JP5338258B2 - Positive photosensitive composition, cured film obtained from the composition, and display element having the cured film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive composition capable of forming a cured film excellent in liquid repellency, a cured film formed of the composition, and a display element having the cured film. <P>SOLUTION: The photosensitive composition comprises a polymer (A) containing fluorine having a fluorine-containing silsesquioxane group and an alkali-soluble functional group, and a 1,2-quinone diazide compound (B). The cured film is formed by baking the composition. The display element having the cured film is also provided. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a photosensitive composition for producing a liquid crystal display element, an EL display element and the like, a transparent film produced from the composition, and a display element comprising the transparent film.

  Patterned transparent films are used in many parts of liquid crystal display elements such as spacers, insulating films, protective films, etc., and various photosensitive compositions have been used so far for liquid crystal display elements, EL display elements, etc. It has been used for display elements (see, for example, Patent Document 1). A patterned transparent film is obtained by applying a photocurable polymer composition to a substrate, irradiating the coating film with light according to the pattern, and washing and removing the uncured film without being irradiated with light. It can be formed of a negative photosensitive material that forms a patterned film and a positive photosensitive material that forms a patterned film by removing the film irradiated with light and solubilized in an alkaline developer. Thus, many photocurable polymer compositions and photosensitive compositions for forming a patterned transparent film have also been proposed (see, for example, Patent Document 2).

On the other hand, in recent years, various types of patterning using an inkjet method have been proposed (see, for example, Patent Document 3). Further, in the patterning by the ink jet method, in order to perform precise ink jet patterning, a partition (bank material) between the pixels may be formed before the application by the ink jet method is performed. This bank material can be formed as a patterned film by a known method using a photocurable polymer composition and a photosensitive composition as described above. Such a bank material is required to have a characteristic that a liquid substance ejected from a head nozzle of an ink jet apparatus does not adhere, that is, ink repellency (see, for example, Patent Document 4 or 5). Thus, the use of the photocurable polymer composition and the photosensitive composition extends not only to the material constituting the layer in the display element but also to a film for an auxiliary role in the manufacture of the display element. With the expansion of such applications, the photocurable polymer composition and the photosensitive composition are required to have various performances as compared with conventional ones.
JP 2004-287232 A JP 2001-261761 A Japanese Patent Laid-Open No. 10-12377 JP-A-11-281815 JP 2004-149699 A

  An object of the present invention is to provide a positive photosensitive composition capable of forming a cured film having excellent liquid repellency. Moreover, this invention makes it a subject to provide the cured film by such a positive photosensitive composition, and the display element which has this film | membrane.

  As a result of diligent studies to solve the above problems, the present inventors have made liquid repellent properties particularly by using a polymer containing a fluorine-containing silsesquioxane group and an alkali-soluble functional group in the photosensitive composition. It discovered that the cured film which was excellent was obtained, and completed this invention shown below.

[1] A photosensitive composition containing a polymer (A) containing fluorine and a 1,2-quinonediazide compound (B), wherein the polymer (A) containing fluorine is represented by the following formula (I): A photosensitive composition having a fluorine-containing silsesquioxane group and an alkali-soluble functional group.
_{- [(R-SiO 1.5)} (Rf-SiO 1.5) n-1] (I)

In the formula (I), R represents a single bond or alkylene having 1 to 20 carbon atoms in which arbitrary methylene may be replaced with oxygen, and arbitrary hydrogen may be replaced with fluorine, and Rf is Independently: a) any methylene optionally substituted with oxygen 1 to 20 carbon fluoroalkyl; b) one or more hydrogens in aryl substituted with fluorine or —CF ₃ 20) a fluoroaryl; c) one or more hydrogens in the aryl substituted with fluorine or —CF ₃ , a C7-20 fluoroarylalkyl; or d) any methylene may be replaced with oxygen. An alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, and an arylalkyl having 7 to 20 carbon atoms in which any methylene may be replaced by oxygen; One or more are any one of a) to c), and n represents an integer of 4 to 24. However, oxygen does not adjoin in R and Rf.

[2] The photosensitive composition according to [1], wherein the fluorine-containing silsesquioxane group is represented by the following formula (II). In the formula (II), R represents a single bond or alkylene having 1 to 20 carbon atoms in which any methylene may be replaced with oxygen, and any hydrogen may be replaced with fluorine, and Rf is Independently: a) any methylene optionally substituted with oxygen 1 to 20 carbon fluoroalkyl; b) one or more hydrogens in aryl substituted with fluorine or —CF ₃ 20) a fluoroaryl; c) one or more hydrogens in the aryl substituted with fluorine or —CF ₃ , a C7-20 fluoroarylalkyl; or d) any methylene may be replaced with oxygen. An alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, an arylalkyl having 7 to 20 carbon atoms in which any methylene may be replaced by oxygen, and Rf One or more of a) ~c) Ru Der any of the. However, oxygen does not adjoin in R and Rf.

