JP2014063148A - Photosensitive resin composition and pattern formation method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which does not contain carboxyl groups or phenolic hydroxyl groups to enable dissolution in developing solutions but contains an aromatic polyester that can be dissolved in a polar solvent and applied onto a substrate.SOLUTION: The photosensitive resin composition contains a fluorine-containing polymer compound (A) that has a repeating unit represented by the general formula (1); a photosensitizer (B); and a polar solvent (C). (In the formula, Ris a divalent organic group which comprises 1-4 hexafluoroisopropanol groups and which is either protected or not protected by a protecting group, and Ris a divalent organic group.)

Description

  The present invention relates to a photosensitive resin composition and a pattern forming method using the same.

  As a material for a semiconductor protective film, polyimide or polybenzoxazole is known, and these are excellent in heat resistance and give a film having low water absorption and dielectric constant.

  As the photosensitive resin composition, polyamic acid and polyamidephenol are known, and these are converted into polyimide or polybenzoxazole by a dehydration reaction by heating. In order to make the polyamic acid or polyamidephenol soluble in a polar solvent and an alkaline developer, a carboxyl group or a phenolic hydroxyl group (hydroxyphenyl group) is contained in the chemical structure.

  In lithography, when the polyamic acid or polyamidephenol is dissolved in a polar solvent, it can be applied to a substrate as a resist solution to form a resist film, and development is possible when polyimide or polybenzoxazole is dissolved in an alkaline developer. Further, by adding a photosensitizer to the polyamic acid or polyamidephenol, a positive type in which the irradiated portion of the resist film is dissolved in an alkali developer by light irradiation, or a negative type photosensitivity in which the irradiated portion is insoluble in the alkaline developer. It becomes a resin composition. The difference between the positive type and the negative type depends on the chemical structure of the polyamic acid or the polyamide phenol. However, since polyimide has a heterocyclic ring, it is not transparent and has a problem that it is difficult to use as a resist.

  On the other hand, bisphenol, which is a compound having two phenolic hydroxyl groups, is known as a raw material monomer for polyester or polyimide.

  Polyester using bisphenol as a raw material monomer is used for a protective film of electronic parts such as a semiconductor substrate, an adhesive, a water treatment film such as filtration, a gas separation film, or a blood dialysis film. Since the polyester does not have a heterocyclic ring, it has higher visible light transparency than polyimide and polybenzoxazole having a heterocyclic ring, and is suitable for optical members such as a transparent protective film. Among them, polyarylate obtained by condensation polymerization of bisphenol A and terephthalic acid or isophthalic acid is known as a super engineering plastic excellent in transparency, weather resistance and flame retardancy. For example, Patent Document 1 discloses a polyimide obtained from a dinitro compound containing bisphenol and an imide ring.

  However, these polyesters and polyimides that use bisphenol as a raw material monomer are insoluble in solvents and difficult to mold.

  For example, Patent Document 2 discloses a photosensitive image forming material that can be developed with an aqueous alkaline developer. The photosensitive image forming material contains a photosensitive polyester or a modified polyester resin having an unsaturated double bond adjacent to the aromatic nucleus in the molecular main chain and having a photosensitive unsaturated double bond and a carboxyl group in the photosensitive layer. It is described that the photosensitive polyester or modified polyester contains a carboxyl group and is soluble in an aqueous alkaline developer.

  However, in the same way as the raw material monomer of polyimide or polybenzoxazole, even if a carboxyl group is introduced into bisphenol in a photosensitive polyester to make it soluble in an alkaline developer, it swells in the developer in lithography, so that it is fine. There is a problem that it is difficult to form a simple pattern. In addition, even if an attempt is made to add a hydroxyl group or a carboxyl group to an aromatic ring in the chemical structure in order to make it soluble in an alkali developer, bisphenol already contains two phenolic hydroxyl groups, and the reaction is multistage. Therefore, there is a problem that the synthesis becomes complicated. Polyester containing a phenolic hydroxyl group protects a part of the phenolic hydroxyl group of the raw material monomer using a trimethylsilyl group, tertiary butoxycarbonyl group, etc. as a protective group, and performs condensation polymerization with an unprotected phenolic hydroxyl group. After obtaining the polyester, it is obtained through a multi-step reaction in which the protecting group is eliminated.

Further, a hexafluoroisopropanol group (—C (CF ₃ ) ₂ OH, hereinafter sometimes referred to as HFIP group) is known as a functional group that imparts appropriate hydrophilicity to the fluoropolymer. In particular, in patterning by lithography during semiconductor manufacturing, a resist containing a fluoropolymer containing a hexafluoroisopropanol group exhibits high transparency and adhesion to the substrate in addition to hydrophilicity when applied as a resist on the substrate. . The resist is generally high in exposure sensitivity in ultraviolet exposure using an argon fluoride laser having a wavelength of 193 nm as a light source, the exposed portion is soluble in an alkali developer, and can be patterned by a photolithography method. .

  For example, in Patent Document 3, in a wavelength region from vacuum ultraviolet light to an optical communication wavelength region, it has high transparency and low refractive index, and has adhesion to a substrate, high film forming property, etching resistance, and durability. A fluorine-containing compound containing a hexafluoroisopropanol group bonded to an aromatic ring is disclosed as an antireflection film material or a resist material. A polymer compound obtained by using a fluorine-containing compound in which a hexafluoroisopropanol group, which is a polar group, is added to phenol or hexanol is soluble in a polar solvent, and is also soluble in an alkaline developer due to its hydrophilicity. is there.

In order to improve the solubility in polar solvents, isopropylidene _{(-C (CH 3) 2 -} ) bisphenol contains - including the site instead of the site, hexafluoro isopropylidene (-C _{(CF 3) 2)} A fluorine-based polymer obtained by copolymerizing fluorine-containing bisphenol as a raw material monomer is known.

  Patent Document 4 discloses a positive photosensitive resin composition comprising 100 parts by weight of hydroxypolyimide and 1 to 50 parts by weight of a diazonaphthoquinone compound, without isolating the hydroxypolyimide from the reaction solution for producing the hydroxypolyimide. A positive photosensitive resin composition using the obtained hydroxypolyimide is disclosed. Patent Document 5 discloses a photosensitive resin composition containing a polyamic acid-polyimide copolymer having a specific structure, that is, a poly (amide acid-imide) copolymer, and a diazonaphthoquinone photosensitizer.

  The means for making the polyester soluble in the developer includes a method of introducing a carboxyl group or a phenolic hydroxyl group into the chemical structure, as in the case of solubilization of the polyamic acid or polyhydroxyamide described above. However, in lithography, since a resin containing a carboxyl group swells in a developer, there is a problem that it is difficult to obtain a fine pattern when used as a resist.

  In the polymerization of polyester, the raw material monomer has a reactive carboxyl group or hydroxyl group, usually a phenolic hydroxyl group, and the carboxyl group and hydroxyl group are subjected to a dehydration condensation reaction to form an ester bond. Is obtained.

  In order to make it soluble in a developer, it is difficult to introduce a phenolic hydroxyl group as a soluble group in addition to a reactive carboxyl group in the polyester chemical structure after the dehydration condensation reaction. There was a problem that required a synthetic operation.

US Patent 3838097 JP-A 61-55643 JP 2004-83900 A JP 2001-296657 A JP 2010-134116 A

  The present invention does not contain a carboxyl group and a phenolic hydroxyl group as a soluble group, can be dissolved in a polar solvent and applied to a substrate, and contains a photosensitive polyester containing an aromatic polyester capable of forming a positive or negative resist pattern. The object is to obtain a resin composition.

  Furthermore, an object of this invention is to obtain the photosensitive resin composition containing the aromatic polyester excellent in transparency.

  In the photosensitive resin composition of the present invention, the fluorine-containing polymer compound (A) which is an aromatic polyester containing a hexafluoroisopropanol group protected with a protecting group or not protected with a protecting group is used. As the raw material monomer of the fluorine-containing polymer compound (A), a fluorine-containing compound containing a phenolic hydroxyl group as a reactive group and a hexafluoroisopropanol group as a soluble group in the same molecule is used. Since the raw material monomer contains a phenolic hydroxyl group, it can undergo a polycondensation reaction with the dicarboxylic acid or a derivative thereof, and a polycondensation reaction with the raw material monomer and the dicarboxylic acid or a derivative thereof to obtain the fluorine-containing polymer compound (A). The fluorine-containing polymer compound (A) containing a hexafluoroisopropanol group which is a soluble group in the molecular structure is soluble in the polar solvent (C). The photosensitive resin composition of this invention contains the said fluorine-containing polymer compound (A), a photosensitive agent (B), and a polar solvent (C). Hereinafter, unless otherwise specified, a hexafluoroisopropanol group protected with a protecting group or not protected with a protecting group may be simply referred to as a “hexafluoroisopropanol group”.

  That is, this invention includes the following inventions 1-16.

[Invention 1]
Repeating unit represented by general formula (1)

(In the formula, R ¹ is a divalent organic group containing 1 to 4 hexafluoroisopropanol groups protected by a protecting group or not protected by a protecting group, and R ² is a divalent organic group. ))-Containing fluorine-containing polymer compound (A),
A photosensitive agent (B);
A photosensitive resin composition comprising a polar solvent (C).

[Invention 2]
The photosensitive resin composition of the invention 1 whose R < ¹ > is group represented by General formula (2).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group, and R ⁴ represents a single bond, oxygen atom, sulfur atom, SO ₂ , CH ₂ , CO, C (CH ₃ ) ₂ , C (CH ₃ ). _{(CH 2 CH 3), C} (CF 3) 2, C (CH 3) (C 6 H 5), CH 2 -C 6 H 4 -CH 2 or benzene, biphenyl, naphthalene, hydrogen atom from cyclohexene or fluorene Is a divalent organic group from which two are separated, a and b are each independently an integer of 0 to 2, and 1 ≦ a + b ≦ 4.
[Invention 3]
The photosensitive resin composition of the invention 1 or the invention 2 whose R < ¹ > is group represented by General formula (3).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group, and R ⁴ represents a single bond, an oxygen atom, a sulfur atom, SO ₂ , CH ₂ , CO, C (CH ₃ ) ₂ , C ( _{CH 3) (CH 2 CH 3} ), C (CF 3) 2, C (CH 3) (C 6 H 5), CH 2 -C 6 H 4 -CH 2 or benzene, biphenyl, naphthalene, cyclohexene or fluorene, This is a divalent organic group in which two hydrogen atoms have been removed from.
[Invention 4]
The photosensitive resin composition of the invention 1-3 whose R < ¹ > is group represented by General formula (4).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group.)
[Invention 5]
The photosensitive resin composition of the invention 1-3 whose R < ¹ > is group represented by General formula (5).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group.)
[Invention 6]
The photosensitive resin composition of the invention 1 whose R < ¹ > is group represented by General formula (6).

