KR20230141763A - Resin composition, resin film, substrate, polymer and polymerizable monomer - Google Patents

Abstract

일반식(Ⅰ) 중에서, R¹은, 적어도 1개의 중합성 기를 포함하는 기이고, R² 및 R³은, 각각 독립적으로 수소원자, 또는 직쇄 혹은 분기의 지방족 탄화수소기이고, R⁴는, 수소원자, 또는 직쇄 혹은 분기의 지방족 탄화수소기로서, 지방족 탄화수소기가 구비하는 수소원자의 일부 또는 전부는, 산기 또는 히드록시기에 의하여 치환되어 있어도 좋고, R⁵는, 2∼4가의 직쇄 또는 분기의 지방족 탄화수소기로서, 지방족 탄화수소기의 수소원자의 일부 또는 전부는, 불소원자 또는 히드록시기에 의하여 치환되어 있어도 좋고, R⁶ 및 R⁷은, 각각 독립적으로 함불소 알킬기를 나타내고, n은 1∼5의 정수를 나타내고, n이 2 이상일 때에, 복수의 R²는 동일하여도 달라도 좋고, 또한 복수의 R³은 동일하여도 달라도 좋고, m은 1∼3의 정수를 나타내고, m이 2 또는 3일 때에, 복수 존재하는 R⁶은 동일하여도 달라도 좋고, 또한 복수 존재하는 R⁷은 동일하여도 달라도 좋다.The present invention relates to a resin composition containing a polymer having a structural unit derived from a polymerizable monomer represented by general formula (I).
[Formula 1]

In general formula (I), R ¹ is a group containing at least one polymerizable group, R ² and R ³ are each independently a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group, and R ⁴ is a hydrogen atom. An atom or a straight-chain or branched aliphatic hydrocarbon group, some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with an acid group or a hydroxy group, and R ⁵ is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group. As, some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, R ⁶ and R ⁷ each independently represent a fluorine-containing alkyl group, and n represents an integer of 1 to 5. , when n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different, m represents an integer of 1 to 3, and when m is 2 or 3, a plurality of R 3 may be present. R ⁶ may be the same or different, and plural R ⁷ may be the same or different.

Description

Resin composition, resin film, substrate, polymer and polymerizable monomer

The present invention relates to resin compositions, resin films, substrates, polymers, and polymerizable monomers. More specifically, a polymerizable monomer having a specific structure, a polymer having a structural unit derived from the polymerizable monomer, a resin composition containing the polymer, a resin film formed using the resin composition, and the resin composition. It relates to a substrate having a pattern formed by.

Fluorine-containing polymers often exhibit physical properties (e.g., water repellency, low refractive index, etc.) that are different from ordinary organic polymers due to the electronic specificity of the fluorine atom. Therefore, the application of fluorine-containing polymers to various functional materials/resin compositions is being studied.

For example, Patent Document 1 describes that a fluorinated polymer containing a repeating unit represented by a specific general formula provides a pattern with high sensitivity and high resolution.

Additionally, Patent Document 2 discloses that a fluorinated polymer containing a repeating unit represented by a specific general formula is effective in forming a fine resist pattern with small roughness.

Patent Document 1: Japanese Patent Laid-Open No. 2018-203996 Patent Document 2: Japanese Patent Laid-Open No. 2018-044034

Fluorine-containing polymers usually have high water repellency and tend to have relatively low solubility in aqueous alkaline solutions.

In order to increase the solubility in an aqueous alkaline solution, attempts are known to introduce, for example, a hexafluoroisopropanol group (-C(CF ₃ ) ₂ -OH) into the polymer.

However, according to the knowledge of the present inventors, there is room for further improvement in the solubility of conventional fluorine-containing polymers in aqueous alkaline solutions.

The present invention has been made in consideration of these circumstances. One of the purposes of the present invention is to provide a resin composition containing a fluorine-containing polymer that can form a resin film with good solubility in an aqueous alkaline solution.

The present inventors have solved the above problems by completing the invention provided below.

The present invention is the following resin composition.

A resin composition containing a polymer having a structural unit derived from a polymerizable monomer represented by the following general formula (I).

In general formula (Ⅰ),

R ¹ is a group containing at least one polymerizable group,

R ² and R ³ are each independently a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group,

R ⁴ is a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with an acid group or a hydroxy group,

R ⁵ is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups,

R ⁶ and R ⁷ each independently represent a fluorinated alkyl group,

n represents an integer of 1 to 5, and when n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different,

m represents an integer of 1 to 3, and when m is 2 or 3, a plurality of R ⁶ may be the same or different, and a plurality of R ⁷ may be the same or different.

In addition, the present invention,

It is a resin film formed by the above resin composition.

Additionally, the present invention relates to the following polymer.

A polymer comprising a structural unit derived from a polymerizable monomer represented by the following general formula (I).

In general formula (Ⅰ),

R ¹ is a group containing at least one polymerizable group,

R ² and R ³ are each independently a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group,

R ⁴ is a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with an acid group or a hydroxy group,

R ⁵ is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups,

R ⁶ and R ⁷ each independently represent a fluorinated alkyl group,

n represents an integer of 1 to 5, and when n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different,

m represents an integer of 1 to 3, and when m is 2 or 3, a plurality of R ⁶ may be the same or different, and a plurality of R ⁷ may be the same or different.

Additionally, the present invention relates to the following polymerizable monomers.

A polymerizable monomer represented by the following general formula (I).

In general formula (Ⅰ),

R ¹ is a group containing at least one polymerizable group,

R ² and R ³ are each independently a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group,

R ⁴ is a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with an acid group or a hydroxy group,

R ⁵ is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups,

R ⁶ and R ⁷ each independently represent a fluorinated alkyl group,

n represents an integer of 1 to 5, and when n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different,

m represents an integer of 1 to 3, and when m is 2 or 3, a plurality of R ⁶ may be the same or different, and a plurality of R ⁷ may be the same or different.

According to the present invention, a resin composition containing a fluorine-containing polymer capable of forming a resin film with good solubility in an aqueous alkaline solution is provided.

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described in detail.

In this specification, the notation “X to Y” in the description of the numerical range indicates not less than X and not more than Y, unless otherwise specified. For example, “1 to 5 mass%” means “1 mass% or more and 5 mass% or less.”

In the notation of a group (atomic group) in this specification, a notation that does not describe whether it is substituted or unsubstituted includes both those without a substituent and those with a substituent. For example, “alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

The notation of “(meth)acrylic” in this specification represents a concept that includes both acrylic and methacryl. The same applies to similar expressions such as “(meth)acrylate.”

In this specification, “organic group” means an atomic group excluding one or more hydrogen atoms in an organic compound, unless otherwise specified. For example, “monovalent organic group” refers to an atomic group excluding one hydrogen atom in an arbitrary organic compound.

Below, from the viewpoint of ease of explanation, the polymerizable monomer is first explained, then the polymer having a structural unit derived from the polymerizable monomer is explained, and then the resin composition containing the polymer is explained. Explain.

<Polymerizable monomer>

The polymerizable monomer (hereinafter also simply referred to as “polymerizable monomer”, “monomer”, etc.) of the present embodiment is represented by the following general formula (I).

In general formula (Ⅰ),

R ¹ is a group containing at least one polymerizable group,

R ² and R ³ are each independently a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group,

R ⁴ is a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with an acid group or a hydroxy group,

R ⁵ is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups,

R ⁶ and R ⁷ each independently represent a fluorinated alkyl group,

n represents an integer of 1 to 5, and when n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different,

m represents an integer of 1 to 3, and when m is 2 or 3, a plurality of R ⁶ may be the same or different, and a plurality of R ⁷ may be the same or different.

R ¹ is preferably a group containing at least one of a (meth)acryloyl group, a vinyl group, and an epoxy group. When R ¹ contains a methacryloyl group, some or all of the hydrogen atoms of the methyl group at the α site of the methacryloyl group may be substituted with fluorine atoms.

As a group containing a (meth)acryloyl group, the (meth)acryloyl group itself is preferably used.

Examples of the group containing a vinyl group include a vinyl group itself, an allyl group, and a group containing a styrene skeleton (for example, CH ₂ = CH-C ₆ H ₄ -).

Examples of groups containing an epoxy group include the epoxy group itself, glycidyl group, and glycidyloxy group.

For the purpose of adjusting the refractive index, the portions that can be the main chain or/and side chain in the polymer of R ¹ may not contain an alicyclic structure. Specific examples include cyclic olefin structures such as norbornene structures.

Examples of the straight-chain or branched aliphatic hydrocarbon group for R ² and R ³ include a straight-chain or branched alkyl group. Examples of straight-chain or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, and hexyl groups. Examples include syl group, heptyl group, octyl group, nonyl group, and decyl group.

The carbon number of the straight-chain or branched aliphatic hydrocarbon group in R ² and R ³ is, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 4.

R ² and R ³ are preferably hydrogen atoms.

Examples of the straight-chain or branched aliphatic hydrocarbon group for R ⁴ include the same straight-chain or branched aliphatic hydrocarbon groups for R ² and R ³ .

