JP2009271442A - Photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition which is alkali-developable while containing a fluorine-containing polymer. <P>SOLUTION: The photosensitive composition comprises a polymer (A) using a compound represented by formula (I) as a constituent monomer, a photosensitive agent (B), a curing agent (C) and a solvent (D). In formula (I), R<SP>1</SP>-R<SP>3</SP>each denote H, F or an aliphatic hydrocarbon group; R<SP>4</SP>denotes a single bond or an alkylene group; R<SP>5</SP>denotes a single bond or an aliphatic hydrocarbon group; R<SP>6</SP>denotes a linear alkylene group; and R<SP>7</SP>denotes H or an aliphatic hydrocarbon group, provided that any one of R<SP>1</SP>-R<SP>7</SP>is F or a group substituted by F. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive composition useful for photolithography and the like.

  Polymers containing fluorine are known to exhibit excellent properties such as water repellency and oil repellency, and various fluorinated polymers and fluorinated monomers therefor have been studied. For example, Patent Document 1 discloses (a) a method of producing a fluorine-containing hydroxy unsaturated ester by reacting a fluorine-containing epoxide and vinyl carboxylic acid, and (a) that the fluorine-containing hydroxy unsaturated ester is easily polymerized. And (c) It is described that this polymer can impart water repellency and oil repellency to fiber products and the like. In Example 2 of Patent Document 1, a compound represented by the formula (a-1) is synthesized, and in Example 1, a compound represented by the formula (a-2) is synthesized.

Patent Document 1 only discloses that the polymer obtained from the fluorine-containing hydroxy unsaturated ester exhibits water repellency and oil repellency, and does not disclose any other characteristics of the polymer.
Japanese Patent Publication No. 44-26286

Since the fluorine-containing polymer contains fluorine atoms, physical properties different from those of ordinary polymers (for example, high water repellency, high oil repellency, low contamination, high heat resistance, low refractive index, etc.) can be expected. Therefore, if the fluoropolymer can be used for photolithography, it becomes possible to provide a molded product having new characteristics. However, there are few fluorine-containing polymers that can be alkali-developed.
An object of the present invention is to provide a photosensitive composition (particularly a positive photosensitive composition) containing a novel fluoropolymer capable of alkali development.

  As a result of intensive studies by the present inventors in order to achieve the above object, it has been found that if a specific fluorine-containing polymer is used, alkali development is possible, and the present invention has been completed.

  The photosensitive composition of the present invention contains a polymer (A) having a compound represented by formula (I) as a constituent monomer, a photosensitive agent (B), a curing agent (C), and a solvent (D).

In formula (I), R ^{1 to} R ³ each independently represent a hydrogen atom, a fluorine atom, or a C _1-13 aliphatic hydrocarbon group which may be substituted with a fluorine atom or a hydroxyl group.
R ⁴ each independently represents a single bond or a C _1-10 alkylene group which may be substituted with a fluorine atom.
R ⁵ represents a single bond or a C _1-15 aliphatic hydrocarbon group which may be substituted with a fluorine atom.
R ⁶ represents a linear C _1-10 alkylene group which may be substituted with a fluorine atom.
R ⁷ represents a hydrogen atom, a C _1-24 aliphatic hydrocarbon group which may be substituted with a fluorine atom or a hydroxyl group, or a C _1-24 aliphatic hydrocarbon in which a part of a methylene unit is replaced with an oxygen atom. Indicates a group.
However, any one of R ^{1 to} R ⁷ is a fluorine atom or a group substituted with a fluorine atom.
In the present specification, “C _ab ” indicates that the carbon number is a to b.

In the compound represented by formula (I), (1) R ⁶ is preferably a linear C _1-10 alkylene group substituted with a fluorine atom, and (2) R ⁷ is preferably a hydrogen atom. .
Hereinafter, the compound represented by the formula (I) may be abbreviated as “compound (I)”. The same applies to compounds represented by other chemical formulas.

  The photosensitizer (B) is usually used as long as it is used for a positive photosensitive composition, and is preferably a quinonediazide compound. The curing agent (C) is preferably a melamine compound.

  The photosensitive composition of the present invention can be alkali-developed despite containing the fluoropolymer. Moreover, the coating film obtained from this composition shows a low refractive index.

The photosensitive composition of the present invention comprises a polymer (A) having a compound represented by formula (I) as a constituent monomer, a photosensitive agent (B), a curing agent (C) and a solvent (D) ( In formula (I), any one of R ^{1 to} R ⁷ is a fluorine atom or a group substituted by a fluorine atom.) The polymer (A), the photosensitive agent (B), and the curing agent (C) may be dissolved in the solvent (D) or may be dispersed. Hereinafter, each component will be described in order.

<Polymer (A)>
First, the compound (I) which is a constituent monomer of the polymer (A) will be described in detail.
In formula (I), R ^{1 to} R ³ each independently represent a hydrogen atom, a fluorine atom, or a C _1-13 aliphatic hydrocarbon group which may be substituted with a fluorine atom or a hydroxyl group. Examples of the C _1-13 aliphatic hydrocarbon group which may be substituted with a fluorine atom or a hydroxyl group include the following groups (1) to (4).

(1) Alkyl groups (including linear, branched and cyclic alkyl groups)
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group , N-nonyl group, n-decyl group, cyclohexyl group, (cyclohexyl) methyl group.

(2) Perfluorinated hydrocarbon group The perfluorinated hydrocarbon group includes the following groups (i) to (iii).

(I) Perfluoro linear alkyl group For example, trifluoromethyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro-n-pentyl group, perfluoro-n -Hexyl group, perfluoro-n-heptyl group, perfluoro-n-octyl group, perfluoro-n-nonyl group, perfluoro-n-decyl group.

(Ii) Perfluoro branched alkyl group For example, perfluoro-1-methylethyl group, perfluoro-2-methylpropyl group, perfluoro-3-methylbutyl group, perfluoro-4-methylpentyl group, perfluoro- 5-methylhexyl group, perfluoro-6-methylheptyl group, perfluoro-7-methyloctyl group, perfluoro-8-methylnonyl group, perfluoro-9-methyldecyl group.

(Iii) Perfluoro cyclic hydrocarbon group, for example, perfluoro monocyclic alkyl group such as perfluorocyclohexyl group; and perfluoro bridged cyclic hydrocarbon group such as 1-perfluoroadamantyl group and 2-perfluoroadamantyl group.

(3) Partially fluorine-substituted hydrocarbon group The partially fluorine-substituted hydrocarbon group includes the following groups (i) to (iv).

(I) Partially fluorine-substituted alkyl group such as a monofluoromethyl group and a difluoromethyl group.

(Ii) An alkyl group substituted with a perfluoro linear alkyl group (hereinafter abbreviated as “perfluoro linear alkyl substituted alkyl group”)
For example, (trifluoromethyl) methyl group, 2- (trifluoromethyl) ethyl group, (perfluoroethyl) methyl group, 2- (perfluoroethyl) ethyl group, (perfluoro-n-propyl) methyl group, 2- (Perfluoro-n-propyl) ethyl, (perfluoro-n-butyl) methyl, 2- (perfluoro-n-butyl) ethyl, (perfluoro-n-pentyl) methyl, 2- (perfluoro Fluoro-n-pentyl) ethyl group, (perfluoro-n-hexyl) methyl group, 2- (perfluoro-n-hexyl) ethyl group, (perfluoro-n-heptyl) methyl group, 2- (perfluoro- n-heptyl) ethyl group, (perfluoro-n-octyl) methyl group, 2- (perfluoro-n-octyl) ethyl group, (perfluoro-n-noni) ) Methyl, 2- (perfluoro -n- nonyl) ethyl group, (perfluoro--n- decyl) methyl, 2- (perfluoro -n- decyl) ethyl.