(In the formula, R ³ is each independently a hydrogen atom or a protecting group, c and d are each independently an integer of 0 to 2, and c + d is 0 to 4. e is an integer of 0 to 3) F and g are each independently an integer of 0 to 2, and 1 ≦ f + g ≦ 4.

In the formula (6), the following formula:

The site represented by represents an aromatic ring, the carbon atom constituting the ring may be substituted with a heteroatom (nitrogen atom, oxygen atom or sulfur atom), and the hydrogen atom may be substituted with a substituent. The substituent may contain a nitrogen atom, an oxygen atom or a sulfur atom. In addition, the circle in a formula shows that the ring which wraps this forms the aromatic ring. )
[Invention 7]
The photosensitive resin composition of the invention 1 or the invention 6 whose R < ¹ > is group represented by General formula (7).

(In the formula, each R ³ is independently a hydrogen atom or a protecting group, and f and g are each independently an integer of 0 to 2, and 1 ≦ f + g ≦ 4.)
[Invention 8]
The photosensitive resin composition of invention 1, invention 6 or invention 7, wherein R ¹ is a group represented by formula (8).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group.)
[Invention 9]
Furthermore, the photosensitive resin composition of the invention 1-8 containing an epoxy compound.

[Invention 10]
The epoxy compound may contain a glycidyl group, and may contain a carbon-carbon double bond, a carbon-carbon triple bond, an aromatic ring or a heterocyclic ring in the chemical structure, and part or all of the hydrogen atoms in the epoxy compound Are each independently an epoxy compound which may be substituted with a fluorine atom, a chlorine atom, an alkyl group or a fluoroalkyl group.

[Invention 11]
Furthermore, the photosensitive resin composition of the invention 9 containing an epoxy resin hardening | curing agent.

[Invention 12]
The photosensitive resin composition of invention 1-11 whose photosensitizer (B) is a photo-acid generator which generate | occur | produces an acid by exposure.

[Invention 13]
The photosensitive resin composition of the invention 1-12 whose photosensitive agent (B) is a photo-acid generator which generate | occur | produces a sulfonic acid by exposure.

[Invention 14]
The photosensitive resin composition of the invention 1-13 whose photosensitive agent (B) is a diazo naphthoquinone compound which generate | occur | produces indenecarboxylic acid by exposure.

[Invention 15]
The polar solvent (C) is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, γ-butyrolactone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide or N-methylpyrrolidone. The photosensitive resin composition of the invention 1-14 which is a polar solvent.

[Invention 16]
A step of applying the photosensitive resin composition of the invention 1 to 15 on a substrate and volatilizing the solvent, a step of exposing the photosensitive resin film obtained after the drying step to a predetermined pattern shape through a photomask, and A pattern forming method comprising a step of developing a photosensitive resin film after exposure to contact with a developer, and a step of heating the photosensitive resin film after development.

  According to the present invention, a photosensitive material containing an aromatic polyester that can be applied to a substrate by dissolving in a polar solvent without containing a carboxyl group and a phenolic hydroxyl group as a soluble group, and capable of forming a positive or negative resist pattern. A resin composition can be obtained.

  Furthermore, the photosensitive resin composition containing aromatic polyester excellent in transparency can be obtained by this invention.

  The photosensitive resin composition of this invention contains the fluorine-containing polymer compound (A) which is aromatic polyester, a photosensitive agent (B), and a polar solvent (C).

  The photosensitive resin composition of the present invention is a solution in which a fluorine-containing polymer compound (A) and a photosensitive agent (B) are dissolved in a polar solvent (C), and is applied to a substrate by lithography and then exposed. A positive or negative resist pattern is formed, and pattern formation is possible.

  The fluorine-containing polymer compound (A) is obtained by converting a fluorine-containing compound containing two phenolic hydroxyl groups and a hexafluoroisopropanol group protected with a protecting group or not protected with a protecting group into phenol in the fluorine-containing compound. The functional hydroxyl group is selectively obtained by a polycondensation reaction with a dicarboxylic acid or a derivative thereof.

  The fluorine-containing polymer compound (A) is soluble in the polar solvent (C) by containing a hexafluoroisopropanol group. The photosensitive resin composition of the present invention, in which a photosensitive agent (B) and a polar solvent (C) are added to the fluorine-containing polymer compound (A), is a liquid at room temperature (5 ° C. to 35 ° C.), and is applied to a substrate or the like. When applied and cured as a coating film, a heterocyclic ring that causes a decrease in transparency is not formed.

  Hereinafter, each of the compositions used in the photosensitive resin composition of the present invention, the fluorine-containing polymer compound (A), the fluorine-containing compound and dicarboxylic acid as raw material monomers for obtaining the fluorine-containing polymer compound (A), or A pattern forming method using the derivative, the photosensitive agent (B), the polar solvent (C), and the photosensitive resin composition will be described in order.

1. Fluorine-containing polymer compound (A) used for photosensitive resin composition
The fluorine-containing polymer compound (A) includes a repeating unit represented by the general formula (1).

(In the formula, R ¹ is a divalent organic group containing 1 to 4 hexafluoroisopropanol groups protected by a protecting group or not protected by a protecting group, and R ² is a divalent organic group. ))-Containing fluorine-containing polymer compound (A),
R ¹ is preferably any group represented by the following general formulas (2) to (8).

(In Formula (2), R ³ is each independently a hydrogen atom or a protecting group, and R ⁴ is a single bond, an oxygen atom, a sulfur atom, SO ₂ , CH ₂ , CO, C (CH ₃ ) ₂ , C ( _{CH 3) (CH 2 CH 3} ), C (CF 3) 2, C (CH 3) (C 6 H 5), CH 2 -C 6 H 4 -CH 2 or benzene, biphenyl, naphthalene, cyclohexene or fluorene, 2 is a divalent organic group in which two hydrogen atoms are separated from each other, a and b are each independently an integer of 0 to 2, and 1 ≦ a + b ≦ 4.)

(In Formula (3), each R ³ is independently a hydrogen atom or a protecting group, and R ⁴ is a single bond, an oxygen atom, a sulfur atom, SO ₂ , CH ₂ , CO, C (CH ₃ ) _{2. , C (CH 3) (CH} 2 CH 3), C (CF 3) 2, C (CH 3) (C 6 H 5), CH 2 -C 6 H 4 -CH 2 or benzene, biphenyl, naphthalene, (It is a divalent organic group in which two hydrogen atoms are separated from cyclohexene or fluorene.)

(In formula (4), each R ³ is independently a hydrogen atom or a protecting group.)

(In Formula (5), each R ³ is independently a hydrogen atom or a protecting group.)

(In Formula (6), R ³ is each independently a hydrogen atom or a protecting group, c and d are each independently an integer of 0 to 2, and c + d is 0 to 4. e is 0 to 0. It is an integer of 3. f and g are each independently an integer of 0 to 2, and 1 ≦ f + g ≦ 4.

In the formula (6), the following formula:

The site represented by represents an aromatic ring, the carbon atom constituting the ring may be substituted with a heteroatom (nitrogen atom, oxygen atom or sulfur atom), and the hydrogen atom may be substituted with a substituent. The substituent may contain a nitrogen atom, an oxygen atom or a sulfur atom. In addition, the circle in a formula shows that the ring which wraps this forms the aromatic ring. )

(In the formula, each R ³ is independently a hydrogen atom or a protecting group, and f and g are each independently an integer of 0 to 2, and 1 ≦ f + g ≦ 4.)

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group.)
The photosensitive resin composition of the present invention can be suitably used for a semiconductor protective film such as a buffer coat film or a rewiring film. Furthermore, since the fluorine-containing polymer compound (A) used in the photosensitive resin composition of the present invention is a polyester, it is more transparent than conventional heterocyclic-containing resins such as photosensitive polyimide and photosensitive polybenzoxazole. It can be suitably used as a protective film for a touch panel display.

In the fluorine-containing polymer compound (A), when R ¹ is a group represented by the above formula (4), formula (5) or formula (8), the transparency when applied to a substrate to form a film is high. preferable.

2. Raw material monomer for polymerizing the fluorine-containing polymer compound (A) The fluorine-containing polymer compound (A) has two phenolic hydroxyl groups and a fluorine-containing compound in which a hexafluoroisopropanol group is bonded to an aromatic ring, Using a dicarboxylic acid or a derivative thereof as a raw material monomer, the fluorine-containing compound and the dicarboxylic acid or a derivative thereof are obtained by a condensation polymerization reaction. That is, the fluorine-containing compound represented by HO—R ¹ —OH and the dicarboxylic acid represented by HOOC—R ² —COOH or a derivative thereof undergo a condensation polymerization reaction to obtain a fluorine-containing resin compound represented by the general formula (1A). It is done.

(In the formula, R ¹ is a divalent organic group containing 1 to 4 hexafluoroisopropanol groups protected by a protecting group or not protected by a protecting group, and R ² is a divalent organic group. .)
The fluorine-containing polymer compound (A) contained in the photosensitive resin composition of the present invention is represented by the following general formulas (2A) to (9A) contained in HO—R ¹ —OH (general formula (1A)). It is obtained by polycondensation of a fluorine-containing compound and a dicarboxylic acid represented by the following general formulas (10) to (11) contained in HOOC-R ² —COOH or a derivative thereof.

2-1. Fluorine-containing compound Examples of the fluorine-containing compound include compounds represented by general formulas (2A) to (8A) contained in HO-R ¹ -OH.