When R ⁴ is a straight-chain or branched aliphatic hydrocarbon group, some or all of the hydrogen atoms of this aliphatic hydrocarbon group may be substituted with an acid group or a hydroxy group. Examples of the acid group include a carboxyl group, a phenolic hydroxy group, a phosphoric acid group, and a hexafluoroisopropanol group (-C(CF ₃ ) ₂ -OH).

R ⁴ is preferably a hydrogen atom.

R ⁵ may be a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group. Some or all of the hydrogen atoms of this straight-chain or branched aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups.

When R ⁵ is a divalent straight-chain or branched aliphatic hydrocarbon group, R ⁵ is preferably a straight-chain or branched alkylene group. Specifically, methylene group (-CH ₂ -), 1,2-ethylene group, 1,6-hexylene group, 1,4-butylene group, 1,6-(2,4,4-trimethylhexylene) group, 1,4-(4-methylpentylene) group, 1,5-(5-methylhexylene) group, 1,6-(6-methylheptylene) group, 1,5-(2,2, 5-trimethylhexylene) group, 1,7-(3,7-dimethyloctylene) group, etc.

When R ⁵ is a trivalent or tetravalent straight-chain or branched aliphatic hydrocarbon group, R ⁵ can be, for example, a group obtained by removing one or two hydrogen atoms from the divalent straight-chain or branched aliphatic hydrocarbon group. .

The carbon number of R ⁵ is, for example, 1 to 12, preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4.

Particularly preferred R ⁵ is a methylene group (-CH ₂ -).

The fluorinated alkyl group of R ⁶ and R ⁷ is preferably a straight-chain or branched fluoroalkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably It is a straight-chain or branched fluoroalkyl group having 1 to 3 carbon atoms.

R ⁶ and R ⁷ are preferably perfluoroalkyl groups. As a result, the hydroxy group bonded to the carbon atom to which R ⁶ and R ⁷ are bonded becomes more susceptible to decomposition in an aqueous alkaline solution, and improvement in solubility in the aqueous alkaline solution can be expected. Additionally, a polymer containing a structural unit derived from a monomer represented by general formula (I) may have a particularly low refractive index.

R ⁶ and R ⁷ are particularly preferably a perfluoromethyl group, perfluoroethyl group, or perfluorobutyl group, and particularly more preferably a perfluoromethyl group (trifluoromethyl group).

n may be an integer of 1 to 5, but is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

m may be an integer of 1 to 3, but is preferably 1 to 2, and more preferably 1.

Particularly preferable structures of the polymerizable monomer represented by general formula (I) are shown in the Examples described later, and examples of other preferable structures are shown below.

<Production (synthesis) method of polymerizable monomer>

The polymerizable monomer represented by general formula (I) is produced, for example, by reacting compound A represented by the following general formula (A) with compound B, which has a polymerizable group and a group that reacts with an epoxy group to form a bond. can do. This reaction is preferably carried out in the presence of a base such as an amine compound.

In general formula (A), the definitions and specific aspects of R ⁵ , R ⁶ , R ⁷ and m are the same as those in general formula (I).

A preferred example of compound B is (meth)acrylic acid. The carboxyl group of (meth)acrylic acid reacts with the epoxy group of Compound A. And in General Formula (I), a compound in which R ¹ is a (meth)acryloyl group, R ² , R ³ and R ⁴ are hydrogen atoms, and n = 1 can be obtained.

Other examples of compound B include vinyl magnesium chloride, allyl magnesium chloride, organic lithium compounds, amine compounds, and glycidol. It is also conceivable to react with the -OH group of another molecule, Compound A, on the epoxy group of Compound A.

In addition, R ⁴ is converted into a straight-chain or branched aliphatic hydrocarbon group by reacting an appropriate compound with the R ⁴ portion of the polymerizable monomer represented by general formula (I) where R ⁴ is a hydrogen atom, or R ⁴ is substituted with an acid group or hydroxy group. It can be converted into a

After synthesis of the polymerizable monomer, it is desirable to conduct appropriate treatment to reduce the amount of unreacted substances, by-products, and other impurities. Appropriate treatments include one or two or more of water washing, precipitation of crystals, and filtration. In addition, in the production (synthesis) of the polymerizable monomer represented by general formula (I), various knowledge known in the field of organic synthetic chemistry can be applied as needed.

In this regard, Compound A can be obtained, for example, by reacting an epoxidation reagent with the carbon-carbon double bond of the compound represented by the following general formula (A'). Examples of epoxidation reagents include peroxides such as metachloroperbenzoic acid.

<Polymer>

The polymer of this embodiment (hereinafter also simply referred to as “polymer”) has a structural unit derived from a polymerizable monomer represented by the general formula (I) above. In other words, the polymer of the present embodiment has a structural unit formed by polymerization of the polymerizable group in R ¹ of the polymerizable monomer represented by general formula (I).

Since General Formula (I) was explained in the section <Polymerizable Monomer> above, further explanation is omitted.

The polymer may be a homopolymer composed only of (i) structural units derived from a polymerizable monomer represented by general formula (I), (ii) structural units derived from a polymerizable monomer represented by general formula (I), and (1) Alternatively, it may be a copolymer having two or more other structural units (copolymerization units).

From the viewpoint of tuning/improvement of various performances, it is preferable that the polymer is (ii) a copolymer.

When the polymer is a copolymer, the monomer constituting the copolymerization unit is not particularly limited as long as it can be copolymerized with the polymerizable monomer represented by General Formula (I). Additionally, when the polymer is a copolymer, the polymer may contain only one copolymerization unit or may contain two or more copolymerization units.

Copolymerization units include, for example, olefins, fluorinated olefins, (meth)acrylic acid esters, fluorinated (meth)acrylic acid esters, norbornene compounds, fluorinated norbornene compounds, styrene-based compounds, fluorinated styrene-based compounds, vinyl ether, and It can be a copolymerized unit derived from one or more monomers selected from the group consisting of fluorinated vinyl ethers. These are preferably used together when a polymerizable monomer represented by general formula (I) in which R ¹ contains a polymerizable carbon-carbon double bond is used.

Preferred copolymerization units include structural units derived from fluorine-containing monomers such as fluorine-containing (meth)acrylic acid ester. By making the copolymerization unit a structural unit derived from a fluorine monomer, it is easy to increase the fluorine content of the entire polymer. This contributes to adjustment of the refractive index of the polymer, adjustment of water repellency, etc.

Specific examples of fluorinated (meth)acrylic acid esters include monomers represented by the general formula CH ₂ = CR'-COO-R ^f . In this general formula, R' is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R ^f is a fluorinated organic group.

Examples of the fluorinated organic group for R ^f include a linear or branched fluorinated alkyl group, a fluorinated alicyclic group, a fluorinated aryl group, and a fluorinated aralkyl group. In the fluorine-containing organic group, all hydrogen atoms may be substituted with fluorine atoms (perfluoro groups may be sufficient), or some hydrogen atoms may be substituted with fluorine atoms. The carbon number of the fluorine-containing organic group is, for example, 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

In addition, when using a polymerizable monomer represented by general formula (I) in which R ¹ contains an epoxy group, the monomer constituting the copolymerization unit may be a monofunctional epoxy compound having only one epoxy group or two or more epoxy groups. Any epoxy compound, such as a polyfunctional epoxy compound, can be used.

Examples of monofunctional epoxy compounds include 4-tert-butylphenyl glycidyl ether, m,p-cresyl glycidyl ether, phenyl glycidyl ether, and cresyl glycidyl ether.

As polyfunctional epoxy compounds, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, glycerol polyglycidyl ether, and diglycerol polyglycidyl ether. Diyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinoldi and polyglycidyl ethers such as glycidyl ether, neopentyl glycol diglycidyl ether, and hydrogenated bisphenol A type diglycidyl ether.

In addition, when using a polymerizable monomer represented by general formula (I) in which R ¹ contains an epoxy group, the monomer constituting the copolymerization unit may be an alicyclic epoxy compound, a polymer having an epoxy structure, or a novolak-based epoxy resin. Compounds such as siloxane-based monomers having an epoxy structure can also be used.

Examples of alicyclic epoxy compounds include 1,2-epoxy-4-vinylcyclohexane (product name: CELLOXIDE 2000, manufactured by Daicel Corporation), which is a monofunctional epoxy, and polyfunctional epoxy. 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Product name: Celoxide 2021P, manufactured by Daicel Co., Ltd.), etc.

Examples of the polymer having an epoxy structure include polymers obtained by polymerizing or copolymerizing a (meth)acrylate monomer having an epoxy structure. Examples of (meth)acrylate monomers having an epoxy structure include glycidyl methacrylate, which is a monofunctional epoxy, and 4-hydroxybutylacrylate glycidyl ether (abbreviated name: 4HBAGE, manufactured by Mitsubishi Chemical Co., Ltd.) Mitsubishi Chemical Corporation), 3,4-epoxycyclohexylmethyl methacrylate (brand name: CYCLOMER M100, manufactured by Daicel Co., Ltd.), etc.