(Iii) An alkyl group substituted with a perfluoro branched chain alkyl group (hereinafter abbreviated as “perfluoro branched chain alkyl substituted alkyl group”)
For example, (perfluoro-1-methylethyl) methyl group, 2- (perfluoro-1-methylethyl) ethyl group, (perfluoro-2-methylpropyl) methyl group, 2- (perfluoro-2-methylpropyl) Ethyl group, (perfluoro-3-methylbutyl) methyl group, 2- (perfluoro-3-methylbutyl) ethyl group, (perfluoro-4-methylpentyl) methyl group, 2- (perfluoro-4-methylpentyl) Ethyl group, (perfluoro-5-methylhexyl) methyl group, 2- (perfluoro-5-methylhexyl) ethyl group, (perfluoro-6-methylheptyl) methyl group, 2- (perfluoro-6-methyl) Heptyl) ethyl group, (perfluoro-7-methyloctyl) methyl group, 2- (perfluoro-7-methyloctyl) ethyl , (Perfluoro-8-methylnonyl) methyl, 2- (perfluoro-8-methylnonyl) ethyl group, (perfluoro-9-methyldecyl) methyl group, 2- (perfluoro-9-methyldecyl) ethyl group.

(Iv) an alkyl group substituted with a perfluorocyclic hydrocarbon group, for example, an alkyl group substituted with a perfluorocyclic alkyl group such as (perfluorocyclohexyl) methyl group, 2- (perfluorocyclohexyl) ethyl group; and Perfluoro-bridged cyclic groups such as (1-perfluoroadamantyl) methyl group, 2- (1-perfluoroadamantyl) ethyl group, (2-perfluoroadamantyl) methyl group, 2- (2-perfluoroadamantyl) ethyl group An alkyl group substituted with a hydrocarbon group.

(4) Hydroxyl-substituted alkyl group For example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group 1-hydroxy-isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group .

R ^{1 to} R ³ are preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. More preferable R ¹ and R ² are a hydrogen atom, and more preferable R ³ is a hydrogen atom and a methyl group.

In formula (I), R ⁴ represents a single bond or a C _1-10 alkylene group which may be substituted with a fluorine atom. Examples of the C _1-10 alkylene group which may be substituted with a fluorine atom include the following groups (1) to (3).

(1) Alkylene group For example, methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n- Decylene group.

(2) Perfluoroalkylene group For example, difluoromethylene group, perfluoroethylene group, perfluoro-n-propylene group, perfluoro-n-butylene group, perfluoro-n-pentylene group, perfluoro-n-hexylene group, Perfluoro-n-heptylene group, perfluoro-n-octylene group, perfluoro-n-nonylene group, perfluoro-n-decylene group.

(3) Partially fluorine-substituted alkylene group For example, 2,2-difluoro-1,3-propylene group, 2,2,3,3-tetrafluoro-1,4-butylene group, 2,2,3,3,4, 4-hexafluoro-1,5-pentylene group, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene group, 2,2,3,3,4,4 , 5,5,6,6-decafluoro-1,7-heptylene group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8- Octylene group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1,9-nonylene group, 2,2,3,3 4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decylene group.

R ⁴ is preferably a single bond, a methylene group, an ethylene group or a propylene group. R ⁴ is more preferably a single bond.

In formula (I), R ⁵ represents a single bond or a C _1-15 aliphatic hydrocarbon group which may be substituted with a fluorine atom. Examples of the C _1-15 aliphatic hydrocarbon group which may be substituted with the fluorine atom of R ⁵ include the following groups (1) to (5).

(1) Chain hydrocarbon group For example, methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group Alkylene groups such as n-decylene group, 1,1-dimethylethylene group, 2-methyl-1,3-propylene group and methylideneethylene group; and alkenylene groups such as ethenylene group and propenylene group.

(2) a monocyclic hydrocarbon group, for example, a cycloalkylene group such as 1,2-cyclohexylene group; and a cycloalkenylene group such as 1,2-cyclohexenylene group.

(3) Divalent bridged cyclic hydrocarbon group Examples of the divalent bridged cyclic hydrocarbon group include, for example, norbornane, norbornene, adamantane, and tetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodeca-4-ene and the like, a group obtained by replacing two hydrogen atoms of a bridged cyclic hydrocarbon with a bond.

(4) Perfluoroalkylene group For example, difluoromethylene group, perfluoroethylene group, perfluoro-n-propylene group, perfluoro-n-butylene group, perfluoro-n-pentylene group, perfluoro-n-hexylene group, Perfluoro-n-heptylene group, perfluoro-n-octylene group, perfluoro-n-nonylene group, perfluoro-n-decylene group.

(5) Partially fluorine-substituted alkylene group For example, 2,2-difluoro-1,3-propylene group, 2,2,3,3-tetrafluoro-1,4-butylene group, 2,2,3,3,4, 4-hexafluoro-1,5-pentylene group, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene group, 2,2,3,3,4,4 , 5,5,6,6-decafluoro-1,7-heptylene group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8- Octylene group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1,9-nonylene group, 2,2,3,3 4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decylene group.

Preferred R ⁵ is a methylene group and an ethylene group.

In the formula (I), R ⁶ represents a linear C _1-10 alkylene group. This alkylene group may not be substituted with a fluorine atom, but is preferably substituted with a fluorine atom. In particular, an alkylene group that is partially fluorine-substituted is preferable, and a linear alkylene group in which carbons at both ends are unsubstituted and the other carbons are fully fluorine-substituted is more preferable. Examples of the linear C _1-10 alkylene group which may be substituted with a fluorine atom include the following groups (1) to (3).

(1) Alkylene group For example, methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n- Decylene group.
(2) Perfluoroalkylene group For example, difluoromethylene group, perfluoroethylene group, perfluoro-n-propylene group, perfluoro-n-butylene group, perfluoro-n-pentylene group, perfluoro-n-hexylene group, Perfluoro-n-heptylene group, perfluoro-n-octylene group, perfluoro-n-nonylene group, perfluoro-n-decylene group.
(3) Partially fluorine-substituted alkylene group For example, 2,2-difluoro-1,3-propylene group, 2,2,3,3-tetrafluoro-1,4-butylene group, 2,2,3,3,4, 4-hexafluoro-1,5-pentylene group, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene group, 2,2,3,3,4,4 , 5,5,6,6-decafluoro-1,7-heptylene group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8- Octylene group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1,9-nonylene group, 2,2,3,3 4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decylene group.

R ⁶ is preferably a fluorine-substituted linear C _1-10 alkylene group, more preferably a fluorine-substituted linear C _3-8 alkylene group, and even more preferably a partially fluorine-substituted A linear C _3-8 alkylene group. As particularly preferred R ⁶ , 2,2-difluoro-1,3-propylene group, 2,2,3,3-tetrafluoro-1,4-butylene group, 2,2,3,3,4,4-hexa Fluoro-1,5-pentylene group, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene group, 2,2,3,3,4,4,5, 5,6,6-decafluoro-1,7-heptylene group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octylene group Can be mentioned.

In the formula (I), R ⁷ is a hydrogen atom, a C _1-24 aliphatic hydrocarbon group which may be substituted with a fluorine atom or a hydroxyl group, or C _{1 in} which a part of a methylene unit is replaced with an oxygen atom. _{-24 represents an} aliphatic hydrocarbon group (such as a hydrocarbon group substituted with an alkoxy group). Examples of the hydrocarbon group that may be substituted with a fluorine atom, a hydroxyl group, an alkoxy group, and the like include the following groups (1) to (4).