[Fluorine-containing compound represented by the general formula (2A)]

(In Formula (2A), R ³ is each independently a hydrogen atom or a protecting group, and R ⁴ is a single bond, oxygen atom, sulfur atom, SO ₂ , CH ₂ , CO, C (CH ₃ ) ₂ , C ( _{CH 3) (CH 2 CH 3} ), C (CF 3) 2, C (CH 3) (C 6 H 5), CH 2 -C 6 H 4 -CH 2 or benzene, biphenyl, naphthalene, cyclohexene or fluorene, And a and b are each independently an integer of 0 to 2, and 1 ≦ a + b ≦ 4.) [Including represented by the general formula (3A) Fluorine compound]

(In Formula (3A), each R ³ is independently a hydrogen atom or a protecting group, and R ⁴ is a single bond, an oxygen atom, a sulfur atom, SO ₂ , CH ₂ , CO, C (CH ₃ ) _{2. , C (CH 3) (CH} 2 CH 3), C (CF 3) 2, C (CH 3) (C 6 H 5), CH 2 -C 6 H 4 -CH 2 or benzene, biphenyl, naphthalene, (It is a divalent organic group in which two hydrogen atoms are separated from cyclohexene or fluorene.)
[Fluorine-containing compound represented by general formula (4A)]

(In formula (4A), each R ³ independently represents a hydrogen atom or a protecting group.)
[Fluorine-containing compound represented by the general formula (5A)]

(In formula (5A), each R ³ independently represents a hydrogen atom or a protecting group.)
[Fluorine-containing compound represented by the general formula (6A)]

(In Formula (6A), R ³ is each independently a hydrogen atom or a protecting group, c and d are each independently an integer of 0 to 2, and c + d is 0 to 4. e is 0 to 0. It is an integer of 3. f and g are each independently an integer of 0 to 2, and 1 ≦ f + g ≦ 4.

In the formula (6A), the following formula:

The site represented by represents an aromatic ring, the carbon atom constituting the ring may be substituted with a heteroatom (nitrogen atom, oxygen atom or sulfur atom), and the hydrogen atom may be substituted with a substituent. The substituent may contain a nitrogen atom, an oxygen atom or a sulfur atom. In addition, the circle in a formula shows that the ring which wraps this forms the aromatic ring. )
[Fluorine-containing compound represented by the general formula (7A)]

(In the formula, each R ³ is independently a hydrogen atom or a protecting group, and f and g are each independently an integer of 0 to 2, and 1 ≦ f + g ≦ 4.)
[Fluorine-containing compound represented by the general formula (8A)]

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group.)
2-2. Protecting group Protecting group R ³ is hydrolyzed and eliminated by the acid generated from the photoacid generator irradiated with light, and as a result, the protected hexafluoropropanol group is a hexafluoropropanol group having an OH group. Become.

Specific examples of the protecting group R ³ include groups represented by the following (L-1) to (L-4).

R ^3A —O—C (═O) — (L-1)
R ^<3A > -O-CHR < ^3B >-(L-2)
SiR ^3C R ^3D R ^3E − (L-3)
R ^3A -C (= O)-(L-4)
Among these, (L-1) and (L-2) function as chemical amplification types and are particularly preferable for use in a resist composition applied to a pattern forming method in which exposure is performed with high energy rays. R ^{3A to} R ^3E are monovalent organic groups.

Examples of the alkoxycarbonyl group (L-1) represented by R ^3A —O—C (═O) — include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and i-propoxy. Examples thereof include a carbonyl group, a cyclohexyloxycarbonyl group, an isobornyloxycarbonyl group, an adamantaneoxycarbonyl group, and the like. Of these, a tert-butoxycarbonyl group, a methoxycarbonyl group, and an ethoxycarbonyl group are preferable, and a tert-butoxycarbonyl group is particularly preferable. A polymer compound containing a hexafluoroisopropanol group (a fluorine-containing polymer compound (A) in which R ³ is hydrogen in the group represented by the general formula (2) or the general formula (6)), pyridine, triethylamine, etc. The target polymer compound protected with a tert-butoxycarbonyl group can be obtained by reacting with tert-butoxycarboxylic anhydride in the presence of the organic base.

As the acetal group (L-2) represented by R ^3A —O—CHR ^3B —, a methoxymethyl group, an ethoxymethyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, 1 -Cyclohexyloxyethyl group, 1-benzyloxyethyl group, 1-phenethyloxyethyl group, 1-ethoxypropyl group, 1-benzyloxypropyl group, 1-phenethyloxypropyl group, 1-ethoxybutyl group, 1-cyclohexyloxy Examples thereof include an ethyl group, a 1-ethoxyisobutyl group, a 1-methoxyethoxymethyl group, a tetrahydropyranyl group, and a tetrahydrofuranyl group. Moreover, the acetal group obtained by adding vinyl ethers with respect to a hydroxyl group can be mentioned. Among these, a methoxymethyl group, an ethoxymethyl group, and a 1-ethoxyethyl group are preferable, and a methoxymethyl group is particularly preferable because of easy availability. A polymer compound containing a hexafluoroisopropanol group (a polymer compound represented by the general formula (2) or (6), wherein R ³ is hydrogen) was treated with sodium hydride or calcium hydride or the like. Then, the polymer compound protected by the target methoxymethyl group can be obtained by making it react with methoxymethyl chloride.

Examples of the silyl group (L-3) represented by SiR ^3C R ^3D R ^3E — include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, and a methyldi-i. -Propylsilyl group, tri-i-propylsilyl group, tert-butyldimethylsilyl group, methyldi-tert-butylsilyl group, tri-tert-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group or triphenylsilyl group Can be mentioned. Among these, a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, and a methyldi-tert-butylsilyl group are preferable, and a trimethylsilyl group is particularly preferable because of its availability. A polymer compound containing a hexafluoroisopropanol group (a polymer compound represented by general formula (2) or general formula (6) and R ³ is hydrogen) is trimethylsilylated in the presence of an organic base such as pyridine or triethylamine. By reacting with chloride, the target polymer compound protected with a trimethylsilyl group can be obtained.

As the acyl group (L-4) represented by R ^3A —C (═O) —, an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a laurylyl group, Myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioroyl group, methacryloyl group, crotonoyl group, oleoyl Group, maleoyl group, fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, Yl group, and a nicotinoyl group or an isonicotinoyl group. Further, those in which part or all of the hydrogen atoms of these thermally labile protecting groups are substituted with fluorine atoms can also be used. Among these, an acetyl group, a pivaloyl group, a benzoyl group, and a naphthoyl group are preferable, and an acetyl group and a benzoyl group are particularly preferable because of easy availability. A polymer compound containing a hexafluoroisopropanol group (a polymer compound represented by general formula (2) or general formula (6), wherein R ³ is hydrogen) is dehydrated in the presence of an organic base such as pyridine or triethylamine. By reacting with acetic acid and benzoic anhydride, the target polymer compound protected with an acetyl group or benzoyl group can be obtained.

2-3. Examples of the above-mentioned fluorine-containing compounds Specific examples of the fluorine-containing compounds represented by the general formula (2A) include the following.

Specific examples of the fluorine-containing compound represented by the general formula (7A) include the following.

The following fluorine-containing compounds give a fluorine-containing polymer compound (A) represented by the general formula (1) by performing a condensation polymerization reaction.

Among the above fluorine-containing compounds, it is preferable that the synthesis is easy, and that the hexafluoroisopropanol group is bifunctional as a raw material for the polymer, and the following structural formula is used as the raw material monomer for the fluorine-containing polymer compound (A). The fluorine-containing compounds (9A) to (11A) are preferably used.

2-4. Synthesis of fluorinated compound Fluorinated compound represented by the general formula (1A), HO—R ¹ —OH (wherein R ¹ is a divalent organic group containing 1 to 4 hexafluoroisopropanol groups) 1A) is a reaction of HO—R ^1X —OH (wherein R ^1X is a divalent organic group not containing a hexafluoroisopropanol group) and hexafluoroacetone or hexafluoroacetone trihydrate. Obtained by.

When hexafluoroacetone is used, hexafluoroacetone is subjected to an addition reaction with HO—R ^1X —OH (not containing a hexafluoroisopropanol group, the same shall apply hereinafter). Since the boiling point of hexafluoroacetone is −28 ° C., in order to keep hexafluoroacetone in the reaction system, it is preferable to use a cooling device or a sealed reactor, and it is particularly preferable to use a sealed reactor.

When hexafluoroacetone trihydrate is used, HO—R ^1X —OH and hexafluoroacetone trihydrate are mixed and reacted. Since the boiling point of hexafluoroacetone trihydrate is 105 ° C., it is easier to handle than hexafluoroacetone. At this time, as the reaction apparatus, a sealed container may be used, but by cooling with water using a reflux condenser,
The amount of hexafluoroacetone or hexafluoroacetone trihydrate used in this reaction is preferably 2.0 molar equivalents or more and 8.0 molar equivalents or less with respect to HO—R ^1X —OH, preferably 2. It is 2 molar equivalents or more and 3.0 molar equivalents or less. If the amount is less than 2.0 molar equivalents, the yield of the fluorine-containing compound is low, and the reaction proceeds even when used in excess of 8.0 molar equivalents, but it is not necessary to use more than 8.0 molar equivalents.

  This reaction can be carried out in a temperature range of 50 ° C. or higher and 200 ° C. or lower, but is preferably 120 ° C. or higher and 130 ° C. or lower. The reaction hardly proceeds at a temperature lower than 50 ° C., and the temperature of the fluorine-containing compound decreases at a temperature higher than 200 ° C., particularly 250 ° C. or higher.

  Although this reaction proceeds without using a catalyst, the reaction can be promoted by using an acid catalyst. Examples of the acid catalyst used include aluminum chloride which is Lewis acid, iron (III) chloride or boron fluoride, benzenesulfonic acid which is an organic sulfonic acid, camphorsulfonic acid (CSA), methanesulfonic acid, p-toluenesulfonic acid. (PTsOH), p-toluenesulfonic acid (pTsOH) monohydrate or pyridinium p-toluenesulfonic acid (PPTS) are preferred, and among these, aluminum chloride, iron (III) chloride, methanesulfonic acid, p-toluenesulfone Acid (pTsOH) monohydrate is particularly preferred because it is readily available. The amount of the catalyst used is 1 mol% or more and 50 mol% or less with respect to 1 mol of 4,4′-biphenol, bis (4-hydroxyphenyl) ether or 1,5-dinaphthol, It is 3 mol% or more and 40 mol% or less. If it is less than 1 mol%, the yield of the fluorine-containing compound (1A) is low, and the reaction proceeds even if it is used in an amount of more than 50 mol%, but it is not necessary to add much.