As a siloxane monomer having an epoxy structure, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (product name: KBM-303, Shin-Etsu Chemical Co., Ltd.), which is a monofunctional epoxy. Etsu Chemical Co., Ltd. product), and 3-glycidoxypropyltrimethoxysilane (brand name: KBM-403, Shin-Etsu Chemical Co., Ltd. product).

Examples of the novolak-based epoxy resin include jER 152 (manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON N730-A (manufactured by DIC Corporation), and YDPN-638 (manufactured by Nippon STEEL Chemical & Materials Co., Ltd.). Material Co., Ltd. products) and the like.

When the polymer is a copolymer, the proportion of structural units derived from the polymerizable monomer represented by general formula (I) in the polymer is, for example, 30 to 90 mol%, preferably 40 to 70 mol%. By appropriately adjusting the ratio of structural units derived from the polymerizable monomer represented by general formula (Ⅰ), for example, the effect of the structural unit derived from the polymerizable monomer represented by general formula (Ⅰ) (solubility in aqueous alkaline solution) etc.), it is easy to achieve other performance improvements.

The ratio of structural units in the polymer can be known through measurement data such as ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR.

Particularly preferable polymers include polymers (copolymers) containing a structural unit represented by the following general formula (II) and a structural unit represented by the following general formula (III).

Among general formulas (Ⅱ) and (Ⅲ),

The definitions and preferred embodiments of R ² to R ⁷ , m and n are the same as those in General Formula (I),

R ⁸ is a hydrogen atom or a methyl group,

R ⁹ is a hydrogen atom or a methyl group,

R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a fluorinated alkyl group.

Preferably, one or both of R ¹⁰ and R ¹¹ are fluorinated alkyl groups.

Examples of the fluorinated alkyl group include the same groups as the fluorinated alkyl groups of R ⁶ and R ⁷ .

Additionally, examples of the fluorinated alkyl group are not limited to perfluoroalkyl groups, and perfluoroalkyl groups in which one of the terminal fluorine atoms is replaced with a hydrogen atom may be used. Examples of perfluoroalkyl groups in which one terminal fluorine atom is replaced with a hydrogen atom include -CF ₂ H, -CF ₂ CF ₂ H, -CF ₂ CF ₂ CF ₂ H, -CF ₂ CF 2 CF _{2 CF 2} H, -CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ H, -CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ H, etc.

Moreover, the fluorine content in the structural unit represented by general formula (III) in the polymer is preferably 40 to 75 mass%, more preferably 45 to 70 mass%. This may make it easier to achieve both solubility in aqueous alkaline solutions and water repellency.

In addition, the composition ratio of the structural unit represented by general formula (III) in the polymer is preferably 30 to 70 mol%, out of a total of 100 mol% of the structural unit represented by general formula (II) and the structural unit represented by general formula (III). Preferably it is 40 to 60 mol%. This may make it easier to achieve both solubility in aqueous alkaline solutions and water repellency.

The fluorine content of the polymer is preferably 30 to 75% by mass, more preferably 40 to 60% by mass. By adjusting the fluorine content, the refractive index can be further optimized, or it can be easier to achieve both solubility in aqueous alkaline solutions and water repellency.

The weight average molecular weight of the polymer is, for example, 3,000 to 30,000, preferably 5,000 to 20,000, and more preferably 6,000 to 15,000.

The dispersion degree of the polymer is, for example, 1.2 to 2.5, preferably 1.4 to 1.8.

The weight average molecular weight and dispersion degree can be determined by gel permeation chromatography.

<Polymer production (synthesis) method>

The polymer of this embodiment can be produced (synthesized) by polymerizing only the polymerizable monomer represented by General Formula (I), or by copolymerizing the polymerizable monomer represented by General Formula (I) with other monomers.

When using a polymerizable monomer represented by general formula (I) in which R ¹ contains a polymerizable carbon-carbon double bond, it is preferable to polymerize the monomer using a radical polymerization initiator in the presence of an appropriate polymerization solvent. .

As a polymerization solvent, any solvent can be used without particular limitation as long as it sufficiently dissolves the monomer and radical polymerization initiator. Specifically, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; Dimethyl sulfoxide, etc. can be mentioned. Of course, polymerization solvents are not limited to these alone. The polymerization solvent may contain only one organic solvent, or may contain two or more organic solvents.

As a radical polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-(5 -methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis(N,N'- Dimethyleneisobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (FUJIFILM Wako Pure Chemical Corporation) , VA-057) and azo-based initiators. In addition, persulfates such as potassium persulfate and ammonium persulfate, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, and t-butyl Peroxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutyl Peroxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di(t-hexylperoxy)cyclohexane, t -Peroxide-based initiators such as butylhydroperoxide and hydrogen peroxide can also be mentioned. Of course, the polymerization initiator is not limited to these alone. Only one polymerization initiator may be used, or two or more polymerization initiators may be used in combination.

When using a polymerizable monomer represented by general formula (I) in which R ¹ contains an epoxy group, it is preferable to polymerize the monomer using a cationic polymerization initiator in the presence of an appropriate polymerization solvent.

Examples of the cationic polymerization initiator include at least one cation selected from aromatic sulfonium, aromatic iodonium, aromatic diazonium, and pyridinium, and BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , and AsF ₆ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- and B(C ₆ F ₅ ) ₄ ^- A thermal cationic polymerization initiator such as an onium salt or aluminum complex consisting of at least one anion selected from the group consisting of can be mentioned.

For polymers obtained by polymerization, it is advisable to appropriately remove or reduce unreacted monomers and impurities by methods known in the technical field of polymer synthesis, such as precipitation using a poor solvent and decantation. desirable.

<Resin composition>

The resin composition of the present embodiment (hereinafter sometimes simply referred to as “resin composition”) contains a polymer having a structural unit derived from a polymerizable monomer represented by the general formula (I) above.

Since the polymerizable monomer represented by general formula (I) and the polymer having structural units derived from the monomer have been described above, further explanation will be omitted.

For example, the resin film formed using the resin composition of this embodiment has good solubility in an aqueous alkaline solution. This is presumed to be due to the fact that the structural unit derived from the polymerizable monomer represented by general formula (I) in the polymer has a functional group represented by -OR ⁴ in addition to the functional group represented by -CR ⁶ R ⁷ OH. It is presumed that the presence of these two functional groups particularly improves the affinity of the polymer for alkaline aqueous solutions.

Additionally, the resin film formed using the resin composition of this embodiment has good adhesion to the substrate. This is also presumed to be due to the fact that the structural unit derived from the polymerizable monomer represented by general formula (I) in the polymer has a functional group represented by -OR ⁴ in addition to the functional group represented by -CR ⁶ R ⁷ OH. In particular, it is presumed that good adhesion to the substrate is developed when the functional group represented by -OR ⁴ interacts with the substrate.

From another viewpoint, the resin film formed using the resin composition of the present embodiment has desirable optical properties resulting from containing fluorine atoms, and is therefore applicable to optical members.

The resin composition of this embodiment typically contains an organic solvent. In other words, the resin composition of this embodiment typically has at least a polymer dissolved or dispersed in an organic solvent. Since the resin composition contains an organic solvent, a resin film can be easily obtained through a process of applying the resin composition onto a substrate and drying it.

As the organic solvent, any organic solvent can be used as long as it can dissolve or disperse the polymer. Specifically, organic solvents such as ester-based, ether-based, ketone-based, hydrocarbon-based, amide-based, alcohol-based, and glycol-based solvents can be mentioned.

Organic solvents that can be preferably used include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, diacetone alcohol, diglyme, methyl isobutyl ketone, and acetic acid 3-. Methoxybutyl, 2-heptanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

Additionally, glycols, glycol ethers, and glycol ether esters can also be used as solvents. Specifically, CELTOL (registered trademark) manufactured by Daicel Co., Ltd. and HYSORB (registered trademark) manufactured by TOHO CHEMICAL INDUSTRY Co., Ltd. You can. More specifically, cyclohexanol acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3- Butylene glycol diacetate, 1,6-hexanediol diacetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, 1, 3-Butylene glycol, propylene glycol-n-propyl ether, propylene glycol-n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol-n-propyl ether, dipropylene glycol-n-butyl Ether, tripropylene glycol methyl ether, tripropylene glycol-n-butyl ether, triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc.

When using an organic solvent, the amount used is not particularly limited, but it is used so that the total solid content (components other than the organic solvent) in the resin composition is usually 5 to 60% by mass, preferably 10 to 50% by mass. By appropriately adjusting the total solid concentration, the ease of thin film formation and uniformity of film thickness tend to improve.

The resin composition of the present embodiment can specifically have the following aspects (i) to (iii). When the resin composition contains a photoacid generator, the resin composition exhibits photosensitivity and patterning by a photolithography process becomes possible. Additionally, by containing a crosslinking agent in the resin composition, the resin composition can be hardened (by external stimuli such as light or heat).

(i) The resin composition contains a polymer and a photoacid generator.

(ii) The resin composition contains a polymer and a crosslinking agent.

(iii) The resin composition contains a polymer, a photoacid generator, and a crosslinking agent.