(1) Hydrocarbon group not containing fluorine or hydroxyl group For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n- Alkyl groups such as hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group, (cyclohexyl) methyl group (linear, Branched and cyclic alkyl groups); and bridged cyclic hydrocarbon groups such as 1-adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group.

(2) Perfluorinated hydrocarbon group The perfluorinated hydrocarbon group includes the following groups (i) to (iii).

(I) Perfluoro linear alkyl group For example, trifluoromethyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro-n-pentyl group, perfluoro-n- Hexyl group, perfluoro-n-heptyl group, perfluoro-n-octyl group, perfluoro-n-nonyl group, perfluoro-n-decyl group, perfluoro-n-undecyl group, perfluoro-n-dodecyl group Perfluoro-n-tridecyl group, perfluoro-n-tetradecyl group, perfluoro-n-pentadecyl group, perfluoro-n-hexadecyl group, perfluoro-n-heptadecyl group, perfluoro-n-octadecyl group, perfluoro group Fluoro-n-nonadecyl group, perfluoro-n-eicosyl group, perfluoro-n-he Neicosyl group.

(Ii) Perfluoro branched alkyl group For example, perfluoro-1-methylethyl group, perfluoro-2-methylpropyl group, perfluoro-3-methylbutyl group, perfluoro-4-methylpentyl group, perfluoro- 5-methylhexyl group, perfluoro-6-methylheptyl group, perfluoro-7-methyloctyl group, perfluoro-8-methylnonyl group, perfluoro-9-methyldecyl group, perfluoro-10-methylundecyl group, Perfluoro-11-methyldodecyl group, perfluoro-12-methyltridecyl group, perfluoro-13-methyltetradecyl group, perfluoro-14-methylpentadecyl group, perfluoro-15-methylhexadecyl group, perfluoro group Fluoro-16-methylheptadecyl group, perfluoro-17 -Methyloctadecyl group, perfluoro-18-methylnonadecyl group, perfluoro-19-methyleicosyl group, perfluoro-20-methylheneicosyl group.

(Iii) Perfluoro cyclic hydrocarbon group, for example, perfluoro cyclic alkyl group such as perfluorocyclohexyl group; and perfluoro bridged cyclic hydrocarbon group such as 1-perfluoroadamantyl group and 2-perfluoroadamantyl group.

(3) Partially fluorine-substituted hydrocarbon group The partially fluorine-substituted hydrocarbon group includes the following groups (i) to (iv).

(I) Partially fluorine-substituted alkyl group such as a monofluoromethyl group and a difluoromethyl group.

(Ii) perfluoro linear alkyl-substituted alkyl group such as (trifluoromethyl) methyl group, 2- (trifluoromethyl) ethyl group, (perfluoroethyl) methyl group, 2- (perfluoroethyl) ethyl group, ( Perfluoro-n-propyl) methyl group, 2- (perfluoro-n-propyl) ethyl group, (perfluoro-n-butyl) methyl group, 2- (perfluoro-n-butyl) ethyl group, (perfluoro -N-pentyl) methyl group, 2- (perfluoro-n-pentyl) ethyl group, (perfluoro-n-hexyl) methyl group, 2- (perfluoro-n-hexyl) ethyl group, (perfluoro-n -Heptyl) methyl group, 2- (perfluoro-n-heptyl) ethyl group, (perfluoro-n-octyl) methyl group, 2- (perfluoro- n-octyl) ethyl group, (perfluoro-n-nonyl) methyl group, 2- (perfluoro-n-nonyl) ethyl group, (perfluoro-n-decyl) methyl group, 2- (perfluoro-n-) (Decyl) ethyl group, (perfluoro-n-undecyl) methyl group, 2- (perfluoro-n-undecyl) ethyl group, (perfluoro-n-dodecyl) methyl group, 2- (perfluoro-n-dodecyl) Ethyl group, (perfluoro-n-tridecyl) methyl group, 2- (perfluoro-n-tridecyl) ethyl group, (perfluoro-n-tetradecyl) methyl group, 2- (perfluoro-n-tetradecyl) ethyl group , (Perfluoro-n-pentadecyl) methyl group, 2- (perfluoro-n-pentadecyl) ethyl group, (perfluoro-n-hexadecyl) methyl Group, 2- (perfluoro-n-hexadecyl) ethyl group, (perfluoro-n-heptadecyl) methyl group, 2- (perfluoro-n-heptadecyl) ethyl group, (perfluoro-n-octadecyl) methyl group, 2- (perfluoro-n-octadecyl) ethyl group, (perfluoro-n-nonadecyl) methyl group, 2- (perfluoro-n-nonadecyl) ethyl group, (perfluoro-n-eicosyl) methyl group, 2- (Perfluoro-n-eicosyl) ethyl group, (perfluoro-n-heneicosyl) methyl group, 2- (perfluoro-n-heneicosyl) ethyl group.

(Iii) Perfluoro branched alkyl-substituted alkyl groups such as (perfluoro-1-methylethyl) methyl group, 2- (perfluoro-1-methylethyl) ethyl group, (perfluoro-2-methylpropyl) methyl group 2- (perfluoro-2-methylpropyl) ethyl group, (perfluoro-3-methylbutyl) methyl group, 2- (perfluoro-3-methylbutyl) ethyl group, (perfluoro-4-methylpentyl) methyl group 2- (perfluoro-4-methylpentyl) ethyl group, (perfluoro-5-methylhexyl) methyl group, 2- (perfluoro-5-methylhexyl) ethyl group, (perfluoro-6-methylheptyl) Methyl group, 2- (perfluoro-6-methylheptyl) ethyl group, (perfluoro-7-methyloctyl) methyl Group, 2- (perfluoro-7-methyloctyl) ethyl group, (perfluoro-8-methylnonyl) methyl group, 2- (perfluoro-8-methylnonyl) ethyl group, (perfluoro-9-methyldecyl) methyl Group, 2- (perfluoro-9-methyldecyl) ethyl group, (perfluoro-10-methylundecyl) methyl group, 2- (perfluoro-10-methylundecyl) ethyl group, (perfluoro-11-methyl) Dodecyl) methyl group, 2- (perfluoro-11-methyldodecyl) ethyl group, (perfluoro-12-methyltridecyl) methyl group, 2- (perfluoro-12-methyltridecyl) ethyl group, (perfluoro -13-methyltetradecyl) methyl group, 2- (perfluoro-13-methyltetradecyl) ethyl group, (perfur B-14-methylpentadecyl) methyl group, 2- (perfluoro-14-methylpentadecyl) ethyl group, (perfluoro-15-methylhexadecyl) methyl group, 2- (perfluoro-15-methylhexadecyl) ) Ethyl group, (perfluoro-16-methylheptadecyl) methyl group, 2- (perfluoro-16-methylheptadecyl) ethyl group, (perfluoro-17-methyloctadecyl) methyl group, 2- (perfluoro- 17-methyloctadecyl) ethyl group, (perfluoro-18-methylnonadecyl) methyl group, 2- (perfluoro-18-methylnonadecyl) ethyl group, (perfluoro-19-methyleicosyl) methyl group, 2- (perfluoro) -19-methyleicosyl) ethyl group, (perfluoro-20-methylhenei) Sill) methyl group, 2- (perfluoro-20-methyl-Heng eicosyl) ethyl.

(Iv) an alkyl group substituted with a perfluorocyclic hydrocarbon group, for example, an alkyl group substituted with a perfluorocyclic alkyl group such as (perfluorocyclohexyl) methyl group, 2- (perfluorocyclohexyl) ethyl group; and Perfluoro-bridged cyclic groups such as (1-perfluoroadamantyl) methyl group, 2- (1-perfluoroadamantyl) ethyl group, (2-perfluoroadamantyl) methyl group, 2- (2-perfluoroadamantyl) ethyl group An alkyl group substituted with a hydrocarbon group.