  This reaction may be solventless or use a solvent. The solvent used is not particularly limited as long as it does not participate in the reaction, but aromatic hydrocarbons such as xylene, toluene, benzene, anisole, diphenyl ether, nitrobenzene or benzonitrile, chlorinated solvents such as chloroform and methylene chloride. Dichloroethane or dichlorobenzene or water is preferred. The amount of the solvent to be used is not particularly limited, but it is not preferable to use a large amount because the yield of the fluorine-containing compound (1A) per unit volume of the reactor decreases.

  In order to carry out this reaction using a sealed reactor (autoclave), the embodiment differs depending on whether hexafluoroacetone or hexafluoroacetone trihydrate is used. When hexafluoroacetone is used, it is preferable to first add the catalyst or solvent into the reactor, and then add hexafluoroacetone while heating the reactor so that the pressure does not exceed 0.5 MPa.

When hexafluoroacetone trihydrate is used, HO—R ^1X —OH and hexafluoroacetone trihydrate are first put in a reactor, and a catalyst or a solvent can be added to carry out the reaction.

  Although there is no special restriction | limiting in reaction time of this reaction, It selects suitably by temperature or the quantity of the catalyst to be used. Therefore, it is preferable to terminate the reaction after confirming that the raw material has been sufficiently consumed by general-purpose analysis means such as gas chromatography. After completion of the reaction, the fluorine-containing compound can be obtained by means such as extraction, distillation, and crystallization. If necessary, the fluorine-containing compound (1A) can be purified by column chromatography or recrystallization.

  For example, the fluorine-containing compound (9A) is obtained by reacting 4,4′-biphenol with hexafluoroacetone or hexafluoroacetone trihydrate, and the fluorine-containing compound (10A) is bis (4-hydroxy). Phenyl) ether is obtained by reacting hexafluoroacetone or hexafluoroacetone trihydrate. The fluorine-containing compound (11A) is obtained by reacting 1,5-dinaphthol with hexafluoroacetone or hexafluoroacetone trihydrate. Is obtained by reacting.

2-5. Dicarboxylic acids and derivatives thereof Dicarboxylic acid derivatives for obtaining a fluorine-containing polymer compound (A) by condensation polymerization with a fluorine-containing compound represented by HO—R ¹ —OH include the following general formulas (10) and (11) It is preferable to use a dicarboxylic acid represented by Dehydration, dealcoholization or dehalogenation of the phenolic hydroxyl group of the fluorine-containing compound represented by HO—R ¹ —OH and the carboxyl group obtained by removing the protective group from the carboxyl group or dicarboxylic acid derivative of the dicarboxylic acid A fluorine-containing polymer compound (A) is obtained by a condensation polymerization reaction involving hydrogen fluoride.

[Dicarboxylic acid represented by general formula (10) or derivative thereof]

(In the formula (10), R ² is a group containing at least one selected from the group consisting of an alkylene group, an arylene group and an alicyclic group, and may contain an oxygen atom, a sulfur atom or a nitrogen atom, A part of the hydrogen atoms contained in the group, arylene group or alicyclic group may be substituted with an alkyl group, a fluorine atom, a chlorine atom or a fluoroalkyl group, and R ⁵ each independently represents a hydrogen atom, a carbon number of 1 to 10 alkyl groups or phenyl groups having 6 to 10 carbon atoms.)
[Dicarboxylic acid derivative represented by general formula (11)]

(In the formula (5), R ² is a group containing at least one selected from the group consisting of an alkylene group, an arylene group and an alicyclic group, and may contain an oxygen atom, a sulfur atom or a nitrogen atom, an alkylene group, A part of hydrogen atoms contained in the arylene group or alicyclic group may be substituted with an alkyl group, a fluorine atom, a chlorine atom or a fluoroalkyl group, and X is independently chlorine, fluorine, bromine or iodine. )
The dicarboxylic acid represented by the general formula (10) or a derivative thereof, or the dicarboxylic acid derivative represented by the general formula (11) is exemplified below in the form of a dicarboxylic acid. As the carboxylic acid as a raw material for the dicarboxylic acid derivative represented by the general formula (10) or the general formula (11), either an aliphatic carboxylic acid or an aromatic carboxylic acid may be used.

  Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid.

  Aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-dicarboxybiphenyl, 3,3′-dicarboxyldiphenyl ether, 3,4′-dicarboxyldiphenyl ether, 4,4′-dicarboxyl Diphenyl ether, 3,3′-dicarboxyldiphenylmethane, 3,4′-dicarboxyldiphenylmethane, 4,4′-dicarboxyldiphenylmethane, 3,3′-dicarboxyldiphenyldifluoromethane, 3,4′-dicarboxyldiphenyldifluoromethane 4,4′-dicarboxyldiphenyldifluoromethane, 3,3′-dicarboxyldiphenylsulfone, 3,4′-dicarboxyldiphenylsulfone, 4,4′-dicarboxyldiphenylsulfone, 3,3′-dicarboxyl Rudiphenyl sulfide, 3,4′-dicarboxyl diphenyl sulfide, 4,4′-dicarboxyl diphenyl sulfide, 3,3′-dicarboxyl diphenyl ketone, 3,4′-dicarboxyl diphenyl ketone, 4,4′-di Carboxyl diphenyl ketone, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (3,4'-dicarboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 2,2 -Bis (3-carboxyphenyl) hexafluoropropane, 2,2-bis (3,4'-dicarboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 1,3- Bis (3-carboxyphenoxy) benzene, 1,4-bis (3-carboxyl) Phenoxy) benzene, 1,4-bis (4-carboxyphenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 3,4 ′-(1,4- Phenylenebis (1-methylethylidene)) bisbenzoic acid, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 2,2-bis (4- (3-carboxyphenoxy) Phenyl) propane, 2,2-bis (4- (4-carboxyphenoxy) phenyl) propane, 2,2-bis (4- (3-carboxyphenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-Carboxyphenoxy) phenyl) hexafluoropropane, bis (4- (3-carboxyphenoxy) phenyl) sulfide, bis (4- (4-cal Boxyphenoxy) phenyl) sulfide, bis (4- (3-carboxyphenoxy) phenyl) sulfone, bis (4- (4-carboxyphenoxy) phenyl) sulfone, 5- (perfluorononenyloxy) isophthalic acid, perfluoro Nonyloxy group-containing 4- (perfluorononenyloxy) phthalic acid carboxylic acid may be mentioned. Further, 2- (perfluorononenyloxy) terephthalic acid or 4-methoxy-5- (perfluorononenyloxy) isophthalic acid can be mentioned. Also, perfluorohexenyloxy group-containing 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) phthalic acid, 2- (perfluorohexenyloxy) terephthalic acid, 4-methoxy-5- (per Fluorohexenyloxy) isophthalic acid. Above all, isophthalic acid, 4,4′-dicarboxybiphenyl, 2,2-bis (4-carboxyphenyl) hexafluoro, due to the availability, ease of polycondensation reaction, and excellent transparency of the polymer. Propane is preferred.

3. Production method of fluorine-containing polymer compound (A) As described above, a fluorine-containing compound represented by HO—R ¹ —OH and a dicarboxylic acid represented by HOOC—R ² —COOH or a derivative thereof undergo a polycondensation reaction. A fluorine-containing polymer compound (A) represented by the formula (1) is obtained.

  For example, the fluorine-containing polymer compound (A) is obtained by polycondensation of the fluorine-containing compound described in 2-1 to 2-4 and the dicarboxylic acid described in 2-5 or a derivative thereof. The above fluorine-containing compound and dicarboxylic acid or a derivative thereof are subjected to a polycondensation reaction under predetermined reaction conditions. At that time, if necessary, the hydrogen atom of the hexafluoroisopropanol group is protected by substitution reaction, and the inventions 1 to 8 The fluorine-containing polymer compound (A) contained in the photosensitive resin composition is obtained.

  The method and conditions for this condensation polymerization reaction are not particularly limited. For example, a composition comprising the fluorine-containing compound described in 2-1 to 2-4 and a dicarboxylic acid represented by the general formula (10) or a derivative thereof or a dicarboxylic acid derivative represented by the general formula (11), A method of melting each other at 150 ° C. or higher and performing a polycondensation reaction without solvent, a method of causing a polycondensation reaction in an organic solvent, preferably 150 ° C. or higher, a polycondensation in an organic solvent at a temperature of −20 to 80 ° C. The method of making it react is mentioned.

  The organic solvent which can be used is not particularly limited as long as both components of the raw material are dissolved, but N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide or hexamethylphosphoric triamide which are amide solvents N-methyl-2-pyrrolidone as an aromatic solvent, benzene, anisole, diphenyl ether, nitrobenzene or benzonitrile, chloroform, dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetra as halogen solvents. Examples include chloroethane, lactone solvents γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone. These organic solvents may be used alone or as a mixture of two or more. It is effective to carry out the reaction in the presence of an acid acceptor such as pyridine or triethylamine together with such an organic solvent.

  In addition to the above-mentioned fluorine-containing compound and dicarboxylic acid or derivative thereof, other diol compounds may be added to obtain a desired heat resistance or solvent solubility as a copolymer component.