Specific examples of photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate. When using a photoacid generator, it may be used individually or two or more types may be used together.

Commercially available photoacid generators include brand names: Irgacure PAG121, Irgacure PAG103, Irgacure CGI1380, Irgacure CGI725 (above, manufactured by BASF, USA), brand names: PAI-101, PAI-106, NAI-105, NAI-106, TAZ-110, TAZ-204 (above, product of Midori Kagaku Co., Ltd.), product name: CPI-200K, CPI-210S, CPI-101A, CPI-110A, CPI-100P, CPI-110P, CPI -100TF, CPI-110TF, HS-1, HS-1A, HS-1P, HS-1N, HS-1TF, HS-1NF, HS-1MS, HS-1CS, LW-S1, LW-S1NF (or more, live birth (San-Apro Ltd. product), brand name: TFE-triazine, TME-triazine or MP-triazine (above, product of Sanwa Chemical CO., LTD.) I can hear it. Of course, the photoacid generators that can be used are not limited to these alone.

When using a photo acid generator, the amount is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, assuming 100 parts by mass of polymer. By using an appropriate amount of photoacid generator, it is possible to achieve both sufficient sensitivity and resolution and storage stability of the composition.

As a cross-linking agent, a compound having a cross-linkable group capable of cross-linking with the -OH moiety and/or -OR ⁴ moiety in the polymer can be used. A crosslinking agent typically contains two or more crosslinkable groups per molecule. A cross-linked structure connecting the polymers is formed, and the resin film hardens. The number of crosslinkable groups contained in one molecule of the crosslinking agent is usually 2 to 8, preferably 2 to 6, and more preferably 2 to 4.

Specific examples of the crosslinking agent include the following compounds (a) to (d). When using a crosslinking agent, only one type may be used, or multiple types may be used together.

(a) Cross-linking agent having an alkoxymethyl group and/or methylol group: for example, benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, Bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl) Cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis (methoxymethyl)biphenyl, hexamethoxymethylmelamine; Commercial products include CYMEL 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (Mitsui) Mitsui Cytec, Ltd. products), NIKALAC MX-270, -280, -290, Nikalac MS-11, Nikalac MW-30, -100, -300, -390, -750 (Sanwa Chemical Co., Ltd. product), 1,4-bis(methoxymethyl)benzene, 4,4'-biphenyl dimethanol, 4,4'-bis(methoxymethyl)biphenyl, commercially available 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A (ASAHI YUKIZAI CORPORATION product), DML-MBPC, DML-MBOC, DML-OCHP, DML- PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, Dimethylol-Bis-C, Dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP- Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethyl Toxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP ( Products from Honshu Chemical Industry Co., Ltd.), etc. can be mentioned. In this embodiment, it is particularly preferable to use a crosslinking agent having an alkoxymethyl group and/or a methylol group.

(b) Compounds having an epoxy group: for example, n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, Glycidyl ethers such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and glycidyl ether of bisphenol A (or F), Adi Glycidyl esters such as diglycidyl phthalate and o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane)carboxylate, 3,4-epoxy-6 -Methylcyclohexylmethyl(3,4-epoxy-6-methylcyclohexane)carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dicyclopentane diene oxide, bis(2, 3-epoxycyclopentyl) ether, or alicyclic epoxy such as Celoxide 2021, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, and EPOLEAD GT401 manufactured by Daicel Co., Ltd., 2, 2'-(((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4, 1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane)) (e.g. Techmore VG3101L (manufactured by Printec Corporation)), Eporite 100MF (Kyoeisha Chemical) Aliphatic polyglycidyl ethers such as (produced by kyoeisha Chemical Co., Ltd.) and EPIOL TMP (produced by NOF CORPORATION), 1,1,3,3, 5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)tri·siloxane (e.g., DMS-E09 (Gelest product)), etc. there is.

(c) Compounds having an isocyanate group: For example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate. , isophorone diisocyanate, hexamethylene diisocyanate, etc.

(d) Compounds having a bismaleimide group: for example, 4,4'-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, bisphenol A diphenyletherbismaleimide, 3, 3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2 ,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1, 3-bis(4-maleimidephenoxy)benzene, etc. can be mentioned.

When the resin composition contains a crosslinking agent, its content is usually 1 to 100 parts by mass, preferably 5 to 50 parts by mass, per 100 parts by mass of the polymer. By setting the content to 1 part by mass or more, a cured film with sufficient mechanical strength can be obtained, and by setting the content to 100 parts by mass or less, the storage stability of the resin composition can be improved.

In this regard, from the viewpoint of the reaction efficiency of the crosslinking agent when the resin composition includes a crosslinking agent, it is preferable that the resin composition includes a photoacid generator and/or a thermal acid generator. Specific examples of photoacid generators are as described above. As a heat acid generator, a known heat acid generator can be used without any particular restrictions.

One of the uses of the resin composition is preferably applied as a protective film for a photosensitive resin film in a photolithography process. That is, the resin composition of this embodiment is preferably used to form a protective film of a photosensitive resin film in a photolithography process.

In the photolithography process, especially the immersion process, the photosensitive resin film is covered with a water-repellent protective film to prevent direct contact between the photosensitive resin film (resist film) and the immersion liquid (usually pure water). There are cases. In this regard, this water-repellent protective film is often referred to as a “topcoat”. Since the resin film formed using the resin composition of this embodiment has good solubility in an aqueous alkaline solution, it can be easily removed with an alkaline developer. Additionally, since the resin film formed using the resin composition of this embodiment is moderately water-repellent, it is possible to suppress the immersion liquid from penetrating into the photosensitive resin film.

In addition, other uses of the resin composition include use as a material that can be patterned by a photolithography process (photosensitive resin composition, photoresist, etc.), and application as an optical member (anti-reflection film, planarization film, etc.).

<Resin film, pattern and substrate>

As explained in the above <Resin Composition> section, a resin film can be formed by using the resin composition of this embodiment.

The formation of the resin film can be performed by rotational coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, inkjet method, etc. After application, it is desirable to pre-bake at 80 to 140°C, preferably 90 to 120°C, to sufficiently volatilize the organic solvent.

The base material forming the resin film is not particularly limited. Examples include glass, silicon wafer, ceramic substrate, aluminum substrate, SiC wafer, GaN wafer, etc. To improve adhesion, the surface of the substrate may be treated with an adhesive aid such as a silane coupling agent.

When the resin composition is photosensitive (such as when it contains a photoacid generator), a base material with a pattern can be obtained by appropriately irradiating (exposure) the resin film to light and then developing it. Below, exposure and development are explained.

As actinic rays used for exposure, for example, X-rays, electron beams, ultraviolet rays, visible rays, etc. can be used. In terms of wavelength, actinic rays of 200 to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably the g-line, h-line, or i-line of a mercury lamp, and the i-line is especially preferable. Additionally, a mixture of two or more light rays may be used. As an exposure device, a contact aligner, mirror projection or stepper is preferred.

When exposing, a photomask with a desired pattern is usually used.

After exposure, the resin film may be heated again as needed (post exposure bake). The temperature is, for example, 80 to 150°C, preferably 90 to 120°C. Moreover, the time is, for example, 30 to 600 seconds, and preferably 30 to 300 seconds.

By developing the exposed resin film, a patterned resin film can be obtained. That is, development is carried out using an appropriate developer, for example, using a method such as an immersion method, a paddle method, or a rotary spray method. Through development, the exposed portion (if positive type) or the unexposed portion (if negative type) is eluted and removed from the resin film, and a substrate with a pattern can be obtained.

The developer that can be used is not particularly limited. For example, aqueous alkaline solutions, more specifically (i) aqueous inorganic alkaline solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, (ii) aqueous solutions of organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; Additionally, organic solvents such as cyclopentanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate may be used.

For example, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the developer.

As a developing solution, an aqueous solution of tetramethylammonium hydroxide is preferable. The concentration of tetramethylammonium hydroxide in this aqueous solution is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass.

After the development process, washing is preferably performed with a rinse solution to remove the developing solution. Examples of the rinse liquid include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These can be used individually or in combination of two or more types.

When the resin composition is crosslinkable (such as when it contains a crosslinking agent), a cured film can be obtained, for example, by heating the resin film. In this case, by heating, the portion corresponding to R ⁴ and/or the -OH portion in the polymer reacts with the crosslinking agent to form a bond.

Heating can be performed using a hot plate, oven, or the like.

The heating temperature is, for example, 50 to 200°C, preferably 80 to 150°C.

The heating time is, for example, 30 to 600 seconds, and preferably 60 to 300 seconds.

<Reference form>

This embodiment can also be expressed as follows.

A resin composition containing a polymer having a structural unit derived from a polymerizable monomer represented by the following general formula (II).

In general formula (Ⅱ),

R ¹ is a group containing at least one polymerizable group,

R ² and R ³ are each independently a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group,

R ⁴ is a crosslinkable group,

R ⁵ is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups,

R ⁶ and R ⁷ each independently represent a fluorinated alkyl group,

n represents an integer of 1 to 5, and when n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different,

m represents an integer of 1 to 3, and when m is 2 or 3, a plurality of R ⁶ may be the same or different, and a plurality of R ⁷ may be the same or different.

