having a fluorinated cyclic acetal structure, but was inferior to those of resists 1-3.

Claims (16)

A fluorinated polymer containing a repeating unit represented by formula (1).

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a C 1 to C 10 linear or C 3 to C 10 branched alkyl group, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms. ^{R 2} to R ⁵ are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine. X is a single bond or a divalent group, and up to 7 hydrogen atoms including the divalent group may be substituted with a fluorine atom Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a car It is a main acid ester group (-COOR), and up to 7 hydrogen atoms contained in the fluorinated alkyl group or the carboxylic acid ester group may be substituted with a fluorine atom. R is a fluorinated alkyl group having 1 to 3 carbon atoms.) The method of claim 1,
^{The fluorinated polymer in which R 2} , R ⁴ , and R ⁵ in the formula (1) are hydrogen atoms. The method of claim 2,
Further, Y in the formula (1) is a trifluoromethyl group, a fluorinated polymer. A composition for forming a resist pattern, comprising the fluorinated polymer according to any one of claims 1 to 3, an acid generator, a basic compound, and a solvent. A film forming step of forming a film by applying the composition for forming a resist pattern according to claim 4 on a substrate,
An exposure step of irradiating exposure with electromagnetic waves or high energy rays having a wavelength of 300 nm or less through a photomask to transfer the pattern of the photomask to the film, and
A method of forming a resist pattern, comprising a developing step of obtaining a pattern by developing a film using a developer. A composition for forming an ink pattern, comprising the fluorinated polymer according to any one of claims 1 to 3, an acid generator and a solvent. A film forming step of forming a film by applying the composition for forming an ink pattern according to claim 6 on a substrate,
An exposure step of irradiating the film with light having a wavelength of 150 nm or more and 500 nm or less through a photomask 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;
A method for forming an ink pattern, comprising an ink pattern forming step of applying ink to the obtained pattern forming film. A film forming step of heating the coating film obtained by applying the composition for forming an ink pattern according to claim 6 on a substrate,
Subsequently, a drawing step of scanning and exposing light having a wavelength of 150 nm or more and 500 nm or less to the film with 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, and
An ink pattern forming method comprising an ink pattern forming step of applying ink to the obtained pattern forming film. Fluorinated monomer represented by formula (4).

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a C 1 to C 10 linear or C 3 to C 10 branched alkyl group, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms. ^{R 2} to R ⁵ are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine. X is a single bond or a divalent group, and up to 7 hydrogen atoms including the divalent group may be substituted with a fluorine atom Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a car It is a main acid ester group (-COOR), and up to 7 hydrogen atoms contained in the fluorinated alkyl group or the carboxylic acid ester group may be substituted with a fluorine atom. R is a fluorinated alkyl group having 1 to 3 carbon atoms.) The method of claim 9,
^{The fluorinated monomer in which R 2} , R ⁴ , and R ⁵ in the above formula (4) are hydrogen atoms. The method of claim 10,
Further, Y in the formula (4) is a trifluoromethyl group, a fluorinated monomer. The step of cyclizing a hydroxycarbonyl compound represented by the following formula (10) or a hydroxyvinyl ether or hydroxyvinyl ester represented by formula (11) to obtain a cyclic hemiacetal compound represented by formula (7) A method for producing a fluorinated monomer represented by formula (4) according to claim 9, including.

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, or a C 1 to C 10 linear or C 3 to C 10 branched alkyl group, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms. ^{R 2} to R ⁵ are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine. X is a single bond or a divalent group, and up to 7 hydrogen atoms including the divalent group may be substituted with a fluorine atom Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a car It is a main acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorine-containing alkyl group or the carboxylic acid ester group may be substituted with a fluorine atom, R is a fluorine-containing alkyl group having 1 to 3 carbon atoms, and Z is hydrogen An atom or a C 1-20 linear, C 3-20 branched or cyclic alkyl group, and some or all of the hydrogen atoms in Z may be substituted with halogen atoms, ether bonds, siloxane bonds, thioether bonds And may contain a carbonyl bond.) Fluorinated cyclic hemiacetal represented by formula (7).

(In the formula, R ² to ^{R 5} are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms and Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorine-containing alkyl group or the carboxylic acid ester group are substituted by a fluorine atom. R is a fluorinated alkyl group having 1 to 3 carbon atoms.) The method of claim 13,
^{Fluorinated cyclic hemiacetal in which R 2} , R ⁴ , and R ⁵ in the above formula (7) are hydrogen atoms. The method of claim 14,
Further, in the formula (7), Y is a trifluoromethyl group, which is a fluorinated cyclic hemiacetal. The hydroxycarbonyl compound represented by the following formula (10) or the hydroxyvinyl ether or hydroxyvinyl ester represented by the formula (11) is cyclized, and the formula ( A method for producing a fluorinated cyclic hemiacetal compound to obtain a fluorinated cyclic hemiacetal compound represented by 7).

(In the formula, R ² to ^{R 5} are a hydrogen atom, a straight chain having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, and among the hydrogen atoms bonded to the carbon atoms in the alkyl group, 7 or less are fluorine atoms and Y is a fluorine-containing alkyl group having 1 to 3 carbon atoms or a carboxylic acid ester group (-COOR), and up to 7 hydrogen atoms included in the fluorine-containing alkyl group or the carboxylic acid ester group are substituted by a fluorine atom. R is a C1-C3 fluorinated alkyl group, Z is a hydrogen atom or a C1-C20 linear, C3-C20 branched or cyclic alkyl group, and some or all of the hydrogen atoms in Z are It may be substituted with a halogen atom, and may contain an ether bond, a siloxane bond, a thioether bond, and a carbonyl bond.)