  Examples of the diol compound to be added include 1,4-cyclohexanediol, 1,3-adamantanediol, catechol, 1,3-benzenediol, 1,4-benzenediol, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxy. Biphenyl, 2,2'-methylenediphenol, 4,4'-methylenediphenol, ethylene glycol, propylene glycol, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (4-hydroxyphenyl) ) -3-methylpropane, 2,2-bis (4-hydroxyphenyl) -butane, 3,3-bis (4-hydroxyphenyl) -pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 3,3-bis (4-hydroxyphenyl) -hexane, 2,2-bis (3- Rolo-4-hydroxyphenyl) -propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis (3-bromo-4-hydroxyphenyl) -propane, 2, 2-bis (3,5-dibromo-4-hydroxyphenyl) -propane, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis (4-hydroxyphenyl) -1, 1,1,3,3,3-hexafluoropropane, 2,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2 , 3-dihydroxypyridine, 2,4-dihydroxypyridine, 4,4′-dihydroxydiphenyl ether, 4,4′-di Mud carboxymethyl diphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, may be mentioned 4,4'-dihydroxydiphenyl sulfone or 4,4'-dihydroxybenzophenone.

4). Photosensitive resin composition As described above, the photosensitive resin composition of the present invention comprises:
Repeating unit represented by general formula (1)

(In the formula, R ¹ is a divalent organic group containing 1 to 4 hexafluoroisopropanol groups protected by a protecting group or not protected by a protecting group, and R ² is a divalent organic group. ))-Containing fluorine-containing polymer compound (A),
A photosensitive agent (B);
A polar solvent (C).

  The polar solvent (C) and the photosensitive agent (B) will be described below.

4-1. Polar solvent (C)
The polar solvent (C) used in the photosensitive resin composition of the present invention is only required to be able to dissolve the fluorine-containing polymer compound (A). Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, γ-butyrolactone , Methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide or N-methylpyrrolidone. Among them, it is preferable to use propylene glycol monomethyl ether acetate, cyclohexanone or γ-butyrolactone widely used as a coating solvent because of good solubility and coating property of the fluorine-containing polymer compound (A).

  The polar solvent (C) may be used alone or in combination of two or more. Moreover, the compounding quantity becomes like this. Preferably it is 100-2000 mass parts with respect to 100 mass parts of fluorine-containing polymer compounds (A), More preferably, it is 200-900 mass parts. That is, it is expressed by mass ratio: fluorinated polymer compound (A): polar solvent (C) = 1: 1 to 20, more preferably 1: 2 to 9. When the polar solvent (C) is less than 1, if the concentration of the solution (photosensitive resin composition) is small with a small amount of the fluorine-containing polymer compound (A), the viscosity becomes high and film formation is difficult. The resin composition is too thin to form a pattern.

4-2. Photosensitizer (B)
In the present invention, the fluorine-containing polymer compound (A) is dissolved in the polar solvent (C), and the photosensitizer (B) is, for example, a photoacid generator that generates acid by the action of high energy rays, or by exposure. A photosensitive resin composition is obtained by adding a diazoquinone photosensitizer as a diazonaphthoquinone compound that generates indenecarboxylic acid.

  The photosensitizer (B) used in the photosensitive resin composition of the present invention includes a photoacid generator that generates acid by the action of high energy rays, or a diazonaphthoquinone compound having a diazonaphthoquinone structure that generates indenecarboxylic acid upon exposure. A photosensitive agent (B) can be used. The photoacid generator is not particularly limited, and any photoacid generator can be selected from those used as an acid generator for chemically amplified resists. Examples of such acid generators include onium sulfonates such as iodonium sulfonate and sulfonium sulfonate, sulfonate esters, N-imido sulfonate, N-oxime sulfonate, o-nitrobenzyl sulfonate, or pyrogallol trismethane sulfonate. it can.

  Specifically, triphenylsulfonium trifluoromethanesulfonate, manufactured by BASF, USA, trade name, Irgacure PAG121, Irgacure PAG103, Irgacure CGI1380, Irgacure CGI725, product name, PAI-101, PAI-106, NAI-105, NAI-106, TAZ-110, TAZ-204, manufactured by San Apro Co., Ltd., trade name, CPI-200K, CPI-210S, CPI-101A, CPI-110A, CPI-100P, CPI-110P, CPI- 100TF, HS-1, HS-1A, HS-1P, HS-1N, HS-1TF, HS-1NF, HS-1MS, HS-1CS, LW-S1, LW-S1NF, manufactured by Sanwa Chemical Co., Ltd. Name TFE- triazine, TME- triazine or MP- triazine.

  Acids generated by the action of light from these photoacid generators are alkane sulfonic acids, aryl sulfonic acids, partially or fully fluorinated aryl sulfonic acids, alkane sulfonic acids and the like. Photoacid generators that generate partially or fully fluorinated alkane sulfonic acids are particularly preferred because they have sufficient acid strength for protecting groups that are difficult to deprotect. Specific examples include triphenylsulfonium trifluoromethanesulfonate or triphenylsulfonium perfluoro-n-octanesulfonate.

  These photoacid generators may be used alone or in combination of two or more. Moreover, the compounding quantity becomes like this. Preferably it is 0.1-20 mass parts with respect to 100 mass parts of fluorine-containing polymer compounds (A), More preferably, it is 0.00 with respect to 100 mass parts of fluorine-containing polymer compounds (A). 5 to 10 parts by mass. If it is less than 0.1, the generation of acid is too little and it is difficult to form a pattern at the time of development. If it is more than 20, the generation of acid is too much and it is difficult to form a pattern.

In addition to the photoacid generator, a photosensitizer (B) as a diazonaphthoquinone photosensitizer, which is a diazonaphthoquinone compound having a diazonaphthoquinone structure, can also be used. In pattern formation using the photosensitive agent (B), the hydroxyl group of the polymer compound having a hexafluoroisopropanol group and the diazo group (C = N ₂ ) of the photosensitive agent (B) form a hydrogen bond, The polymer compound having a hexafluoroisopropanol group becomes insoluble in the developer. On the other hand, in the photosensitizer (B), the diazonaphthoquinone structure disappears and an indenecarboxylic acid structure is formed by a photoreaction by irradiation with high energy rays. Therefore, it becomes insoluble in the unexposed area and soluble in the exposed area with respect to the developer, and pattern formation is possible. The photosensitizer (B) is a dissolution-inhibiting photosensitizer (B) and is generally applied to a photosensitive polyimide resin composition (see Patent Document 3 and Patent Document 4).

  Usually, a diazonaphthoquinone photosensitizer that is a diazonaphthoquinone compound having a diazonaphthoquinone structure is used as a naphthoquinone diazide sulfonate ester. This is obtained by a condensation reaction between a naphthoquinone diazide sulfonic acid chloride and a compound having a phenolic hydroxyl group. Examples of naphthoquinonediazidesulfonic acid constituting naphthoquinonediazidesulfonic acid chloride include 1,2-naphthoquinone-2-diazide-5-sulfonic acid and 1,2-naphthoquinone-2-diazide-4-sulfonic acid.

  Specific examples of the diazonaphthoquinone photosensitizer include 1,3-bis {3- [4- (1,2-naphthoquinone-2-diazido-4-sulfoxy) phenyl] ureidomethyl} benzene, 1- [4 -(1,2-naphthoquinone-2-diazido-4-sulfoxy) phenyl] -3-phenylurea, 1-benzyl-3- [4- (1,2-naphthoquinone-2-diazido-4-sulfoxy) phenyl] Urea compounds such as urea, 2-amino-4,6-bis (1,2-naphthoquinone-2-diazide-4-sulfoxy) pyrimidine, 4,4′-bis (1,2-naphthoquinone-2-diazide- 4-sulfonylamino) diaminodiphenyl ether, 4- (1,2-naphthoquinone-2-diazido-4-sulfonylamino) -1- (1,2-naphthoquinone-2-diazide-4-sulfonyloxy) benzene N-methyl-1,2-bis (1,2-naphthoquinone-2-diazido-4-sulfonylamino) ethane, 2- (1,2-naphthoquinone-2-diazide-4-sulfonylamino) -1- (1 1,2-naphthoquinone-2-diazido-4-sulfonyloxy) ethane, 1,3-bis {3- [4- (1,2-naphthoquinone-2-diazido-5-sulfoxy) phenyl] ureidomethyl} benzene, -[4- (1,2-naphthoquinone-2-diazide-5-sulfoxy) phenyl] -3-phenylurea, 1-benzyl-3- [4- (1,2-naphthoquinone-2-diazide-5-sulfoxy) ) Phenyl] urea, urea compounds such as 2-amino-4,6-bis (1,2-naphthoquinone-2-diazide-5-sulfoxy) pyrimidine, 4,4′-bis (1,2-naphthoquinone-2) -Diazide-5-sulfo Ruamino) diaminodiphenyl ether, 4- (1,2-naphthoquinone-2-diazido-5-sulfonylamino) -1- (1,2-naphthoquinone-2-diazido-5-sulfonyloxy) benzene, N-methyl-1, 2-bis (1,2-naphthoquinone-2-diazido-5-sulfonylamino) ethane, 2- (1,2-naphthoquinone-2-diazide-5-sulfonylamino) -1- (1,2-naphthoquinone-2) -Diazide-5-sulfonyloxy) ethane.

  These diazonaphthoquinone photosensitizers may be used alone or in combination of two or more. Moreover, the compounding quantity becomes like this. Preferably it is 5-40 mass parts with respect to 100 mass parts of fluorine-containing polymer compounds (A), More preferably, it is 10-30 masses with respect to 100 mass parts of fluorine-containing polymer compounds (A). Part. If it is less than 5 or more than 40, it is difficult to form a pattern.

4-3. Epoxy compound As a constituent of the photosensitive resin composition, an epoxy compound may be used for the purpose of improving transparency or heat resistance. It can be mixed with an epoxy compound and cured by heating or light irradiation to obtain a cured product.

  The epoxy compound contains a glycidyl group, may contain a carbon-carbon double bond, a carbon-carbon triple bond, an aromatic ring or a heterocyclic ring in the chemical structure, and part or all of the hydrogen atoms in the epoxy compound Each independently may be substituted with a fluorine atom, a chlorine atom, an alkyl group or a fluoroalkyl group.

  The epoxy compound may be a resin, and in that case, the number average molecular weight is preferably 10,000 or less.

  Examples of such epoxy compounds include resin phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol aralkyl. Resin, phenol trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin or aminotriazine-modified phenol resin compound, and epichlorohydride An epoxy compound modified with epoxy by bringing it into contact with phosphorus is exemplified.