In general formula (II), the specific aspects of R ¹ , R ² , R ³ , R ⁵ , R ⁶ and R ⁷ are the same as those in general formula (I).

In General Formula (II), the chemical structure of R ⁴ is not particularly limited as long as it can form a bond by reacting with a cross-linkable group provided in the cross-linking agent. R ⁴ can specifically be a hydrogen atom, an acid group, or a straight-chain or branched aliphatic hydrocarbon group substituted with a hydroxy group. For specific aspects of the straight-chain or branched aliphatic hydrocarbon group substituted by an acid group or a hydroxy group, refer to the explanation in General Formula (I).

Although embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. In addition, the present invention is not limited to the above-described embodiments, and modifications and improvements within the range that can achieve the purpose of the present invention are included in the present invention.

(Example)

Embodiments of the present invention will be described in detail based on examples and comparative examples. Please note in advance that the present invention is not limited to the examples.

1. Synthesis of polymerizable monomers

[Synthesis of MA-IPA-HFA]

In a 300 mL three-neck round bottom flask, methacrylic acid (17.22 g, 200 mmol) and acetonitrile (35 ml) were mixed, cooled on ice, and triethylamine (10.1 g, 100 mmol) was slowly added dropwise. After that, it was heated to 60°C, and BTHB-epo (22.41 g, 100 mmol) (Central Glass Co., Ltd.) was added over 1 hour. Also, it was stirred at 80°C for 2 hours.

After the reaction solution was cooled to room temperature, it was washed with 5% by mass sodium bicarbonate water, 0.1% hydrochloric acid water, and distilled water once each, and concentrated with an evaporator to obtain a concentrated solution. 120 g of heptane was added to the concentrate to precipitate crystals, which were then filtered and dried. In this way, MA-IPA-HFA (21.7 g, yield 70%) was obtained.

¹ H-NMR (Acetone-d6): 7.02ppm(br,1H), 6.12ppm(m,1H), 5.90ppm(br,1H), 5.67ppm(quin,J=1.6Hz,1H), 4.56ppm( br,1H), 4.25ppm(dd,J=11.6Hz,4.4Hz,1H), 4.17ppm(dd,J=11.6Hz,6.4Hz,1H), 2.31ppm(dd,J=15.2Hz,3.2Hz, 1H), 2.24ppm(qdd,1H), 1.93ppm(dd,J=1.6Hz,0.8Hz,3H)

¹⁹ F-NMR(Acetone-d6): -76.3ppm(q,9.2Hz,3F), -79.6ppm(q,9.6Hz,3F)

In addition, the above-mentioned “BTHB-epo” was synthesized as follows.

In a 3 L three-necked round bottom flask, BTHB (166.46 g, 800 mmol) (Central Glass Company Limited) and dichloromethane (800 mL) were mixed, cooled on ice, and mCPBA (195.26 g, 792 mmol) was added in portions. Next, after stirring at 35°C overnight, washing was performed once with 10% by mass sodium thiosulfate water and once with 5% by mass sodium bicarbonate water, and concentrated with an evaporator to obtain a concentrate. The concentrate was distilled under reduced pressure (2 kPa, 67-70°C recovered) to obtain BTHB-epo (146.9 g, yield 82%) (“mCPBA” is an abbreviation for metachloroperbenzoic acid).

¹ H-NMR (CDCl ₃ ): 4.30ppm (s, 1H, OH group), 3.32ppm (br, 1H), 2.93ppm (t, 4.4Hz, 1H), 2.60ppm (dd, 4.4Hz, 2.4Hz, 1H), 2.47ppm(dd,15.2Hz,3.6Hz,1H), 1.86ppm(ddd,15.2Hz,8.8Hz,1.6Hz,1H)

¹⁹ F-NMR: -78.5ppm(q,12.4Hz,6F)

[Synthesis of A-IPA-HFA]

A-IPA-HFA (19.2 g, yield 65%) was obtained by the same procedure as the synthesis of MA-IPA-HFA, except that acrylic acid was used instead of methacrylic acid.

¹ H-NMR (Acetone-d6): 6.40ppm (ddd, J = 17.6Hz, 1.6Hz, 0.4Hz, 1H), 6.18ppm (ddd, J = 17.6Hz, 10.4Hz, 0.4Hz, 1H), 5.93ppm (dd,1H), 4.55ppm(m,1H), 4.27ppm(dd,J=11.6Hz,4.0Hz,1H), 4.18ppm(dd,J=11.6Hz,6.0Hz,1H), 2.30ppm(dd ,J＝15.2Hz,3.2Hz,1H), 2.19ppm(qdd,1H)

¹⁹ F-NMR(Acetone-d6): -76.3ppm(q,9.2Hz,3F), -79.6ppm(q,10.8Hz,3F)

[Synthesis of αCF3A-IPA-HFA]

αCF3A-IPA-HFA (14.5 g, yield 40%) was obtained by the same procedure as the synthesis of MA-IPA-HFA, except that α-trifluoromethylacrylic acid was used instead of methacrylic acid.

¹ H-NMR (Acetone-d6): 6.99ppm(br,1H), 6.08ppm(m,1H), 5.85ppm(br,1H), 5.55ppm(quin,J=1.6Hz,1H), 4.49ppm( br,1H), 4.23ppm(dd,J=11.6Hz,4.4Hz,1H), 4.13ppm(dd,J=11.6Hz,6.4Hz,1H), 2.28ppm(dd,J=15.2Hz,3.2Hz, 1H), 2.19ppm(qdd,1H)

¹⁹ F-NMR: -63.5ppm(s,3F(α-CF3)), -76.1ppm(q,9.2Hz,3F(HFIP)), -79.4ppm(q,9.6Hz,3F(HFIP))

2. Preparation of polymer using the above polymerizable monomer

Before explaining the polymer manufacturing procedure, methods for measuring various physical properties of the polymer will be explained.

[Measurement of molar ratio of each structural unit]

The molar ratio of each structural unit in the polymer was determined from measurement data of ¹ H-NMR, ¹⁹ F-NMR, or ¹³ C-NMR.

[Measurement of molecular weight distribution of polymer]

The weight average molecular weight (Mw) and molecular weight dispersion (ratio of number average molecular weight (Mn) and weight average molecular weight (Mw); Mw/Mn) of the polymer can be measured using high-speed gel permeation chromatography (hereinafter sometimes referred to as GPC). . Tosoh Corporation product, model HLC-8320GPC) was used. Specifically, an ALPHA-M column and an ALPHA-2500 column (all manufactured by Tosoh Corporation) were connected in series, and measurement was performed using tetrahydrofuran (THF) as a developing solvent. As a detector, a refractive index difference measurement detector was used.

Mw and Mn are values obtained using polystyrene as a standard material.

[Synthesis of fluoropolymer resin 1]

In a 1000 mL glass flask equipped with a stirrer, 31.0 g (0.1 mol) of MA-IPA-HFA and hexafluoroisopropyl methacrylate (product of Central Glass Company Limited. Hereinafter referred to as HFIP) were placed at room temperature (about 20°C). Add 23.6 g (0.1 mol) of methyl ethyl ketone (represented as -M) and 110 g of methyl ethyl ketone (hereinafter referred to as MEK), and add 2,2'-azobis(2-methylbutyronitrile) (Tokyo Chemical Industry Co., Ltd. ) (Tokyo Chemical Industry Co., Ltd. product, hereinafter referred to as AIBN) was added in an additional 1.6 g (0.01 mol). Then, the inside of the flask was degassed while stirring. After that, the inside of the flask was replaced with nitrogen gas, the temperature was raised to an internal temperature of 75°C, and reaction was carried out for 6 hours. When 500 g of n-heptane was added dropwise to the reaction system, a transparent viscous substance was precipitated. This viscous substance was isolated by decantation. The isolated viscous material was dried under reduced pressure at 60°C to obtain 46.4 g of fluoropolymer resin 1 as a transparent viscous material with a yield of 85%.

As a result of NMR measurement, the composition ratio of each structural unit of fluoropolymer 1 was, in mol%, structural unit derived from MA-IPA-HFA: structural unit derived from HFIP-M = 51:49.

Additionally, as a result of GPC measurement, Mw = 16,000 and Mw/Mn = 1.8.

[Synthesis of fluoropolymer resin 2]

The same procedure as the synthesis of fluoropolymer resin 1 except that 1H,1H,5H-octafluoropentyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as OFP-M) was used instead of HFIP-M. As a result, fluorine-containing resin 2 containing the above structural units was obtained with a yield of 83%.

As a result of NMR measurement, the composition ratio of each structural unit of fluoropolymer 2 was, in mol%, structural unit derived from MA-IPA-HFA: structural unit derived from OFP-M = 50:50.

Additionally, as a result of GPC measurement, Mw = 15,300, Mw/Mn = 1.7.