[3] The photosensitive composition according to [1] or [2], wherein the alkali-soluble functional group is one or both of a carboxyl group and a phenolic hydroxyl group.

[4] The polymer (A) containing fluorine is a radical polymerizable monomer (a-1) having the fluorine-containing silsesquioxane group and a radical polymerizable functional group; the radical polymerizable functional group; The photosensitive composition as described in any one of [1]-[3] which is a radical polymer of the radically polymerizable monomer containing the radically polymerizable monomer (a-2) which has an alkali-soluble functional group.

[5] The radical polymerizable functional group is CH ₂ ═CH—, CH ₂ ═CHO—, CH ₂ ═C (
The photosensitive composition according to [4], which is one or more selected from the group consisting of CH ₃ ) —COO—, CH ₂ ═CH—COO—, and a functional group represented by the following formula (III).

[6] A radical polymerizable monomer other than the radical polymerizable monomers (a-1) and (a-2) having the radical polymerizable functional group in the monomer of the polymer (A) containing fluorine ( The photosensitive composition as described in [4] or [5] containing a-3).

[7] The photosensitive composition according to [6], wherein the other radical polymerizable monomer (a-3) is one or more selected from the group consisting of a ( meth) acrylic acid derivative and a styrene derivative.

[8] The photosensitive composition according to any one of [1] to [7], further containing an alkali-soluble polymer (C).

[9] The alkali-soluble polymer (C) is composed of a radical polymerizable monomer having an unsaturated carboxylic acid, a radical polymerizable monomer having an unsaturated carboxylic acid anhydride, and a radical polymerizable monomer having a phenolic hydroxyl group. The photosensitive composition as described in [8], which is a radical polymer of a radically polymerizable monomer containing one or more selected from the group consisting of:

[10] The photosensitive composition according to any one of [1] to [9], further containing a solvent.

[11] A cured film obtained by baking the film of the photosensitive composition according to any one of [1] to [10].

[12] A display device having the cured film according to [11].

  The photosensitive composition of the present invention can form a cured film having excellent liquid repellency. Moreover, since the said cured film can be used as a transparent film, an insulating film, or a protective film, the display element which has such a cured film can be comprised.

1. Photosensitive composition of the present invention The photosensitive composition of the present invention contains a polymer (A) containing fluorine and a 1,2-quinonediazide compound (B). The polymer (A) containing fluorine may be one type or two or more types. The 1,2-quinonediazide compound (B) may be one kind or two or more kinds.

1-1. Polymer containing fluorine (A)
The polymer (A) containing fluorine has a fluorine-containing silsesquioxane group represented by the following formula (I) and an alkali-soluble functional group. The fluorine-containing silsesquioxane group may be one kind or two or more kinds.
_{- [(R-SiO 1.5)} (Rf-SiO 1.5) n-1] (I)

  In the formula (I), R represents a single bond or alkylene having 1 to 20 carbon atoms in which arbitrary methylene may be replaced with oxygen, and arbitrary hydrogen may be replaced with fluorine. However, oxygen does not adjoin in R. The alkylene preferably has 1 to 10 carbon atoms.

In the formula (I), Rf is independently: a) a fluoroalkyl having 1 to 20 carbon atoms in which arbitrary methylene may be replaced by oxygen; b) one or more hydrogens in aryl are fluorine or- fluoroaryl having 6 to 20 carbon atoms of which is replaced by CF _3; c) 1 or more hydrogen is fluorine or carbon atoms are replaced by -CF ₃ 7 to 20 fluoroarylalkyl in aryl; or, d) optionally In which methylene of 1 to 20 carbons may be substituted with oxygen, aryl having 6 to 20 carbons, or arylalkyl of 7 to 20 carbon atoms in which any methylene may be replaced with oxygen. One or more of Rf is any one of a) to c). However, oxygen is not adjacent to Rf. From the viewpoint of the liquid repellency of the cured film to be formed, Rf is preferably 4 or more of any one of a) to c), and more preferably all of any of a) to c). .

  In said formula (I), n represents the integer of 4-24. n is preferably 6 to 18, and more preferably 8.

  The fluorine-containing silsesquioxane group is preferably a group represented by the following formula (II) from the viewpoint of liquid repellency of the formed cured film.

  In formula (II), R and Rf have the same meaning as R and Rf in formula (I). Moreover, oxygen does not adjoin in R and Rf.

  Examples of R include ethylene, propylene, and butylene. Of these, R is preferably propylene.