(4) Alkyl group substituted with a hydroxyl group or an alkoxy group, for example, 2-hydroxyethyl group, 2-hydroxypropyl group, methoxymethyl group, 2- (2-methoxyethoxy) ethyl group.

Preferred R ⁷ is a hydrogen atom, a methyl group, a tert-butyl group, and a 1-methyl-1-cyclohexyl group, a bridged cyclic hydrocarbon group, a perfluoro linear alkyl-substituted alkyl group, and a perfluoro branched chain alkyl substituted. It is an alkyl group. Preferred bridged cyclic hydrocarbon groups include a 1-adamantyl group, a 2-methyl-2-adamantyl group, and a 2-ethyl-2-adamantyl group. Preferred perfluoro linear alkyl-substituted alkyl groups include (trifluoromethyl) methyl group, (perfluoroethyl) methyl group, (perfluoropropyl) methyl group, (perfluorobutyl) methyl group, and (perfluoropentyl) methyl. Group, (perfluorohexyl) methyl group, (perfluoroheptyl) methyl group, (perfluorooctyl) methyl group, (perfluorononyl) methyl group, and (perfluorodecyl) methyl group. Preferred perfluoro branched alkyl-substituted alkyl groups include (perfluoro-1-methylethyl) methyl group, (perfluoro-2-methylpropyl) methyl group, (perfluoro-3-methylbutyl) methyl group, (perfluoro -4-methylpentyl) methyl group, (perfluoro-5-methylhexyl) methyl group, perfluoro-6-methylheptyl) methyl group, (perfluoro-7-methyloctyl) methyl group, (perfluoro-8- Examples include methylnonyl) methyl group, (perfluoro-9-methyldecyl) methyl group, and methoxymethyl group. R ⁷ is particularly preferably a hydrogen atom.

In formula (I), R ⁴ is preferably a single bond. In particular, (meth) acrylic acid ester in which R ¹ and R ² are hydrogen atoms, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a single bond is preferable as the compound (I). In addition, the description with "(meth) acrylic acid ester" in this specification means at least 1 sort (s) chosen from the group which consists of acrylic acid ester and methacrylic acid ester. The same applies to notations such as “(meth) acrylic acid”.

More preferable compounds (I) include methacrylic acid esters (R ³ = methyl group) represented by the chemical formulas of Groups 1 to 44. An acrylic ester in which R ³ is a hydrogen atom in the chemical formulas of Groups 1 to 44 is also a more preferable compound (I).

Compound (I) can be produced, for example, as follows.
First, the compound (dicarboxylic acid anhydride) or the compound (dicarboxylic acid) represented by the formula (Ic) is esterified using the compound (diol) represented by the formula (Ia). Thus, the compound represented by the formula (Id) (hydroxyl group-containing dicarboxylic acid monoester) can be produced.

In formulas (Ia) to (Id), R ⁵ and R ⁶ are the same as those in formula (I).

The compound (Id) is then used to esterify or transesterify the compound represented by formula (Ie) (carboxylic acid halide, carboxylic anhydride, carboxylic acid, or carboxylic acid ester). In I), a compound (carboxylic acid) in which R ⁷ is a hydrogen atom can be produced. Furthermore, various compounds (I) can be produced by esterifying the COOR ⁷ group (R ⁷ = H) of the compound (I).

In the formula (Ie), R ^{1 to} R ⁴ are the same as those in the formula (I), and R ⁸ is a halogen atom; an acyloxy group (R ⁹ COO—), a sulfonyloxy group (R ¹⁰ SO ₃ —); A hydroxyl group; or an alkoxy group (R ¹¹ O—) (wherein R ^{9 to} R ¹¹ each independently represents a hydrocarbon group). Preferable R ⁸ is chlorine atom; (meth) acryloyloxy group, acetyloxy group, trifluoroacetyloxy group, methylsulfonyloxy group and p-tolylsulfonyloxy group; hydroxyl group; and methoxy group, ethoxy group, propoxy group and butoxy Group;

  Examples of compound (Ia) include fluorine-containing diols. As fluorine-containing diols, (1) partially fluorine-substituted diols such as 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol and 2,2,3,3,4 , 4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol (these are available from Daikin Chemicals Sales); 2,2,3,3-tetrafluoro- 1,4-butanediol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, and 2,2,3,3,4,4,5,5,6,6, 7,7,8,8,9,9-hexadecafluoro-1,10-decanediol (these are available from Aldrich Chemical Company); and 2,2-difluoro-1,3-propanediol, 2 , 2,3,3,4,4,5,5,6,6-deca Luo-1,7-heptanediol, and 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1,9-nonanediol; and (2) perfluorinated diols such as difluoromethanediol, 1,2-perfluoroethanediol, 1,3-perfluoro-n-propanediol, 1,4-perfluoro-n-butanediol, 1,5 -Perfluoro-n-pentanediol, 1,6-perfluoro-n-hexanediol, 1,7-perfluoro-n-heptanediol, 1,8-perfluoro-n-octanediol, 1,9-per Fluoro-n-nonanediol, and 1,10-perfluoro-n-decanediol; and the like.

  Examples of the compound (Ib) include succinic anhydride, 2,2-dimethylsuccinic anhydride, glutaric anhydride, 3-methylglutaric anhydride, perfluoroglutaric anhydride, maleic anhydride, itaconic anhydride. 2,3-norbornane dicarboxylic acid anhydride, 2-norbornene-5,6-dicarboxylic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 1,2,5,6-tetrahydrophthalic acid anhydride, 3 , 4,5,6-tetrahydrophthalic anhydride and the like.

  Compound (Ic) includes saturated aliphatic dicarboxylic acid, unsaturated dicarboxylic acid, alicyclic dicarboxylic acid, bridged cyclic hydrocarbon dicarboxylic acid, and fluorine-containing saturated aliphatic dicarboxylic acid. Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and undecane. A diacid, dodecanedioic acid, etc. are mentioned. Examples of the unsaturated dicarboxylic acid include maleic acid and itaconic acid. Examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,2,5,6-tetrahydrophthalic acid, 3,4,5,6-tetrahydrophthalic acid, and the like. Examples of the bridged cyclic hydrocarbon dicarboxylic acid include 2,3-norbornane dicarboxylic acid and 2-norbornene-5,6-dicarboxylic acid. Examples of the fluorine-containing saturated aliphatic dicarboxylic acid include perfluorosuccinic acid, perfluoroglutaric acid, perfluoroadipic acid, perfluorosuberic acid, and perfluoroazeline acid. The fluorine-containing saturated aliphatic dicarboxylic acid can be obtained from, for example, Daikin Chemicals Sales Co., Ltd.

Compound (Ie) includes (1) carboxylic acid halide (R ⁸ = halogen atom), (2) carboxylic acid anhydride (R ⁸ = acyloxy group or sulfonyloxy group), (3) carboxylic acid (R ⁸ = Hydroxyl group) and (4) carboxylic acid ester (R ⁸ = alkoxy group). Examples of the carboxylic acid halide (Ie) include (meth) acryloyl chloride. Examples of the carboxylic acid (Ie) include (meth) acrylic acid. Examples of the carboxylic acid ester (Ie) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. As the carboxylic acid anhydride (Ie), a mixed acid anhydride (for example, acetic acid / (meth) acrylic acid anhydride, trihydric acid) composed of carboxylic acid (Ie) (R ⁸ = hydroxyl group) and other carboxylic acid or sulfonic acid. Fluoroacetic acid / (meth) acrylic anhydride, methanesulfonic acid / (meth) acrylic anhydride, and p-toluenesulfonic acid / (meth) acrylic anhydride) can also be used, but from the same carboxylic acid (Ie) It is preferable to use a symmetrical acid anhydride (for example, (meth) acrylic anhydride).