  These are commercially available, trade name, manufactured by Dainippon Ink Industry Co., Ltd., bisphenol A type, trade name, Epicron 840, manufactured by Asahi Denka Kogyo Co., Ltd., trade name, Adeka Resin EP-4901, cresol novolac type Nippon Ink Industries Co., Ltd., trade name, Epicron N-600 series, dicyclopentadiene Dainippon Ink Industries, trade name, Epicron HP-7200 series, triazine Nissan Chemical Industries, trade name , TEPIC series and the like.

  You may use together an epoxy compound and the hardening | curing agent for epoxy resins. Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, mercaptan compounds, imidazole compounds, polysulfide resin compounds, and phosphorus compounds. Specifically, diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, triethylenetetramine, polyalkylene glycol polyamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Thermal curing of acid, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2-methylimidazole, triphenylphosphine, 2-ethyl-4-methylimidazole, BF3-amine complex, guanidine derivatives, etc. And UV curing agents such as diphenyliodonium hexafluorophosphate or triphenylsulfonium hexafluorophosphate.

  The content ratio of the fluorine-containing polymer compound (A) and the epoxy compound is represented by mass ratio, and the fluorine-containing polymer compound (A) epoxy compound is 10:90 to 90:10, preferably 30:70 to 70: 30 and more preferably 40:60 to 60:40.

  The content ratio of the epoxy compound and the epoxy resin curing agent is 70:30 to 99: 1, preferably 90:10 to 99:30, more preferably 40:60 to 60:40, expressed as a mass ratio. is there.

5. Pattern Forming Method The solution-like photosensitive resin composition is wet-formed on a substrate such as a glass substrate or a silicon substrate. For example, after the photosensitive resin composition is applied onto the substrate using a spin coater or the like, the polar solvent (C) is removed by pre-baking, that is, heating to include the fluorine-containing polymer compound (A). A coating film is obtained. This coating film is subjected to pattern exposure by lithography and then developed to obtain a positive type or negative type pattern. Specifically, by irradiating the coating film with high energy rays through a photomask on which a pattern is formed, generating an acid from the photoacid generator in the irradiated area, and proceeding with a chemical reaction involving the generated acid A positive type or negative type pattern is formed by changing the solubility of the coating film of the irradiated portion in the developer.

  Three methods for forming a positive pattern are illustrated. The first technique is achieved by using the epoxy resin curing agent. The photosensitive resin composition containing the epoxy resin curing agent is applied on a substrate and then pre-baked, whereby the hexafluoroisopropanol group and the epoxy compound react to insolubilize in the developer. Thereafter, high energy rays are irradiated, and the acid generated at the irradiated portion cleaves the ester bond of the main chain of the polymer compound, so that the carboxylic acid moiety and the phenol moiety are generated and solubilized in the developer. That is, a positive pattern is obtained.

  In the second method, the hexafluoroisopropanol group of the fluorine-containing polymer compound (A) is protected with a protective group such as a tert-butoxycarbonyl group or a methoxymethyl group, insolubilized in a developer, and then on the substrate. Form a coating film. The deprotection reaction occurs due to the action of the acid generated in the irradiated part, and the irradiated part is solubilized in the developer. That is, a positive pattern is obtained.

  In the third method, after a polymer compound containing a hexafluoroisopropanol group and the diazonaphthoquinone photosensitizer are mixed, a coating film is formed on a substrate. The irradiated portion is solubilized in the developer by the action of indenecarboxylic acid generated in the irradiated portion, and the unirradiated portion is insolubilized in the developer by the hydrogen bond between the diazo group and the hexafluoroisopropanol group. That is, a positive pattern is obtained.

  When a negative pattern is formed, the epoxy resin curing agent is not used, or an epoxy resin curing agent that does not react with the hexafluoroisopropanol group at the pre-baking temperature is used. When the photosensitive resin composition is used, the coating film remains soluble in the developer even after pre-baking, and the acid generated in the irradiated area serves as a catalyst to accelerate the reaction between the hexafluoroisopropanol group and the epoxy compound. Then, the irradiated part becomes insoluble in the developer. That is, a negative pattern is obtained.

  Thereafter, the positive pattern and the negative pattern are heated and fired to complete the reaction between the epoxy compound remaining in the pattern and the hexafluoroisopropanol group. As a temperature at the time of thermal firing, a general epoxy resin curing temperature of 180 ° C. or higher is preferable. In order to obtain a thin film having high hardness and high heat resistance, a high temperature is preferable, but the upper limit of temperature depends on a display manufacturing process or a semiconductor manufacturing process. For example, the upper limit of the heating temperature is 250 ° C. in the overcoat film forming process in a general liquid crystal display.

  Similarly, when a diazonaphthoquinone photosensitizer is used, heat treatment is performed at 250 ° C. after pattern formation, whereby indenecarboxylic acid or the photosensitizer is volatilized by thermal decomposition to obtain a final pattern.

  Examples of the developer used in the method for forming a positive pattern or a negative pattern using the photosensitive resin composition of the present invention include quaternary ammonium hydroxide aqueous solutions such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, ethanol There are amine-based aqueous solutions such as amine or propylamine. Among them, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide is most common.

  The high energy rays used in the method for forming a positive pattern or a negative pattern using the photosensitive resin composition of the present invention include an ultraviolet ray having a wavelength of the ultraviolet region or less, specifically, a wavelength of 400 nm or less, or an electron beam. Is mentioned. As ultraviolet light, ultraviolet light from a high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) or extreme ultraviolet An example is light (wavelength 13.5 nm).

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

  In the present invention, the photomask is a semiconductor circuit pattern or the like formed on a transparent substrate such as a glass substrate or a quartz substrate, and is developed by irradiating light through the photomask on which the semiconductor circuit pattern or the like is posted. It is a master used in a semiconductor manufacturing process by lithography, which is a transfer technique. The photosensitive resin is a resin that undergoes a chemical change by irradiation with high energy rays such as ultraviolet rays and changes the solubility or affinity for the solvent. The raw material monomer is a raw material compound used for polycondensation reaction to obtain a polymer compound, and the phenolic hydroxyl group is a hydroxyl group bonded to an aromatic ring.

  Although an Example is shown concretely, this invention is not limited to a following example.

A fluorine-containing compound containing a phenolic hydroxyl group and a hexafluoroisopropanol group was synthesized and subjected to condensation polymerization with a dicarboxylic acid derivative to obtain a polyarylate resin as a fluorine-containing polymer compound (A) (Synthesis Examples 1 to 7). Subsequently, it melt | dissolved in the polar solvent (C), the photosensitive agent (B) was added, and it was set as the photosensitive resin composition. The photosensitive resin composition was applied to a substrate, subjected to pattern exposure, then immersed in an alkaline developer and patterned to evaluate the patterns (Examples 1 to 17).

  Subsequently, a polyarylate resin containing two phenolic hydroxyl groups (carboxylic acid) and no hexafluoroisopropanol group was polymerized (Synthesis Examples 8 to 11). A photosensitizer (B) and a polar solvent were added to the polyarylate resin to obtain a photosensitive resin composition, which was subjected to exposure, development and heat treatment under the same conditions as in Examples 1 to 17, and the resulting patterns were evaluated. (Comparative Examples 1-4).

[Identification and property evaluation methods for compounds]
The identification method of the synthesized fluorine-containing compound and the physical property evaluation method of the polyarylate resin as the fluorine-containing polymer compound (A) are shown in the following (1) to (3).

(1) NMR (Nuclear Magnetic Resonance) Measurement Using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.) with a resonance frequency of 400 MHz, ¹ H-NMR and ¹⁹ F-NMR were measured.

(2) DI-MS (mass spectrometry spectrum) measurement A mass spectrometry spectrum was measured using a mass spectrometer (manufactured by JEOL Ltd., model number, JMS-T100GC).

(3) Molecular weight measurement Gel permeation chromatography (GPC) measurement using tetrahydrofuran (THF) as a solvent was performed, and the molecular weight was calculated in terms of polystyrene.

  The evaluation method after pattern formation using the photosensitive resin composition obtained from the polyarylate resin is shown in (4), and the used exposure machine is shown in (5).

(4) Patterning evaluation An optical microscope (model number MM-40) manufactured by Nikon Corporation was used.

(5) A mask aligner (model number MA6) manufactured by Exposure Machine Z-Microtech Co., Ltd. was used.

[Synthesis Example 1]
<Synthesis of fluorinated compound (B)>
As shown in the following reaction formula, 4,4′-biphenol (A) is reacted with hexafluoroacetone to give a fluorine-containing compound (B), that is, 3,3′-bis (1,1,1,3, 3,3-Hexafluoro-2-hydroxypropan-2-yl) -4,4′-biphenol was synthesized.

At room temperature (20 ° C.), 250 g of xylene was placed in a stainless steel autoclave, 100 g (0.54 mol) of 4,4′-biphenol (A) as a raw material was added, and further 1 g of CH ₃ SO ₃ H was added. . Next, after adding 196 g (1.18 mol) of hexafluoroacetone, the temperature was gradually raised and the reaction was continued for 8 hours with stirring at 110 ° C.

  The reaction product containing unreacted raw materials was filtered, and the filtration residue was dissolved in isopropyl ether and washed with water. The separated organic layer was dehydrated by adding anhydrous magnesium sulfate. Isopropyl ether was removed by distillation under reduced pressure, and hexane as a poor solvent was added to precipitate a fluorine-containing compound (B). Thus, the fluorine-containing compound (B) was obtained with a yield of 78%.

  The analysis results of the obtained fluorine-containing compound (B) are shown below.

¹ H-NMR (solvent, d-DMSO, TMS): δ10.8 (1H, s), 8.6 (1H, s), 7.7 (1H, s), 7.5 (1H, dd, J = 8.6 Hz), 7.0 (1H, d, J = 8.3 Hz)
¹⁹ F-NMR (solvent, d-DMSO, CCl ₃ F): δ-72.8 (12F, s)
DI-MS (FD +): m / z 518.06 (M +)
<Synthesis of fluorinated polymer compound (A) which is a polycondensate containing a repeating unit represented by Structural Formula (D)>
Next, in a reaction vessel equipped with a stirrer, the fluorine-containing compound (B), ie, 3,3′-bis (1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl ) -4,4′-biphenol (25.91 g, 0.05 mol) was prepared and dissolved in a mixed solvent of 167 g of N-methylpyrrolidone and 8.7 g of pyridine which had been dehydrated and purified in advance. Next, 10.15 g (0.05 mol) of isophthalic acid chloride was added, and the mixture was stirred at room temperature for 5 hours, and the polycondensation reaction shown below was performed to obtain a reaction solution.