Among the Rf, examples of the fluoroalkyl (a) having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen include trifluoromethyl, 2,2,2-trifluoroethyl, 3,3, 3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 3,3,4,4,4-pentafluorobutyl, 2,2, 2-trifluoro-1-trifluoromethylethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 2, 2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3,4,4,5,5- Octafluoropentyl, 3, 3, -Trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2, 2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perfluoro-1H, 1H, 2H, 2H-tetradecyl, tetradecyl-1, 1,2,2-tetrahydrododecyl and (3-heptafluoroisopropoxy) propyl.

Among the Rf, examples of the fluoroaryl (b) having 6 to 20 carbon atoms in which one or more hydrogens in the aryl are replaced by fluorine or —CF ₃ include, for example, pentafluorophenyl and α, α, α-tri And fluorotolyl.

Among the Rf, examples of the fluoroarylalkyl (c) having 7 to 20 carbon atoms in which one or more hydrogens in aryl are replaced with fluorine or —CF ₃ include pentafluorophenylpropyl.

  Of the Rf, any methylene may be replaced by oxygen having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and any methylene may be substituted by oxygen having 7 to 20 carbon atoms Examples of the alkyl (d) include phenyl, propyl, butyl, methylphenyl, ethylphenyl, and propylphenyl.

  (A) to (c) in Rf are 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3, Selected from the group consisting of 3,3-pentafluoropropyl, 3,3,4,4,4-pentafluorobutyl, and 3,3,4,4,5,5,6,6,6-nonafluorohexyl It is preferably one or more, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,4,4,5, It is more preferably one or more selected from the group consisting of 5,6,6,6-nonafluorohexyl, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,6, Be one or both of 6,6-nonafluorohexyl But more preferably, it is even more preferably the same group.

  The alkali-soluble functional group is an acidic group that is ionized with a 2.38 wt% tetramethylammonium hydroxide aqueous solution or an aqueous solution having equivalent alkalinity. One or more alkali-soluble functional groups may be used. Examples of the alkali-soluble functional group include a carboxyl group and a phenolic hydroxyl group. The alkali-soluble functional group is preferably one or both of a carboxyl group and a phenolic hydroxyl group. The carboxyl group is preferable from the viewpoint of improving developability, and the phenolic hydroxyl group is preferable from the viewpoint of improving the transparency of the formed cured film.

  In the fluorine-containing polymer (A), the ratio of the fluorine-containing silsesquioxane group to the total amount of the fluorine-containing silsesquioxane group and the alkali-soluble functional group is the liquid repellency of the formed cured film. From the viewpoint, it is preferably 0.1 to 70 mol%, more preferably 0.5 to 50 mol%, and still more preferably 1 to 30 mol%.

In the polymer (A) containing fluorine, the ratio of the alkali-soluble functional group to the total amount of the fluorine-containing silsesquioxane group and the alkali-soluble functional group is from the viewpoint of developability of the photosensitive composition, It is preferably 1 to 50 mol%, more preferably 3 to 40 mol%, and even more preferably 5 to 30 mol%. In addition, the alkali solubility of the photosensitive composition of the present invention refers to a film having a thickness of 0.01 to 100 μm formed by spin coating of the photosensitive composition and heating at 120 ° C. for 30 minutes. The film does not remain when immersed in 38% by weight tetramethylammonium hydroxide aqueous solution for 5 minutes and rinsed with pure water.

  The fluorine-containing polymer (A) is not particularly limited as long as it is a polymer having the above-mentioned fluorine-containing silsesquioxane group and an alkali-soluble functional group, but the fluorine-containing silsesquioxane group and radical polymerizability are not limited. Radical weight of radical polymerizable monomer comprising a radical polymerizable monomer (a-1) having a functional group and a radical polymerizable monomer (a-2) having the radical polymerizable functional group and the alkali-soluble functional group. The combination is preferable from the viewpoint of controlling the liquid repellency of the formed cured film and the developability of the photosensitive composition.

The radical polymerizable functional group may be a group that generates radicals by heat or light. The radical polymerizable functional group may be one type or two or more types. Examples of the radical polymerizable functional group include CH ₂ ═CH—, CH ₂ ═CHO—, CH ₂ ═C (CH ₃ ) —COO—, CH ₂ ═CH—COO—, and the following formula (III). Group to be used. Among these, CH ₂ ═C (CH ₃ ) —COO— or CH ₂ ═CH—COO— is preferable.

  The radical polymerizable monomer (a-1) may be a compound in which the fluorine-containing silsesquioxane group and the radical polymerizable functional group are directly bonded, or the fluorine-containing silsesquioxane group. And a compound in which the radical polymerizable functional group is bonded via another organic group such as a divalent organic group. The radical polymerizable monomer (a-1) may be one type or two or more types.