  The esterification reaction between compound (Ia) and compound (Ib) or compound (Ic) can be carried out under ordinary conditions known in the field of organic synthesis. The esterification reaction between compound (Ia) and compound (Ib) is carried out, for example, with stirring while refluxing in the presence of 4-dimethylaminopyridine and pyridine. This reaction mixture can be purified by, for example, a liquid separation operation using toluene and hydrochloric acid. The reaction between compound (Ia) and compound (Ic) is carried out, for example, with stirring while refluxing in the presence of concentrated sulfuric acid, magnesium sulfate and chloroform. This reaction mixture can be purified by a liquid separation operation using, for example, chloroform and a saturated aqueous sodium carbonate solution.

  The esterification reaction or transesterification reaction between compound (Id) and compound (Ie) can also be carried out under ordinary conditions known in the field of organic synthesis. The reaction between compound (Id) and compound (Ie) is, for example, (1) stirring at room temperature in the presence of THF; (2) stirring at reflux in the presence of 4-dimethylaminopyridine and pyridine; Or (3) stirring and refluxing in the presence of concentrated sulfuric acid, magnesium sulfate and chloroform. This reaction mixture can be purified by a liquid separation operation using, for example, toluene and hydrochloric acid.

  The polymer (A) has a structural unit represented by the formula (II) derived from the compound (I).

Descriptions and preferred specific examples of R ^{1 to} R ⁷ in formula (II) are the same as those in formula (I).

The polymer (A) is preferably a homopolymer of one compound (I), but may be a copolymer synthesized from two or more compounds (I), for example, R ⁷ is a hydrogen atom. And a copolymer of compound (I) and R ( ⁷ ) other than a hydrogen atom. The polymer (A) is a copolymer of one or more compounds (I) (particularly the compound (I) in which R ⁷ is a hydrogen atom) and one or more other monomers. May be. Examples of other monomers include (meth) acrylic acid esters other than compound (I).

  The polymer (A) can be produced by, for example, a known polymerization method (for example, bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization) using a radical polymerization initiator or a radical initiator. The reaction mode may be batch, semi-continuous or continuous. The reaction vessel is not particularly limited, and for example, a glass vessel or a stainless steel vessel can be used.

  The radical polymerization initiator is not particularly limited, and for example, azo compounds (for example, 2,2'-azobis (isobutyronitrile)), peroxide compounds, redox compounds, and the like can be used. As the polymerization temperature, a temperature suitable for the radical polymerization initiator to be used is employed.

  Examples of the solvent or dispersion medium for polymerization include ester solvents such as ethyl acetate and n-butyl acetate; ketone solvents such as acetone and methyl isobutyl ketone; aromatic solvents such as toluene; and hydrocarbon solvents such as cyclohexane. Solvents: Alcohol solvents such as isopropyl alcohol and ethylene glycol monomethyl ether. Water, chlorofluorocarbon solvents, ethers, cyclic ethers, fluorocarbons, perfluoroethers and the like can also be used. These solvents or dispersion media can be used alone or in combination of two or more.

  The number average molecular weight (Mn) of a polymer (A) is 2,000-100,000 normally in polystyrene conversion, Preferably it is 4,000-15,000, More preferably, it is 12,000-14,000. The dispersity (weight average molecular weight / number average molecular weight) is not particularly limited, but is usually 1.2 or more and 60 or less (preferably 30 or less, more preferably 10 or less).

<Photosensitive agent (B)>
As the photosensitive agent (B), those known in the field of photosensitive compositions can be used. A typical photosensitizer (B) is a quinonediazide compound (particularly a naphthoquinonediazide compound). Preferred naphthoquinone diazide compounds include o-naphthoquinone diazide sulfonic acid compounds (for example, o-naphthoquinone diazide-5-sulfonic acid, o-naphthoquinone diazide-4-sulfonic acid, etc.) and polyhydric phenols (preferably three phenolic hydroxyl groups). It is an ester with polyhydric phenol).

  Examples of the polyhydric phenol include (i) a compound in which a benzene ring having one or more hydroxyl groups (hereinafter abbreviated as “hydroxyl group-containing benzene ring”) is bonded via a carbonyl group, (ii) A compound in which a hydroxyl group-containing benzene ring is bonded via an alkylene group (preferably a methylene group), and (iii) a dihydropyran ring and a first hydrogen group-containing benzene ring are condensed, and the condensed dihydro A compound in which a second hydrogen group-containing benzene ring is bonded to the pyran ring portion is exemplified.

  Examples of the polyhydric phenol (i) include di, tri, tetra, or pentahydroxybenzophenone (preferably 2,3,4,4'-tetrahydroxybenzophenone and the like).

  Examples of the polyphenol of the above (ii) include compounds represented by the formulas (101) to (107).

  Examples of the polyphenol of (iii) include compounds represented by formulas (108) to (111).

  As the polyhydric phenol, those classified into the above (iii) are preferable, and among them, the compound (110) is more preferable.

<Curing agent (C)>
As a hardening | curing agent (C), the compound which has a thermosetting effect can be used, For example, a melamine compound is mentioned. A preferred melamine compound is represented by, for example, formula (III).

In formula (III), R ^{300 to} R ³⁰⁵ each independently represent a hydrogen atom, a linear C _1-12 alkyl group or a branched C _3-10 alkyl group. However, the total number of hydrogen atoms among R ^{300 to} R ³⁰⁵ is 4 or less.

Examples of the linear C _1-12 alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, An n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, and the like can be mentioned. A methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group are preferable. And a straight chain C _1-6 alkyl group such as a group.

Examples of the branched C _3-10 alkyl group include an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethyl-n-hexyl group, and preferably an isobutyl group, a sec-butyl group, Examples thereof include branched C _3-5 alkyl groups such as a tert-butyl group.

  Preferred examples of the melamine compound represented by the formula (III) include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine and the like. Hexamethoxymethyl melamine (also referred to as hexamethoxymethylol melamine) and hexaethoxymethyl melamine are more preferable.

  Further, the curing agent (C) is a guanamine compound such as tetramethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, tetrapropoxymethylbenzoguanamine, tetrabutoxymethylbenzoguanamine, and compounds represented by formulas (IV-1) to (IV-6) It may be.

<Contents of polymer (A), photosensitive agent (B) and curing agent (C)>
Content of polymer (A), photosensitive agent (B) and curing agent (C) in the photosensitive composition (based on a total of 100 parts by mass of the polymer (A), the photosensitive agent (B) and the curing agent (C) Amount) is as follows.
Polymer (A): Preferably about 30-70 mass parts, More preferably, about 40-60 mass parts.
Photosensitive agent (B): Preferably about 10-60 mass parts, More preferably, about 20-50 mass parts.
Curing agent (C): Preferably it is about 5-30 mass parts, More preferably, it is about 10-20 mass parts.

If the amount of the polymer (A) is within the above range, the solubility in the developer is sufficient, it is difficult to cause film loss in the development step, and the exposure amount when forming a pattern by photolithography is preferable. .
By making the amount of the photosensitive agent (B) within the above range, the film loss in the development process at the time of pattern formation can be reduced, and the exposure time for forming a pattern by photolithography can be shortened.
When the amount of the curing agent (C) is within the above range, the exposure amount when forming a pattern by photolithography can be reduced. Moreover, the shape of the pattern after development is good, and the mechanical strength of the pattern after heating and curing the pattern is sufficient.

<Solvent (D)>
The solvent (D) may be appropriately selected according to the solubility of the polymer (A), the photosensitive agent (B), and the curing agent (C) to be used, the applicability of the photosensitive composition, and the like.