  After completion of the reaction, the reaction solution was gradually poured into 1.5 kg of a 50% by weight aqueous methanol solution in a large beaker, which was a poor solvent, to precipitate a polymer. After filtering this polymer, it was dried under reduced pressure at a temperature of 100 ° C. for 8 hours in a vacuum dryer. The polymer was a polyarylate resin as a fluorine-containing polymer compound (A) which is a polycondensate containing a repeating unit represented by the structural formula (D), and was obtained in 27.5 g and a yield of 85%. . The weight average molecular weight (Mw) of the resin was 15,000, polydispersity, weight average molecular weight / number average molecular weight (Mw / Mn) = 2.1.

[Synthesis Example 2]
<Synthesis of fluorinated polymer compound (A), which is a copolycondensate containing repeating units represented by structural formulas (D) and (E)>
Fluorine-containing compound (B), that is, 3,3′-bis (1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl) -4,4′-biphenol 12.96 g (0.0250 mol) and 10.15 g (0) of isophthalic acid chloride in the same manner as in Synthesis Example 1 except that 8.40 g of 2,2-bis (4-hydroxyphenyl) -hexafluoropropane was used. 0.0500 mol), as shown in the following reaction formula, a polycondensate as a fluorine-containing polymer compound (A), which is a copolycondensate containing repeating units represented by structural formulas (D) and (E): An arylate resin of 22.8 g was obtained with a yield of 82%. The resin had a weight average molecular weight (Mw) of 13,000 and a polydispersity (Mw / Mn) = 2.5.

[Synthesis Example 3]
<Synthesis of fluorinated compound (F) and fluorinated compound (G)>
As shown in the following reaction formula, bis (4-hydroxyphenyl) ether and hexafluoroacetone were reacted to synthesize a fluorine-containing compound (F) and a fluorine-containing compound (G).

Under room temperature (20 ° C.), 150 g of xylene was put into a stainless steel autoclave, 25 g (0.16 mol) of bis (4-hydroxyphenyl) ether as a raw material was added, and 0.25 g of CH ₃ SO ₃ H was further added. Next, after adding 57 g (0.34 mol) of hexafluoroacetone, the temperature was gradually raised and the reaction was continued for 8 hours with stirring at 110 ° C.

  The reaction product containing the starting material in the reaction system was filtered, and the filter residue was dissolved in isopropyl ether and washed with water, and anhydrous magnesium sulfate was added to the separated organic layer for dehumidification. Distillation under reduced pressure was performed to distill off isopropyl ether, and hexane as a poor solvent was added to precipitate a fluorine-containing polymerizable monomer. From the results of DI-MS analysis, the obtained solid was obtained as a fluorine-containing polymerizable monomer (G) which is a monosubstituted product of a hexafluoroisopropanol group and a fluorine-containing polymerizable compound which is a disubstituted formula of a hexafluoroisopropanol group. It was a mixture of monomers (F), and the abundance ratio was F: G = 2: 3. The analysis results are shown below.

DI-MS (FD +): m / z 534.05 (M +), 368.51 (M +)
<Synthesis of Fluorine-Containing Polymer Compound (A) which is a Copolycondensation Product Containing Repeating Units Represented by Structural Formulas (H) and (I)>
Subsequently, in a reaction vessel equipped with a stirrer, a mixture of the fluorine-containing polymerizable monomers (F) and (G) (the abundance ratio is F: G = 2: 3 in molar ratio) 2.26 g (0 .0052 mol) was prepared and dissolved in a mixed solvent of 16 g of N-methylpyrrolidone and pyridine, 1.01 g, which had been purified by dehydration in advance. Next, 1.45 g (0.0052 mol) of 4,4′-biphenyldicarbonyl dichloride was added, and the mixture was stirred at room temperature for 5 hours, and the polycondensation reaction shown below was performed to obtain a reaction solution.

  After completion of the reaction, the same operation as in Synthesis Example 1 was performed, and a polyarylate resin as a fluoropolymer compound (A), which is a copolycondensate containing repeating units represented by structural formulas (H) and (I), 2.89 g was obtained with a yield of 87%.

[Synthesis Example 4]
<Synthesis of fluorinated compound (J)>
As shown in the following reaction formula, 1,5-naphthol was reacted with hexafluoroacetone to synthesize a fluorine-containing polyhydric phenol as the fluorine-containing compound (J).

Under room temperature (20 ° C.), 150 g of toluene was put in a stainless steel autoclave, 25 g (0.54 mol) of 1,5-naphthol as a raw material was added, and CH ₃ SO ₃ H and 0.25 g were further added. Next, 57 g (0.34 mol) of hexafluoroacetone was added, and the reaction was continued with stirring for 8 hours while the temperature was gradually raised and maintained at 100 ° C.

  The reaction product containing the starting material in the reaction system was filtered, and the filter residue was dissolved in isopropyl ether and washed with water, and anhydrous magnesium sulfate was added to the separated organic layer for dehumidification. Distilled under reduced pressure to distill off isopropyl ether, and hexane as a poor solvent was added to precipitate a fluorine-containing polyphenol having the structural formula (J). Thus, a fluorine-containing compound (J) having a structural formula was obtained in a yield of 76%.

  The analysis results of the fluorine-containing compound (J) product are shown below.

¹ H-NMR (solvent, d-DMSO, TMS) δ 10.4 (2H, br), 7.82 (2H, d, J = 9.2 Hz), 7.52 (2H, d, J = 8. (3Hz)
¹⁹ F-NMR (solvent, d-DMSO, CCl ₃ F) δ-73.7 (12F, s)
<Synthesis of fluorinated polymer compound (A) which is a polycondensate containing a repeating unit represented by Structural Formula (K)>
Next, in a reaction vessel equipped with a stirrer, the fluorine-containing compound (J), that is, 2,6-bis (1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl) -1,5-Dinaphthol, 1.97 g (0.004 mol), was prepared and dissolved in a mixed solvent of 12.9 g of N-methylpyrrolidone and 0.70 g of pyridine that had been dehydrated and purified in advance. Next, 0.81 g (0.004 mol) of isophthalic acid chloride was added and stirred at room temperature for 5 hours to carry out the polycondensation reaction shown below to obtain a reaction solution.

  After completion of the reaction, the reaction solution is added to a mixture of 100 mL of water and 100 mL of methanol, and the resulting precipitate is filtered off and dried under vacuum at room temperature (20 ° C.), whereby the repeating unit represented by the structural formula (K) 2.14 g of a polycondensate as a fluorine-containing polymer compound containing (A) was obtained in a yield of 86%. The resin had a weight average molecular weight (Mw) of 12000 and Mw / Mn = 2.2.

[Synthesis Example 5]
<Synthesis of fluorinated polymer compound (A) which is a copolycondensate containing repeating units represented by structural formulas (K) and (L)>
The fluorine-containing compound (J) used in Synthesis Example 4, that is, 2,6-bis (1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl) -1,5- Except that dinaphthol was added to 0.99 g (0.00200 mol) and 0.459 g (0.00200 mol) of bisphenol A was used, 0.81 g (0.004 mol) of isophthalic acid chloride was prepared in the same manner as in Synthesis Example 4. Mol) 1.71 g of a polyarylate resin as a fluorine-containing polymer compound (A) which is a copolycondensate containing repeating units represented by structural formulas (K) and (L) was obtained at a rate of 87%. The weight average molecular weight (Mw) of the resin was 14000 and Mw / Mn = 2.7.

[Synthesis Example 6]
<Synthesis of fluorinated polymer compound (A) which is a polycondensate containing a repeating unit represented by Structural Formula (M)>
In a reaction vessel equipped with a stirrer, 3.00 g of the polyarylate resin obtained in Synthesis Example 1, 1.01 g (0.0046 mol) of tertiary butoxycarboxylic acid anhydride, and 0.39 g (0.005 mol) of pyridine. , 6 g of N-methylpyrrolidone was added, and the mixture was stirred at room temperature for 5 hours, and the polycondensation reaction shown below was performed to obtain a reaction solution.

  After completion of the reaction, the reaction solution is added to a mixed solution of 100 mL of water and 100 mL of methanol, and the resulting precipitate is filtered off and dried at room temperature under vacuum, whereby a part of the hexafluoroisopropanol group is a tertiary butoxycarbonyl group. As a polymer containing the substituted repeating unit of the structural formula (M), 3.04 g of a fluorine-containing polymer compound (A) was obtained with a yield of 90%. Mw of the resin was 18000 and Mw / Mn = 2.8.

[Synthesis Example 7]
<Synthesis of fluorinated polymer compound (A) which is a polycondensate containing a repeating unit represented by Structural Formula (N)>
In a reaction vessel equipped with a stirrer, 2.89 g of the polyarylate resin obtained in Synthesis Example 4, 0.066 g of sodium hydride (40% by mass of mineral oil), 0.37 g of methoxymethyl chloride (0.0046 mol) ), 0.39 g (0.005 mol) of pyridine and 6 g of tetrahydrofuran were added, and the mixture was stirred for 5 hours in an ice bath, and the polycondensation reaction shown below was performed to obtain a reaction solution.

  After completion of the reaction, the reaction solution is added to a mixed solution of 100 mL of water and 100 mL of methanol, and the resulting precipitate is filtered off and dried at room temperature under vacuum, whereby a part of the hexafluoroisopropanol group is replaced with a methoxymethyl group. 2.50 g (yield 82%) of a polymer containing the repeating unit of the structural formula (N) was obtained. Mw of the resin was 14000 and Mw / Mn = 2.6.

Examples 1-17
Next, as shown in Table 1, to each polyarylate resin obtained in Synthesis Examples 1 to 7 as the fluorine-containing polymer compound (A), a photosensitive agent (B), an epoxy compound, and a polar solvent (C) are added. In addition, a photosensitive resin composition was obtained as a uniform solution.