[Synthesis of fluoropolymer resin 3]

In a 1000 mL glass flask equipped with a stirrer, 29.6 g (0.1 mol) of A-IPA-HFA, 23.6 g (0.1 mol) of HFIP-M, 105 g of MEK, and 1.6 g of AIBN were added at room temperature (about 20°C). Additional g (0.01 mol) was added and degassed while stirring. After that, the inside of the flask was replaced with nitrogen gas, the temperature was raised to 75°C, and reaction was carried out for 6 hours. Next, 400 g of n-heptane was added dropwise to the reaction system, and a transparent viscous substance was precipitated. This viscous material was isolated by decantation. The isolated viscous material was dried under reduced pressure at 60°C to obtain 46.2 g of fluoropolymer resin 3 as a transparent viscous material with a yield of 87%.

As a result of NMR measurement, the composition ratio of each structural unit of fluoropolymer 3 was, in mol%, structural unit derived from A-IPA-HFA: structural unit derived from HFIP-M = 52:48.

Additionally, as a result of GPC measurement, Mw = 18,000, Mw/Mn = 1.8.

[Synthesis of fluoropolymer resin 4]

Fluorine-containing resin 4 containing the above structural units was obtained with a yield of 84% by following the same procedure as the synthesis of fluorine-containing resin 3, except that OFP-M was used instead of HFIP-M.

As a result of NMR measurement, the composition ratio of each structural unit of fluoropolymer 4 was, in mol%, structural unit derived from A-IPA-HFA: structural unit derived from OFP-M = 51:49.

Additionally, as a result of GPC measurement, Mw = 16,300, Mw/Mn = 1.7.

[Synthesis of fluoropolymer resin 5]

In a 1000 mL glass flask equipped with a stirrer, add 36.4 g (0.1 mol) of αCF3A-IPA-HFA, 23.6 g (0.1 mol) of HFIP-M, 120 g of MEK, and 1.6 g of AIBN at room temperature (about 20°C). Additional g (0.01 mol) was added and degassed while stirring. After that, the inside of the flask was replaced with nitrogen gas, the temperature was raised to 75°C, and reaction was carried out for 6 hours. When 550 g of n-heptane was added dropwise to the reaction system, a transparent viscous substance was precipitated. This viscous material was isolated by decantation. The isolated viscous material was dried under reduced pressure at 60°C to obtain 49.2 g of fluoropolymer resin 5 as a transparent viscous material with a yield of 82%.

As a result of NMR measurement, the composition ratio of each structural unit of fluoropolymer 5 was, in mol%, structural unit derived from αCF3A-IPA-HFA: structural unit derived from HFIP-M = 50:50.

Additionally, as a result of GPC measurement, Mw = 15,000 and Mw/Mn = 1.6.

[Synthesis of fluoropolymer resin 6]

Fluorine-containing resin 6 containing the above structural units was obtained with a yield of 81% by following the same procedure as the synthesis of fluorine-containing resin 5, except that OFP-M was used instead of HFIP-M.

As a result of NMR measurement, the composition ratio of each structural unit of fluoropolymer 6 was, in mol%, structural unit derived from αCF3A-IPA-HFA: structural unit derived from OFP-M = 49:51.

Additionally, as a result of GPC measurement, Mw = 14,300 and Mw/Mn = 1.5.

[Synthesis of fluoropolymer resin 7]

The above structural unit was synthesized using the same procedure as the synthesis of fluoropolymer 3, except that hexafluoroisopropyl acrylate (product of Central Glass Company Limited, hereinafter referred to as HFIP-A) was used instead of HFIP-M. Fluorine-containing resin 7 was obtained with a yield of 83%.

As a result of NMR measurement, the composition ratio of each structural unit of fluoropolymer 7 was, in mol%, structural unit derived from A-IPA-HFA: structural unit derived from HFIP-A = 50:50.

Additionally, as a result of GPC measurement, Mw = 15,800, Mw/Mn = 1.6.

[Synthesis of fluoropolymer resin 8]

By following the same procedure as the synthesis of fluorine-containing resin 1, except that HFIP-A was used instead of HFIP-M, fluorine-containing resin 8 containing the above structural units was obtained with a yield of 82%.

As a result of NMR measurement, the composition ratio of each structural unit of fluoropolymer 8 was, in mol%, structural unit derived from MA-IPA-HFA: structural unit derived from HFIP-A = 51:49.

Additionally, as a result of GPC measurement, Mw = 14,300 and Mw/Mn = 1.5.

3. Preparation of comparative fluororesin

[Comparative synthesis of fluoropolymer resin 1]

In a 1000 mL glass flask equipped with a stirrer, methacrylic acid-5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl was placed at room temperature (about 20°C). (Product of Central Glass Company Limited. Hereinafter referred to as MA-BTHB-OH), 29.4 g (0.1 mol), HFIP-M, 23.6 g (0.1 mol), MEK, 110 g, AIBN 1.6 g (0.01 mol) ) was added and degassed while stirring. After that, the inside of the flask was replaced with nitrogen gas, the temperature was raised to 75°C, and reaction was carried out for 6 hours. When 500 g of n-heptane was added dropwise to the reaction system, a transparent viscous substance was precipitated. This viscous material was isolated by decantation. The isolated viscous material was dried under reduced pressure at 60°C, and 42.4 g of comparative fluoropolymer resin 1 was obtained as a transparent viscous material with a yield of 80%.

As a result of NMR measurement, the composition ratio of each structural unit of comparative fluoropolymer 1 was, in mol%, structural unit derived from MA-BTHB-OH: structural unit derived from HFIP-M = 50:50.

Additionally, as a result of GPC measurement, Mw = 13,000 and Mw/Mn = 1.4.

[Comparative synthesis of fluoropolymer resin 2]

Comparative fluorinated resin 2 containing the above structural units was obtained in a yield of 80% by following the same procedure as the synthesis of comparative fluorinated resin 1, except that OFP-M was used instead of HFIP-M.

As a result of NMR measurement, the composition ratio of each structural unit of comparative fluoropolymer 2 was, in mol%, structural unit derived from MA-BTHB-OH: structural unit derived from OFP-M = 50:50.

Additionally, as a result of GPC measurement, Mw = 12,300 and Mw/Mn = 1.4.

[Comparative synthesis of fluoropolymer resin 3]

First, in a 1000 mL glass flask equipped with a stirrer, acrylic acid-5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl ( 27.9 g (0.1 mol) of Central Glass Company Limited (hereinafter referred to as A-BTHB-OH), 23.6 g (0.1 mol) of HFIP-M, and 103 g of MEK were added. After that, 1.6 g (0.01 mol) of AIBN was added to the flask and degassed while stirring.

After that, the inside of the flask was replaced with nitrogen gas, the temperature was raised to 75°C, and reaction was carried out for 6 hours. When 500 g of n-heptane was added dropwise to the reaction system, a transparent viscous substance was precipitated. This viscous material was isolated by decantation. The isolated viscous material was dried under reduced pressure at 60°C, and 41.7 g of comparative fluoropolymer resin 3 was obtained as a transparent viscous material with a yield of 80%.

As a result of NMR measurement, the composition ratio of each structural unit of comparative fluoropolymer 3 was, in mol%, structural unit derived from A-BTHB-OH: structural unit derived from HFIP-M = 49:51.

Additionally, as a result of GPC measurement, Mw = 12,900, Mw/Mn = 1.4.

[Comparative synthesis of fluoropolymer resin 4]

Except that OFP-M was used instead of HFIP-M, comparative fluorine-containing resin 4 containing the above structural units was obtained with a yield of 78% by the same procedure as the synthesis of comparative fluorine-containing resin 3.

As a result of NMR measurement, the composition ratio of each structural unit of comparative fluoropolymer 4 was, in mol%, structural unit derived from A-BTHB-OH: structural unit derived from OFP-M = 49:51.

Additionally, as a result of GPC measurement, Mw = 12,100, Mw/Mn = 1.3.

[Comparative synthesis of fluoropolymer resin 5]

In a 1000 mL glass flask equipped with a stirrer, 2-trifluoromethylacrylic acid-5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentane was added at room temperature (about 20°C). 34.8 g (0.1 mol) of -2-yl (manufactured by Central Glass Company Limited, hereinafter referred to as αCF3A-BTHB-OH), 23.6 g (0.1 mol) of HFIP-M, and 110 g of MEK were added. After that, 1.6 g (0.01 mol) of AIBN was added to the flask and degassed while stirring.

After that, the inside of the flask was replaced with nitrogen gas, the temperature was raised to 75°C, and reaction was carried out for 6 hours. When 500 g of n-heptane was added dropwise to the reaction system, a transparent viscous substance was precipitated. This viscous material was isolated by decantation. The isolated viscous material was dried under reduced pressure at 60°C, and 41.7 g of comparative fluoropolymer resin 5 was obtained as a transparent viscous material with a yield of 80%.

As a result of the NMR measurement, the composition ratio of each structural unit of comparative fluoropolymer 5 was, in mol%, structural unit derived from αCF3A-BTHB-OH: structural unit derived from HFIP-M = 49:51.

Additionally, as a result of GPC measurement, Mw = 13,900 and Mw/Mn = 1.5.