  Examples of the solvent (D) include ethylene glycols (methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, etc.), propylene glycols (propylene glycol monomethyl ether). , Propylene glycol monomethyl ether acetate, etc.), N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, N, N-dimethylformamide, ketones (4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol), cyclohexanone Etc.), carboxylic acid esters (ethyl acetate, n-butyl acetate, ethyl pyruvate, ethyl lactate, n-butyl lactate, etc.).These solvents may be used alone or in combination of two or more.

  Content of a solvent (D) is about 40-95 mass% with respect to the whole photosensitive composition, Preferably it is about 70-90 mass%. If the amount of solvent is the said range, a photosensitive composition will show favorable applicability | paintability and a uniform coating film will be formed.

<Other additives (E)>
If necessary, the photosensitive composition of the present invention may further contain other additives (E) such as a surfactant.

  Surfactants include silicone surfactants [for example, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (above Toray Silicone Co., Ltd.) Manufactured), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (above made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (above GE Toshiba Silicone) Surfactants having a siloxane bond, etc.]; fluorine-based surfactants [for example, Florard FC430, FC431 (above Sumitomo 3M) Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183 (the above are manufactured by Dainippon Ink and Chemicals), Ftop EF301, EF303 EF351, EF352 (made by Shin-Akita Kasei Co., Ltd.), Surflon S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Laboratory) , BM-1000, BM-1100 (the above is a surfactant having a fluorocarbon chain, such as manufactured by BM Chemie), etc .; a silicone-based surfactant having a fluorine atom [Megafac R08, BL20, F475, F477] F443 (above, Dainippon Ink & Chemicals, Inc.) and other siloxane bonds and And the like having a fluorocarbon chain]. These surfactants can be used alone or in combination of two or more.

  When the surfactant is used, the amount used is, for example, about 0.0005 mass% to 0.6 mass%, preferably 0.001 mass% to 0.5 mass, when the entire photosensitive composition is 100 mass%. It is about mass%. When the amount of the surfactant used is within the above range, a flat coating film can be easily obtained by applying the photosensitive composition.

  Furthermore, the photosensitive composition of the present invention contains various additives or additive components (epoxy resins, oxetane compounds, ultraviolet absorbers, antioxidants, chelating agents, etc.) to the extent that the effects of the present invention are not impaired. May be. In addition, the photosensitive composition of the present invention may contain a functional substance according to the application. For example, when producing a color filter etc., the photosensitive composition of this invention may contain the pigment | dye, a pigment, etc.

The photosensitive composition of the present invention can be used in a wide range of fields utilizing photocuring action, and may be any of a stereolithography product and a resist film. It can be used for manufacturing plasma display panels. Furthermore, the present invention is not limited to development (patterning, etc.), and can be used for applications where development is not performed (for example, a protective film, a planarization film, etc.).
Hereinafter, the case of patterning by photolithography will be described in more detail.

<Patterning by photolithography>
When patterning the photosensitive composition of the present invention by photolithography, each component is mixed in a solvent, and then usually filtered through a filter having a pore size of about 0.2 μm or less to prepare the photosensitive composition of the present invention. It is preferable. By filtering, the uniformity when applying the photosensitive composition is improved.

When forming a pattern from the photosensitive composition of this invention by photolithography, it can process by the following processes, for example.
(1) The process of apply | coating a photosensitive composition on a support body (2) The process of removing a solvent (3) The process of exposing to the coating film obtained by application | coating through the mask pattern corresponding to a target pattern (4) ) Development step (5) Step of irradiating the obtained pattern with ultraviolet rays (6) Step of heating the pattern

  In applying the photosensitive composition, it is desirable to mix each component of the photosensitive composition in a solvent in advance and then filter with a filter having a pore size of about 0.2 μm or less. By filtering, the uniformity when applying the photosensitive composition is improved.

  The support on which the photosensitive composition is applied can be appropriately set depending on the application, for example, a silicon wafer on which an image sensor such as a solid coupled device such as a CCD or CMOS is formed, a transparent glass plate, a quartz wafer or the like. May be.

  The method for forming the coating film of the photosensitive composition on the support is not particularly limited, and spin coating, roll coating, bar coating, die coating, dip coating, casting coating, roll coating, slit & coating A normal coating method such as a spin coating method or a slit coating method can be appropriately employed.

  After apply | coating the photosensitive composition of this invention on a support body, a coating film can be formed by removing volatile components, such as a solvent, by heating (for example, 70-120 degreeC heating).

  When exposing a coating film, a light beam is irradiated to a coating film through the mask pattern corresponding to the target pattern. As the light beam, for example, g-line, h-line, i-line, and the like can be used, and an exposure machine such as a g-line stepper, h-line stepper, or i-line stepper may be used. The irradiation amount of light in the irradiation region is appropriately selected depending on the type and content of the polymer (A), the type and content of the photosensitive agent (B), and the like. Moreover, you may heat the coating film produced in this way. By heating, the coating film is cured by the action of the curing agent (C), and the mechanical strength of the coating film is improved. The heating temperature in the case of heating is, for example, about 80 to 150 ° C.

  The development may be performed by bringing the support provided with the coating film into contact with an ordinary developer. Although there is no restriction | limiting in particular as a developing solution, For example, alkaline aqueous solution (preferably tetramethylammonium hydroxide aqueous solution) etc. are used. A surfactant may be mixed in the developer as necessary. The pattern is formed by shaking off the developer and then washing with water to remove the developer. In some cases, the developer is shaken off, rinsed with a rinse solution, and then washed with water. This rinsing can remove the residue of the photosensitive composition remaining on the support during development. Thus, a pattern is formed from the coating film.

  The obtained pattern is irradiated with ultraviolet rays. The photosensitive component remaining in the pattern is decomposed by ultraviolet irradiation.

  The pattern is heated after the pattern is irradiated with ultraviolet light. This heating can improve the mechanical strength of the pattern. This heating temperature is usually about 100 to 220 ° C. When the heating temperature is within the above range, curing proceeds sufficiently.

  In addition, after apply | coating the photosensitive composition of this invention to a support body, you may thermoset without patterning. The coating film thus obtained has excellent characteristics (flattening characteristics) for eliminating a step on the coated surface, and can be used as a planarizing film or a protective film.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and appropriate modifications are made within a range that can meet the above and the following purposes. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
In Examples, “%” and “parts” representing the content or amount used represent “% by mass” and “parts by mass” unless otherwise specified.

Synthesis Example 1: Synthesis of Compound (I-1) Fluorine-containing diol (2,2,3,3,4,4,5,5-octafluoro-1,6-hexane represented by the formula (Ia-1) Diol, CAS No. 355-74-8, manufactured by Daikin Chemicals Sales Co., Ltd.) 10.0 g (38 mmol), succinic anhydride 3.8 g (38 mmol), 4-dimethylaminopyridine 0.47 g (3.8 mmol) ) And 50 g of pyridine were added, followed by stirring for 2.5 hours while refluxing. Thereafter, the reaction solution was cooled to room temperature, 100 mL of toluene was added, and the organic layer was washed twice with 50 mL of hydrochloric acid and twice with 50 mL of water. The organic layer was taken out, dried by adding magnesium sulfate, and filtered. Carbolafine was added to the filtrate, stirred at 60 ° C. for 1 hour, and filtered through celite. After the solvent of the filtrate was distilled off with a rotary evaporator, the filtrate was dried under reduced pressure at 60 ° C. to obtain 12.4 g of a fluorine-containing compound (fluorinated dicarboxylic acid monoester) represented by the formula (Id-1).