The photosensitive resin compositions obtained in Examples 1 to 17 were applied to a silicon wafer having a diameter of 4 inches using a spin coater under the conditions of 1000 rpm and 50 sec. After coating, pre-baking at 80 ° C. for 3 minutes, and then using an exposure machine, contact exposure is performed for 1 minute through a 70 μm / 70 μm line and space mask, followed by heating at 110 ° C. for 3 minutes, and 2.38. Development was carried out by contact with a 1% by weight aqueous solution of tetramethylammonium hydride (TMAH) for 1 minute. After washing with water, heat treatment was performed at 180 ° C. for 3 minutes to obtain a pattern. The evaluation results of the pattern are shown in Table 2. In any case, the resist pattern collapse (pattern collapse) and the pattern shape change due to swelling were not observed, and a good pattern was obtained.

Next, as shown in Synthesis Examples 8 to 11 below, fluorinated polymer compounds containing carboxylic acids but not containing hexafluoroisopropanol groups were synthesized.

[Synthesis Example 8]
<Synthesis of Allylate Resin Containing Repeating Unit Represented by Structural Formula (O)>
In a reaction vessel equipped with a stirring device, 3.00 g (0.016 mol) of 4,4′-biphenol, 3.514 g (0.016 mol) of pyromellitic anhydride, 2.78 g (0.035 mol) of pyridine. ), 26 g of N-methylpyrrolidone was added, and the mixture was stirred at room temperature for 5 hours and subjected to the polycondensation reaction shown below to obtain a reaction solution.

  After completion of the reaction, the reaction solution is added to 200 mL of methanol, and the resulting precipitate is filtered off and then dried under reduced pressure at room temperature (20 ° C.) in a vacuum dryer to obtain a polyarylate containing a repeating unit of the structural formula (O). 6.30 g of resin was obtained with a yield of 97%. Mw of the resin was 14000 and Mw / Mn = 2.6.

[Synthesis Example 9]
<Synthesis of Allylate Resin Containing Repeating Unit Represented by Structural Formula (P)>
In a reaction vessel equipped with a stirrer, 3.00 g of a polyarylate resin containing a repeating unit of the structural formula (O), 2.26 g (0.0103 mol) of tertiary butoxycarboxylic acid anhydride, 0.88 g of pyridine (0. 0113 mol) and 10 g of N-methylpyrrolidone were added and stirred at 80 ° C. for 5 hours, and the polycondensation reaction shown below was performed to obtain a reaction solution.

  After completion of the reaction, the reaction solution is added to a mixed solution of 100 mL of water and 100 mL of methanol, and the resulting precipitate is filtered off and dried under reduced pressure at room temperature (20 ° C.) in a vacuum dryer to obtain a hexafluoroisopropanol group. 3.41 g of a polyarylate resin containing a repeating unit of the structural formula (P) in which a part was substituted with a tertiary butoxycarbonyl group was obtained in a yield of 85%. Mw of the resin was 18000 and Mw / Mn = 2.7.

[Synthesis Example 10]
<Synthesis of Allylate Resin Containing Repeating Unit Represented by Structural Formula (Q)>
In a reaction vessel equipped with a stirrer, 2.56-g (0.016 mol) of 1,5-dinaphthol, 3.514 g (0.016 mol) of pyromellitic anhydride, 2.78 g (0.035 mol) of pyridine, 26 g of N-methylpyrrolidone was added and stirred at room temperature for 5 hours, and the polycondensation reaction shown below was performed to obtain a reaction solution.

  After completion of the reaction, the reaction solution was added to 200 mL of methanol, and the resulting precipitate was filtered off and then dried under reduced pressure in a vacuum dryer at room temperature (20 ° C.) to obtain a polyarylate containing a repeating unit of the structural formula (Q). 5.46 g of resin was obtained with a yield of 90%. Mw of the resin was 13000 and Mw / Mn = 2.8.

[Synthesis Example 11]
<Synthesis of Allylate Resin Containing Repeating Unit Represented by Structural Formula (R)>
In a reaction vessel equipped with a stirrer, 3.00 g of a polyarylate resin containing a repeating unit of the structural formula (Q), 2.48 g (0.011 mol) of tertiary butoxycarboxylic acid anhydride, 0.96 g (0. 012 mol) and 10 g of N-methylpyrrolidone were added and stirred at 80 ° C. for 5 hours, and the polycondensation reaction shown below was performed to obtain a reaction solution.

  After completion of the reaction, the reaction solution was added to a mixed solution of 100 mL of water and 100 mL of methanol, and the resulting precipitate was filtered off and dried under reduced pressure in a vacuum dryer at room temperature (20 ° C.) to obtain a fluorine-containing polymer compound (A ), 3.34 g of a polymer containing a repeating unit of the structural formula (R) in which a part of the hexafluoroisopropanol group was substituted with a tertiary butoxycarbonyl group was obtained in a yield of 83%. Mw of the resin was 17000 and Mw / Mn = 2.6.

Comparative Examples 1-4
Next, as shown in Table 3, each of the polyarylate resin obtained in Synthesis Examples 8 to 11, which is a fluorine-containing polymer compound containing a carboxylic acid but not containing a hexafluoroisopropanol group, is combined with a photosensitive agent and a polar solvent. Was added to obtain a uniform solution to obtain a photosensitive resin composition.

Table 4 shows the results of evaluating the patterns obtained by performing exposure, development and heat treatment under the same conditions as in Examples 1 to 17. In any case, no pattern collapse was observed, but obvious swelling was visually observed and the pattern shape was poor.

  As is clear when the results of Examples 1 to 17 and the results of Comparative Examples 1 to 4 are compared, since the polyarylate resin of the present invention does not contain a carboxyl group, the pattern does not swell and has a good pattern shape. I found it to give.

Claims (16)

Repeating unit represented by general formula (1)

(In the formula, R ¹ is a divalent organic group containing 1 to 4 hexafluoroisopropanol groups protected by a protecting group or not protected by a protecting group, and R ² is a divalent organic group. ))-Containing fluorine-containing polymer compound (A),
A photosensitive agent (B);
A photosensitive resin composition comprising a polar solvent (C). The photosensitive resin composition of Claim 1 whose R < ¹ > is group represented by General formula (2).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group, and R ⁴ represents a single bond, oxygen atom, sulfur atom, SO ₂ , CH ₂ , CO, C (CH ₃ ) ₂ , C (CH ₃ ). _{(CH 2 CH 3), C} (CF 3) 2, C (CH 3) (C 6 H 5), CH 2 -C 6 H 4 -CH 2 or benzene, biphenyl, naphthalene, hydrogen atom from cyclohexene or fluorene Is a divalent organic group from which two are separated, a and b are each independently an integer of 0 to 2, and 1 ≦ a + b ≦ 4. The photosensitive resin composition of Claim 1 or Claim 2 whose R < ¹ > is group represented by General formula (3).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group, and R ⁴ represents a single bond, an oxygen atom, a sulfur atom, SO ₂ , CH ₂ , CO, C (CH ₃ ) ₂ , C ( _{CH 3) (CH 2 CH 3} ), C (CF 3) 2, C (CH 3) (C 6 H 5), CH 2 -C 6 H 4 -CH 2 or benzene, biphenyl, naphthalene, cyclohexene or fluorene, This is a divalent organic group in which two hydrogen atoms have been removed from. The photosensitive resin composition of any one of Claim 1 thru | or 3 whose R < ¹ > is group represented by General formula (4).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group.) The photosensitive resin composition of any one of Claims 1 thru | or 3 whose R < ¹ > is group represented by General formula (5).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group.) The photosensitive resin composition of Claim 1 whose R < ¹ > is group represented by General formula (6).

(In the formula, R ³ is each independently a hydrogen atom or a protecting group, c and d are each independently an integer of 0 to 2, and c + d is 0 to 4. e is an integer of 0 to 3) F and g are each independently an integer of 0 to 2, and 1 ≦ f + g ≦ 4.
In the formula (6), the following formula:

The site represented by represents an aromatic ring, the carbon atom constituting the ring may be substituted with a heteroatom (nitrogen atom, oxygen atom or sulfur atom), and the hydrogen atom may be substituted with a substituent. The substituent may contain a nitrogen atom, an oxygen atom or a sulfur atom. ) The photosensitive resin composition of Claim 1 or Claim 6 whose R < ¹ > is group represented by General formula (7).

(In the formula, each R ³ is independently a hydrogen atom or a protecting group, and f and g are each independently an integer of 0 to 2, and 1 ≦ f + g ≦ 4.) The photosensitive resin composition of Claim 1, Claim 6, or Claim 7 whose R < ¹ > is group represented by General formula (8).

(In the formula, each R ³ independently represents a hydrogen atom or a protecting group.) Furthermore, the photosensitive resin composition of any one of Claim 1 thru | or 8 containing an epoxy compound. The epoxy compound may contain a glycidyl group, and may contain a carbon-carbon double bond, a carbon-carbon triple bond, an aromatic ring or a heterocyclic ring in the chemical structure, and part or all of the hydrogen atoms in the epoxy compound Are each independently an epoxy compound which may be substituted with a fluorine atom, a chlorine atom, an alkyl group or a fluoroalkyl group. Furthermore, the photosensitive resin composition of Claim 9 containing an epoxy resin hardening | curing agent. The photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) is a photoacid generator that generates an acid upon exposure. The photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) is a photoacid generator that generates sulfonic acid upon exposure. The photosensitive resin composition according to any one of claims 1 to 13, wherein the photosensitive agent (B) is a diazonaphthoquinone compound that generates indenecarboxylic acid upon exposure. The polar solvent (C) is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, γ-butyrolactone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide or N-methylpyrrolidone. The photosensitive resin composition of any one of Claims 1 thru | or 14 which is a polar solvent. A photosensitive resin film obtained by applying the photosensitive resin composition according to any one of claims 1 to 15 on a support substrate and volatilizing and drying the solvent, and a photosensitive resin film obtained after the drying step are used as a photomask. A pattern forming method comprising: exposing to a predetermined pattern shape via a contact; developing the exposed photosensitive resin film in contact with a developer; and heating the developed photosensitive resin film .