[Comparative synthesis of fluoropolymer resin 6]

Except that OFP-M was used instead of HFIP-M, comparative fluorine-containing resin 6 containing the above structural units was obtained in a yield of 75% by the same procedure as the synthesis of comparative fluorine-containing resin 5.

As a result of NMR measurement, the composition ratio of each structural unit of comparative fluoropolymer 6 was, in mol%, structural unit derived from αCF3A-BTHB-OH: structural unit derived from OFP-M = 49:51.

Additionally, as a result of GPC measurement, Mw = 14,100, Mw/Mn = 1.5.

[Comparative synthesis of fluoropolymer resin 7]

Comparative fluorinated resin 7 containing the above structural units was obtained with a yield of 82% by following the same procedure as the synthesis of comparative fluorinated resin 3, except that HFIP-A was used instead of HFIP-M.

As a result of NMR measurement, the composition ratio of each structural unit of comparative fluoropolymer 7 was, in mol%, structural unit derived from A-BTHB-OH: structural unit derived from HFIP-A = 50:50.

Additionally, as a result of GPC measurement, Mw = 13,100, Mw/Mn = 1.5.

4. Preparation of photosensitive resin composition

[Preparation of photosensitive resin composition 1]

20 parts by mass of the prepared fluoropolymer resin 1, 2 parts by mass of hexamethoxymethylmelamine (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as HMMM) as an acid cross-linking agent, and Irgacure as a photoacid generator. A solution was obtained by mixing 1 part by mass of PAG121 (manufactured by BASF) with 77 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as a solvent. The obtained solution was filtered through a 0.2㎛ membrane filter. In this way, photosensitive resin composition 1 was prepared.

[Preparation of photosensitive resin composition 2]

Photosensitive resin composition 2 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that fluorine-containing resin 2 was used instead of fluorine-containing resin 1.

[Preparation of photosensitive resin composition 3]

Photosensitive resin composition 3 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that fluorine-containing resin 3 was used instead of fluorine-containing resin 1.

[Preparation of photosensitive resin composition 4]

Photosensitive resin composition 4 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that fluorine-containing resin 4 was used instead of fluorine-containing resin 1.

[Preparation of photosensitive resin composition 5]

Photosensitive resin composition 5 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that fluorine-containing resin 5 was used instead of fluorine-containing resin 1.

[Preparation of photosensitive resin composition 6]

Photosensitive resin composition 6 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that fluorine-containing resin 6 was used instead of fluorine-containing resin 1.

[Preparation of photosensitive resin composition 7]

Photosensitive resin composition 7 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that fluorine-containing resin 7 was used instead of fluorine-containing resin 1.

[Preparation of photosensitive resin composition 8]

Photosensitive resin composition 8 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that fluorine-containing resin 8 was used instead of fluorine-containing resin 1.

[Preparation of comparative photosensitive resin composition 1 (comparative 1)]

Comparative photosensitive resin composition 1 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that comparative fluorinated resin 1 was used instead of fluorinated resin 1.

[Preparation of comparative photosensitive resin composition 2 (comparative 2)]

Comparative photosensitive resin composition 2 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that comparative fluorinated resin 2 was used instead of fluorinated resin 1.

[Preparation of comparative photosensitive resin composition 3 (comparative 3)]

Comparative photosensitive resin composition 3 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that comparative fluorinated resin 3 was used instead of fluorinated resin 1.

[Preparation of comparative photosensitive resin composition 4 (comparative 4)]

Comparative photosensitive resin composition 4 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that comparative fluorinated resin 4 was used instead of fluorinated resin 1.

[Preparation of comparative photosensitive resin composition 5 (comparative 5)]

Comparative photosensitive resin composition 5 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that comparative fluorine-containing resin 5 was used instead of fluorine-containing resin 1.

[Preparation of comparative photosensitive resin composition 6 (comparative 6)]

Comparative photosensitive resin composition 6 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that comparative fluorinated resin 6 was used instead of fluorinated resin 1.

[Preparation of comparative photosensitive resin composition 7 (comparative 7)]

Comparative photosensitive resin composition 7 was prepared in the same manner as the preparation of photosensitive resin composition 1, except that comparative fluorinated resin 7 was used instead of fluorinated resin 1.

5. Evaluation of patterns

"4. Using Photosensitive Resin Compositions 1 to 8 and Comparative Photosensitive Resin Compositions 1 to 7 obtained in “Preparation of Photosensitive Resin Composition”, patterning performance was evaluated and compared as follows. The results are shown in Table 1.

[Formation of pattern]

First, a 10 cm circular alkali-free substrate was washed with ultrapure water and then with acetone. Afterwards, UV ozone treatment was performed on this substrate for 5 minutes using a UV ozone treatment device. In this way, the substrate used for evaluation was prepared.

Next, 「4. Using the photosensitive resin compositions 1 to 8 and the comparative photosensitive resin compositions 1 to 7 obtained in “Preparation of a photosensitive resin composition,” the photosensitive resin compositions were applied to the substrate after UV ozone treatment described above using a spin coater at a rotation speed of 1,000 rpm, and then applied on a hot plate. By heating at 100°C for 120 seconds, a coating film with a thickness of 5 μm was formed.

Using a mask aligner (SUSS MicroTec product), an i-line (wavelength 365 nm) is applied to the formed resin film between a mask with a line and space of 10 μm (L/S = 10 μm/10 μm). ) was irradiated and exposed. Afterwards, heat treatment was performed on a hot plate at 100°C for 150 seconds. In this way, a resin film was obtained after exposure.

The obtained post-exposure resin film was evaluated for developer solubility and patterning (sensitivity, resolution) as follows.

[Developer solubility]

After exposure on the glass substrate, the resin film was immersed in an alkaline developer for each glass substrate at room temperature for 60 seconds to evaluate its solubility in the alkaline developer. As an alkaline developer, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) was used. Solubility was evaluated by measuring the film thickness (exposed part and unexposed part) of the resin film after immersion using a contact-type film thickness meter. When the resin film was completely dissolved, it was called “soluble,” and when the resin film remained undissolved, it was called “insoluble.”

[Patterning performance (sensitivity, resolution)]

First, in the above [formation of pattern], the optimal exposure amount (Eop) (mJ/cm2) when forming a line and space pattern was determined and used as an index of sensitivity. “Optimum exposure amount (Eop)” refers to the exposure amount that can form a pattern with L/S = 10 μm/10 μm as is when using a mask with L/S = 10 μm/10 μm.

Additionally, the obtained pattern was observed under a microscope to evaluate resolution. Those where line edge roughness (LER) could not be confirmed were rated as “excellent,” those where line edge roughness (LER) could not be confirmed were rated as “good,” and those where line edge roughness (LER) was noticeable were rated as “impossible.” In this regard, those for which a pattern could not be obtained are indicated with “-”.

[Evaluation of refractive index of cured film]

First, a cured film for refractive index evaluation was created as described in [Formation of Pattern] above, except that the entire surface was exposed without a mask. The refractive index of this cured film was measured using a prism coupler (Metricon Corporation product, 2010/M, wavelength 632 nm).

[Evaluation of adhesion of cured film]

As described in [Formation of Pattern] above, a glass substrate on which a pattern was formed was prepared. In addition, in the above [formation of the pattern], the same operation was performed except that a silicon wafer was used as the substrate instead of a glass substrate, and a silicon wafer on which the pattern was formed was created.

A crosscut test (JIS K 5600 5-6) was performed using the glass substrate on which these patterns were formed and the silicon wafer on which the patterns were formed. In the judgment, those with a crosscut test result of classification 0 were designated as passing (○), and the others were designated as failing (×).

The results of each of the above evaluations are collectively shown in Table 1.

As shown in Table 1, the unexposed portion of the resin film (film to which the pattern was exposed) formed using the photosensitive resin compositions 1 to 8 was well dissolved in the alkaline developer.

Additionally, by using the photosensitive resin compositions 1 to 8, a substrate with a good pattern could be obtained.

In addition, the refractive index of the resin film formed using the photosensitive resin compositions 1 to 8 was the same as that of the resin film formed using the comparative photosensitive resin compositions 1 to 7, and it was found to be applicable to optical members.

Moreover, the adhesion of the resin films formed using photosensitive resin compositions 1 to 8 to the substrate was good.

6. Evaluation of polymer water repellency, solubility in developer, and swelling/solubility in water (water repellency)

Fluorinated resins 1 to 8 and comparative fluorinated resins 1 to 7 were dissolved in a mixed solvent of 95% by mass of n-heptane and 5% by mass of n-hexyl alcohol, respectively, to obtain a solution for film formation with a solid content concentration of 2.5% by mass.

Next, each film-forming solution was spin-coated on a silicon wafer and baked at 110°C to obtain a substrate for evaluation on which a uniform resin film was formed.

The static contact angle of the obtained resin film with pure water was measured. The contact angle was measured using DMs-601 manufactured by Kyowa Interface Science Co., Ltd. The measurement method used the droplet method. Under a temperature condition of 23 ± 2°C in a clean room, a 0.5 μL drop of pure water was dropped onto a horizontally installed resin film, and the value was measured 1 second after the droplet was dropped. . The contact angle was calculated using the θ/2 method.