The structure of compound (Id-1) was identified by ¹ H-NMR (EX-270; manufactured by JEOL Ltd.).
¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ , room temperature): 2.4-2.7 (4H, m), 3.77 (2H, t, J = 15 Hz), 4.04 (2H, t, J = 15 Hz), 6.02 (1H, bs), 9.14 (1H, bs)

  Next, 5.3 g (34 mmol) of methacrylic anhydride, 0.42 g (3.4 mmol) of 4-dimethylaminopyridine, and 50 g of pyridine were added to 12.4 g (34 mmol) of compound (Id-1), followed by refluxing. The mixture was stirred for 2.5 hours. Thereafter, the reaction solution was cooled to room temperature, 100 mL of toluene was added, and the organic layer was washed twice with 50 mL of hydrochloric acid and twice with 50 mL of water. The organic layer was taken out, dried by adding magnesium sulfate, and filtered. Carbolafine was added to the filtrate, stirred at 60 ° C. for 1 hour, and filtered through celite. After the solvent of the filtrate was distilled off with a rotary evaporator, the filtrate was dried under reduced pressure at 60 ° C. to obtain 13.4 g of a compound represented by the formula (I-1) (fluorinated methacrylate ester).

The structure of compound (I-1) was identified by ¹ H-NMR (EX-270; manufactured by JEOL Ltd.).
¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ , room temperature): 1.95 (3H, s), 2.3-2.7 (4H, m), 3.75 ( 2H, t, J = 15 Hz), 4.05 (2H, t, J = 15 Hz), 5.56 (1H, d, J = 1.0 Hz), 6.10 (1H, d, J = 1.0 Hz) ), 9.29 (1H, bs)

Synthesis Example 2: Synthesis of Polymer Aa A 500 mL four-necked flask equipped with a dropping funnel, a Dimroth cooling tank, a thermometer and a mechanical stirrer was charged with 15.0 g of methyl isobutyl ketone, and nitrogen gas was stirred for 15 minutes while stirring. Then, the temperature was raised to 90 ° C. as it was. To a 200 mL beaker, 13.4 g (31 mmol) of compound (I-1), 0.154 g (0.94 mmol) of 2,2′-azobis (isobutyronitrile), and 53 g of methyl isobutyl ketone were added and stirred at room temperature. To a homogeneous solution. This solution was added to the dropping funnel and dropped into a four-necked flask kept at 90 ° C. over 1 hour. After completion of dropping, the inside of the four-necked flask was kept at 90 ° C. and stirred for 4 hours to obtain a colorless solution. The inside of the four-necked flask was cooled to room temperature, the obtained colorless solution was transferred to a 1 L eggplant type flask, the solvent was distilled off with a rotary evaporator, and then dried under reduced pressure at 60 ° C. to obtain 13.4 g of polymer Aa. It was. The number average molecular weight (Mn) of the polymer Aa was 13,000, the weight average molecular weight (Mw) was 23,000, and the dispersity (Mw / Mn) was 1.74.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer Aa were measured by the GPC method (polystyrene conversion) under the following conditions.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector: RI
Test solvent: 2% THF solution

Synthesis Example 3: Synthesis of Compound (I-2) Fluorine-containing diol represented by formula (Ia-2) (2,2,3,3,4,4,5,5,6,6,7,7- 15.0 g (41 mmol) of dodecafluoro-1,8-octanediol, CAS No. 90177-96-1, manufactured by Daikin Chemicals Sales Co., Ltd., 4.1 g (41 mmol) of succinic anhydride, 4-dimethylamino After adding 0.51 g (4.1 mmol) of pyridine and 55 g of pyridine, the mixture was stirred for 2.5 hours while refluxing. Thereafter, the reaction solution was cooled to room temperature, 100 mL of toluene was added, and the organic layer was washed twice with 50 mL of hydrochloric acid and twice with 50 mL of water. The organic layer was taken out, dried by adding magnesium sulfate, and filtered. Carbolafine was added to the filtrate, stirred at 60 ° C. for 1 hour, and filtered through celite. After the solvent of the filtrate was distilled off with a rotary evaporator, the filtrate was dried under reduced pressure at 60 ° C. to obtain 16.8 g of a compound represented by the formula (Id-2) (fluorinated dicarboxylic acid monoester).

The structure of the compound (Id-2) was identified by ¹ H-NMR (EX-270; manufactured by JEOL Ltd.).
¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ , room temperature): 2.3-2.7 (4H, m), 3.72 (2H, t, J = 15 Hz), 4.07 (2H, t, J = 15 Hz), 6.05 (1H, bs), 9.19 (1H, bs)

  Next, 5.6 g (36 mmol) of methacrylic anhydride, 0.45 g (3.6 mmol) of 4-dimethylaminopyridine, and 50 g of pyridine were added to 16.8 g (36 mmol) of compound (Id-2), and the mixture was refluxed. The mixture was stirred for 2.5 hours. Thereafter, the reaction solution was cooled to room temperature, 100 mL of toluene was added, and the organic layer was washed twice with 50 mL of hydrochloric acid and twice with 50 mL of water. The organic layer was taken out, dried by adding magnesium sulfate, and filtered. Carbolafine was added to the filtrate, stirred at 60 ° C. for 1 hour, and filtered through celite. The filtrate was evaporated using a rotary evaporator, and then dried under reduced pressure at 60 ° C. to obtain 17.4 g of a compound represented by the formula (I-2) (fluorinated methacrylate ester).

The structure of the compound (I-2) was identified by ¹ H-NMR (EX-270; manufactured by JEOL Ltd.).
¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ , room temperature): 1.96 (3H, s), 2.3-2.7 (4H, m), 3.72 ( 2H, t, J = 15 Hz), 4.02 (2H, t, J = 15 Hz), 5.51 (1H, d, J = 1.0 Hz), 6.16 (1H, d, J = 1.0 Hz) ), 9.24 (1H, bs)

Synthesis Example 4: Synthesis of Polymer Ab A 500 mL four-necked flask equipped with a dropping funnel, a Dimroth cooling tank, a thermometer and a mechanical stirrer was charged with 16.0 g of methyl isobutyl ketone, and nitrogen gas was stirred for 15 minutes while stirring. Then, the temperature was raised to 90 ° C. as it was. To a 200 mL beaker, 17.4 g (33 mmol) of compound (I-2), 0.162 g (0.98 mmol) of 2,2′-azobis (isobutyronitrile) and 56 g of methyl isobutyl ketone were added and stirred at room temperature. To a homogeneous solution. This solution was added to the dropping funnel and dropped into a four-necked flask kept at 90 ° C. over 1 hour. After completion of dropping, the inside of the four-necked flask was kept at 90 ° C. and stirred for 4 hours to obtain a colorless solution. The inside of the four-necked flask was cooled to room temperature, and the resulting colorless solution was transferred to a 1 L eggplant-shaped flask, the solvent was distilled off with a rotary evaporator, and then dried under reduced pressure at 60 ° C. to obtain 17.3 g of polymer Ab. It was. The number average molecular weight (Mn) of the polymer Ab was 12,400, the weight average molecular weight (Mw) was 24,000, and the dispersity (Mw / Mn) was 1.90. The molecular weight of the polymer Ab was measured in the same manner as in the case of the polymer Aa.

Synthesis Example 5: Synthesis of Polymer Ac A 500 mL four-necked flask equipped with a dropping funnel, a Dimroth cooling tank, a thermometer and a mechanical stirrer was charged with 20 g of methyl isobutyl ketone, and nitrogen gas was introduced into the flask for 15 minutes while stirring. After flowing, the temperature was raised to 90 ° C. In a 200 mL beaker, 10.1 g (24 mmol) of the compound represented by formula (a-1) (fluorinated methacrylate ester), 0.40 g (2.4 mmol) of 2,2′-azobis (isobutyronitrile), Then, 10.0 g of methyl isobutyl ketone was added and stirred at room temperature to make a uniform solution. This solution was added to the dropping funnel and dropped into a four-necked flask kept at 90 ° C. over 1 hour. After completion of dropping, the inside of the four-necked flask was kept at 90 ° C. and stirred for 4 hours to obtain a colorless solution. The inside of the four-necked flask was cooled to room temperature, the obtained colorless solution was transferred to a 1 L eggplant type flask, the solvent was distilled off with a rotary evaporator, and then dried under reduced pressure at 60 ° C. to obtain 9.9 g of polymer Ac. It was. The number average molecular weight (Mn) of the polymer Ac was 3,800, the weight average molecular weight (Mw) was 6,300, and the dispersity (Mw / Mn) was 1.65. The molecular weight of the polymer Ac was measured in the same manner as in the case of the polymer Aa.

Production Example 1: Production of photosensitive composition 1 Polymer Aa: 49 parts, ester of phenol compound represented by formula (110) as photosensitizer (B) and o-naphthoquinonediazide-5-sulfonic acid, 40 parts, After mixing 11 parts of hexamethoxymethylol melamine as the curing agent (C) and 400 parts of 4-hydroxy-4-methyl-2-pentanone as the solvent (D), the mixture was filtered through a membrane filter having a pore size of 0.2 μm and photosensitive composition. Product 1 was obtained.

Production Example 2: Production of Photosensitive Composition 2 A photosensitive composition 2 was obtained in the same manner as in Production Example 1 except that the polymer Ab was used instead of the polymer Aa.

Production Example 3 Production of Photosensitive Composition 3 A photosensitive composition 3 was obtained in the same manner as in Production Example 1 except that the polymer Ac was used instead of the polymer Aa.

Example 1: Evaluation of characteristics of photosensitive compositions 1 to 3 The characteristics (developability, refractive index, and average transmittance) of photosensitive compositions 1 to 3 and their coating films were evaluated as follows. The results are shown in Table 1.

(1) Developability [Including UV irradiation process]
Photosensitive compositions 1 to 3 were applied onto a silicon wafer by spin coating so that the film thickness became 1 μm, and heated at 90 ° C. for 1 minute to remove volatile components, thereby forming a coating film. After irradiating the obtained coating film with ultraviolet light having a wavelength of 300 to 450 nm at 200 mJ / cm ² , the film thickness was measured with an optical interference film thickness meter (VM1200; manufactured by Dainippon Screen Mfg. Co., Ltd.). The film thickness at this time is d ₁ .
The coating film after the ultraviolet irradiation was heated at 110 ° C. for 1 minute, immersed in a developer (2.38% tetramethylammonium hydroxide aqueous solution) for 1 minute, then washed with water and dried, and then the film thickness was measured. . The film thickness at this time is d _2.
Substrate thicknesses d ₁ and d ₂ were substituted into the following formula to obtain a developed film ratio of 1.
Development residual film ratio 1 (%) = d ₂ / d ₁ × 100

[When UV irradiation process is not included]
Photosensitive compositions 1 to 3 were applied onto a silicon wafer by spin coating so that the film thickness became 1 μm, and heated at 90 ° C. for 1 minute to remove volatile components, thereby forming a coating film. The film thickness of the obtained coating film was measured with an optical interference film thickness meter (VM1200; manufactured by Dainippon Screen Mfg. Co., Ltd.). The film thickness at this time is d ₃ .
This coating film was heated at 110 ° C. for 1 minute, immersed in a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 1 minute, then washed with water and dried, and then the film thickness was measured. The film thickness at this time is d ₄ .
Substrate thickness d ₃ and d ₄ were substituted into the following formula to obtain a residual film ratio of 2.
Development residual film ratio 2 (%) = d ₄ / d ₃ × 100

(2) Refractive index The photosensitive compositions 1-3 were apply | coated with the spin coat method on the silicon wafer, the volatile component was removed by heating at 90 degreeC for 1 minute, and the coating film was formed. Subsequently, the obtained coating film was irradiated with ultraviolet light having a wavelength of 300 to 450 nm at 200 mJ / cm ² and heated at 180 ° C. for 3 minutes. In addition, application | coating by a spin coat method was adjusted so that the film thickness of a coating film might be set to 1.0 micrometer after the said heating at 180 degreeC. The refractive index at 550 nm of the heated coating film was measured with a spectroscopic ellipsometer (M-220; manufactured by JASCO Corporation). The refractive index is preferably as low as possible.

(3) Average transmittance The photosensitive compositions 1 to 3 are applied on a quartz wafer by spin coating so that the film thickness becomes 1.0 μm, and the volatile components are removed by heating at 90 ° C. for 1 minute. A coating film was formed. This coating film was irradiated with ultraviolet light having a wavelength of 300 to 450 nm at 200 mJ / cm ² and heated at 180 ° C. for 3 minutes. The transmittance in the visible region (400 to 700 nm) of the coated film after heating was measured with a spectrophotometer (DU-640; manufactured by BECKMAN), and the average transmittance (T0) value was calculated. Higher average transmittance is preferable.

  Photosensitive compositions 1 and 2 are examples of the present invention containing polymer Aa and polymer Ab obtained from compound (I-1) and compound (I-2), respectively. On the other hand, the photosensitive composition 3 is a comparative example containing the polymer Ac obtained from the compound (a-1). As shown from the results in Table 1, the coatings obtained from the photosensitive compositions 1 and 2 of the present invention were dissolved by immersion in the developing solution after the ultraviolet irradiation, but the photosensitive composition of the comparative example was lost. The coating film obtained from 3 remained almost even when immersed in the developer. As is clear from this result, the photosensitive compositions 1 and 2 of the present invention were excellent in developability. Moreover, the coating film obtained from the photosensitive compositions 1 and 2 of this invention showed the low refractive index and the high average transmittance | permeability.

  The photosensitive composition of the present invention can be alkali-developed, and the coating film obtained therefrom has a low refractive index. Therefore, the photosensitive composition of the present invention is a clear material for forming a material such as a microlens; a protective film such as a solid-state imaging device, a liquid crystal display and a color filter, a resist lower layer film, and an upper layer and lower layer film of a microlens. It is useful as a coating agent;

Claims (5)

A photosensitive composition comprising a polymer (A) having a compound represented by formula (I) as a constituent monomer, a photosensitive agent (B), a curing agent (C), and a solvent (D).

[In Formula (I), R ^{1 to} R ³ each independently represent a hydrogen atom, a fluorine atom, or a C _1-13 aliphatic hydrocarbon group which may be substituted with a fluorine atom or a hydroxyl group.
R ⁴ each independently represents a single bond or a C _1-10 alkylene group which may be substituted with a fluorine atom.
R ⁵ represents a single bond or a C _1-15 aliphatic hydrocarbon group which may be substituted with a fluorine atom.
R ⁶ represents a linear C _1-10 alkylene group which may be substituted with a fluorine atom.
R ⁷ represents a hydrogen atom, a C _1-24 aliphatic hydrocarbon group which may be substituted with a fluorine atom or a hydroxyl group, or a C _1-24 aliphatic hydrocarbon in which a part of a methylene unit is replaced with an oxygen atom. Indicates a group.
However, any one of R ^{1 to} R ⁷ is a fluorine atom or a group substituted with a fluorine atom. ] The photosensitive composition according to claim 1, wherein in the compound represented by the formula (I), R ⁶ is a linear C _1-10 alkylene group substituted with a fluorine atom. The photosensitive composition according to claim 1 or 2, wherein in the compound represented by formula (I), R ⁷ is a hydrogen atom.   The photosensitive composition according to claim 1, wherein the photosensitive agent (B) is a quinonediazide compound.   The photosensitive composition according to claim 1, wherein the curing agent (C) is a melamine compound.