The results are shown in Table 2.

Additionally, a substrate for measuring the developer dissolution rate was created by forming a resin film with a film thickness of 10 μm on a glass substrate using the above film-forming solution, and the developer dissolution rate of the resin film was measured using this substrate.

Specifically, the substrate for measuring the dissolution rate of the developer was immersed in an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38% by mass, which is the developer. Immersion time: 10s, 20s, 30s, … Changed to , the relationship between immersion time and residual film thickness was obtained. And from this relationship, the dissolution rate (DR: Dissolution Rate) of the resin film was obtained.

In this regard, the residual film thickness was measured using a laser microscope (VX-1100, manufactured by KEYENCE CORPORATION).

Additionally, the evaluation substrate (different from the one used for contact angle evaluation and developer solubility evaluation) obtained as described above was cut in half, and the half was immersed in pure water for 30 minutes at a temperature of 23 ± 2°C, and then taken out. . When immersed, about 1 cm of water was allowed to exist above the substrate.

By comparing the immersed and non-immersed substrates, swelling and dissolution of the film were evaluated. The specific evaluation method is as follows.

Evaluation was made by observing the substrate with or without immersion using a laser microscope. The laser microscope used was Keyence's VX-1100. The evaluation criteria are as follows.

○ (good): Swelling and dissolution of the membrane did not occur. In other words, the membrane had excellent water repellency.

× (bad): Swelling and dissolution of the membrane occurred. In other words, the water repellency of the membrane decreased.

The above evaluation results are collectively shown in Table 3.

As shown in Tables 2 and 3, by using a resin composition containing a polymer having a structural unit derived from a polymerizable monomer represented by the general formula (I), it is insoluble in water (is water-repellent) and is alkali-resistant. A resin film that was well soluble in the developer was able to be formed. This result shows, for example, that the resin composition of this embodiment can be suitably applied to forming a protective film of a photosensitive resin film in a liquid immersion photolithography process.

This application claims priority based on Japanese Patent Application No. 2021-019618 filed on February 10, 2021, and the entire disclosure thereof is incorporated into this specification.

Claims (35)

A resin composition containing a polymer having a structural unit derived from a polymerizable monomer represented by the following general formula (I).
[Formula 1]

In general formula (Ⅰ),
R ¹ is a group containing at least one polymerizable group,
R ² and R ³ are each independently a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group,
R ⁴ is a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with an acid group or a hydroxy group,
R ⁵ is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups,
R ⁶ and R ⁷ each independently represent a fluorinated alkyl group,
n represents an integer of 1 to 5, and when n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different,
m represents an integer of 1 to 3, and when m is 2 or 3, a plurality of R ⁶ may be the same or different, and a plurality of R ⁷ may be the same or different.
According to paragraph 1,
When R ¹ is a group containing at least one of a (meth)acryloyl group, a vinyl group, and an epoxy group, and R ¹ contains a methacryloyl group, the hydrogen atom of the methyl group at the α site of the methacryloyl group A resin composition in which part or all of may be substituted with fluorine atoms.
According to claim 1 or 2,
A resin composition where R ⁴ is a hydrogen atom.
According to any one of claims 1 to 3,
A resin composition in which R ⁶ and R ⁷ are perfluoroalkyl groups.
According to any one of claims 1 to 4,
A resin composition in which R ⁶ and R ⁷ are trifluoromethyl groups.
According to any one of claims 1 to 5,
A resin composition where R ⁵ is a methylene group.
According to any one of claims 1 to 6,
A resin composition in which R ² and R ³ are hydrogen atoms.
According to any one of claims 1 to 7,
The polymer is olefin, fluorinated olefin, (meth)acrylic acid ester, fluorinated (meth)acrylic acid ester, norbornene compound, fluorinated norbornene compound, styrene-based compound, fluorinated styrene-based compound, vinyl ether and fluorinated vinyl. A resin composition further comprising a copolymerization unit derived from one or more monomers selected from the group consisting of ethers.
According to any one of claims 1 to 8,
A resin composition in which the polymer contains a structural unit represented by the following general formula (II) and a structural unit represented by the following general formula (III).
[Formula 2]

Among general formulas (Ⅱ) and (Ⅲ),
The definitions of R ² to R ⁷ , m and n are the same as those in the above general formula (I),
R ⁸ is a hydrogen atom or a methyl group,
R ⁹ is a hydrogen atom or a methyl group,
R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a fluorinated alkyl group.
According to any one of claims 1 to 9,
A resin composition in which the fluorine content of the polymer is 30 to 75% by mass.
According to any one of claims 1 to 10,
A resin composition containing an organic solvent.
According to any one of claims 1 to 11,
A resin composition used to form a protective film on a photosensitive resin film in a photolithography process.
According to any one of claims 1 to 11,
A resin composition containing a photoacid generator.
According to any one of claims 1 to 11,
A resin composition containing a crosslinking agent.
According to any one of claims 1 to 11,
A resin composition containing a photoacid generator and a crosslinking agent.
A resin film formed by the resin composition according to any one of claims 1 to 15.
A resin film formed by the resin composition of claim 14 or 15,
A resin film in which a portion corresponding to R ⁴ in the polymer reacts with the cross-linking agent to form a bond.
A substrate having a pattern formed by the resin composition of claim 13 or 15.
A polymer comprising a structural unit derived from a polymerizable monomer represented by the following general formula (I).
[Formula 3]

In general formula (Ⅰ),
R ¹ is a group containing at least one polymerizable group,
R ² and R ³ are each independently a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group,
R ⁴ is a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with an acid group or a hydroxy group,
R ⁵ is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups,
R ⁶ and R ⁷ each independently represent a fluorinated alkyl group,
n represents an integer of 1 to 5, and when n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different,
m represents an integer of 1 to 3, and when m is 2 or 3, a plurality of R ⁶ may be the same or different, and a plurality of R ⁷ may be the same or different.
According to clause 19,
When R ¹ is a group containing at least one of a (meth)acryloyl group, a vinyl group, and an epoxy group, and R ¹ contains a methacryloyl group, the hydrogen atom of the methyl group at the α site of the methacryloyl group A polymer that may have some or all of it substituted with fluorine atoms.
According to claim 19 or 20,
A polymer where R ⁴ is a hydrogen atom.
According to any one of claims 19 to 21,
A polymer wherein R ⁶ and R ⁷ are perfluoroalkyl groups.
According to any one of claims 19 to 22,
A polymer wherein R ⁶ and R ⁷ are trifluoromethyl groups.
According to any one of claims 19 to 23,
A polymer where R ⁵ is a methylene group.
According to any one of claims 19 to 24,
A polymer where R ² and R ³ are hydrogen atoms.
According to any one of claims 19 to 25,
A group consisting of olefins, fluorinated olefins, (meth)acrylic acid esters, fluorinated (meth)acrylic acid esters, norbornene compounds, fluorinated norbornene compounds, styrene-based compounds, fluorinated styrene-based compounds, vinyl ethers, and fluorinated vinyl ethers. A polymer further comprising a copolymerization unit derived from one or more monomers selected from .
According to any one of claims 19 to 26,
A polymer containing a structural unit represented by the following general formula (II) and a structural unit represented by the following general formula (III).
[Formula 4]

Among general formulas (Ⅱ) and (Ⅲ),
The definitions of R ² to R ⁷ , m and n are the same as those in the above general formula (I),
R ⁸ is a hydrogen atom or a methyl group,
R ⁹ is a hydrogen atom or a methyl group,
R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a fluorinated alkyl group.
According to any one of claims 19 to 27,
A polymer with a fluorine content of 30 to 75% by mass.
A polymerizable monomer represented by the following general formula (I).
[Formula 5]

Among general formula (Ⅰ),
R ¹ is a group containing at least one polymerizable group,
R ² and R ³ are each independently a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group,
R ⁴ is a hydrogen atom or a straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with an acid group or a hydroxy group,
R ⁵ is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, and some or all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups,
R ⁶ and R ⁷ each independently represent a fluorinated alkyl group,
n represents an integer of 1 to 5, and when n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different,
m represents an integer of 1 to 3, and when m is 2 or 3, a plurality of R ⁶ may be the same or different, and a plurality of R ⁷ may be the same or different.
According to clause 29,
When R ¹ is a group containing at least one of a (meth)acryloyl group, a vinyl group, and an epoxy group, and R ¹ contains a methacryloyl group, the hydrogen atom of the methyl group at the α site of the methacryloyl group A polymerizable monomer that may have some or all of it substituted with a fluorine atom.
According to claim 29 or 30,
A polymerizable monomer where R ⁴ is a hydrogen atom.
According to any one of claims 29 to 31,
A polymerizable monomer in which R ⁶ and R ⁷ are perfluoroalkyl groups.
According to any one of claims 29 to 32,
A polymerizable monomer in which R ⁶ and R ⁷ are trifluoromethyl groups.
According to any one of claims 29 to 33,
A polymerizable monomer where R ⁵ is a methylene group.
According to any one of claims 29 to 34,
A polymerizable monomer in which R ² and R ³ are hydrogen atoms.