  Examples of the radical polymerizable monomer (a-1) include γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane. γ-Methacryloxypropylhepta (trifluoropropyl) -T8-silsesquioxane can be synthesized by a method disclosed in Japanese Patent Application Laid-Open No. 2004-123698 (for example, Example 14).

  The radical polymerizable monomer (a-2) may be a compound in which the alkali-soluble functional group and the radical polymerizable functional group are directly bonded, or the alkali-soluble functional group and the radical polymerizable functional group. A compound in which a group is bonded via another organic group such as a divalent organic group may be used. The radical polymerizable monomer (a-2) may be one type or two or more types.

  Examples of the radical polymerizable monomer (a-2) include a radical polymerizable monomer having an unsaturated carboxylic acid, a radical polymerizable monomer having an unsaturated carboxylic acid anhydride, and a radical polymerizable monomer having a phenolic hydroxyl group. More specifically, methacrylic acid, hydroxystyrene, and 4-hydroxyphenyl vinyl ketone are mentioned. Methacrylic acid and hydroxystyrene are preferable from the viewpoint of easy availability, and 4-hydroxyphenyl vinyl ketone is preferable from the viewpoint of enhancing the transparency and heat resistance of the formed cured film.

  In radical polymerization, the radical polymerizable monomers (a-1) and (a-2) are in an amount corresponding to a desired ratio of the fluorine-containing silsesquioxane group and the alkali-soluble functional group in the fluorine-containing polymer (A). Used in

  The monomer of the polymer (A) containing fluorine includes other radical polymerizable monomers (a-) having the radical polymerizable functional group other than the radical polymerizable monomers (a-1) and (a-2). 3) may be further included. The radical polymerizable monomer (a-3) has the radical polymerizable functional group and a further group other than the fluorine-containing silsesquioxane group and the alkali-soluble functional group. The radical polymerizable monomer (a-3) may be one type or two or more types.

  For example, the radically polymerizable monomer (a-3) has a radically polymerizable functional group and a crosslinkable functional group, so that a rigid film is formed by a crosslinking reaction performed when the film of the crosslinkable composition is fired. And from the viewpoint of increasing the heat resistance of the formed cured film. The crosslinkable functional group may be one kind or two or more kinds. Examples of the crosslinkable functional group include epoxy such as glycidyl; oxetanyl; and isocyanate. The crosslinkable functional group is preferably epoxy or oxetanyl.

Examples of the radical polymerizable monomer (a-3) include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate ; glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, α-ethyl Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3 -(Meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 2- (meth) acryloyloxyethyl isocyanate, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylate-2 -Aminoe (Meth) acrylic acid derivatives such as chill; and styrene derivatives such as glycidyl vinyl benzyl ether. The radical polymerizable monomer (a-3) is at least one selected from the group consisting of a ( meth) acrylic acid derivative and a styrene derivative as described above, which is one of sputtering resistance and transparency of the formed cured film. Or it is preferable from a viewpoint of improving both.

  Among the above specific examples, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3-ethyl-3- (meth) acryloxymethyl oxetane are easily available. It is preferable from the viewpoint of improving the solvent resistance, water resistance, acid resistance, alkali resistance, heat resistance, and transparency of the obtained patterned transparent film.

  In the radical polymerization, the radical polymerizable monomer (a-3) is used in such an amount that the effects of the present invention and the intended function of the radical polymerizable monomer (a-3) can be obtained. For example, the amount of the radical polymerizable monomer (a-3) used in the radical polymerization is preferably 50 to 90 mol% in the monomer forming the polymer (A) containing fluorine, and preferably 55 to 85 mol%. Is more preferable, and it is still more preferable that it is 60-80 mol%.

  The polymer (A) containing fluorine is obtained by radical polymerization of the radical polymerizable monomers containing the radical polymerizable monomers (a-1) and (a-2). This radical polymerization can be performed by a known method.

  The polymerization method of the polymer (A) containing fluorine is not particularly limited, but radical polymerization in a solution using a solvent is preferable. A known polymerization initiator can be used for this radical polymerization. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator used, but is usually in the range of 50 to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. Further, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

  The solvent used in the radical polymerization is preferably a solvent that dissolves the radical polymerizable monomer as the raw material and the polymer (A) containing fluorine as the product. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether, propylene. Examples include glycol monomethyl ether, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N, N-dimethylformamide, acetic acid, and water. The solvent may be one kind or two or more kinds.

  As the polymerization initiator, a compound that generates a radical by heat, an azo initiator such as azobisisobutyronitrile, and a peroxide initiator such as benzoyl peroxide can be used. The addition amount of the polymerization initiator is preferably 1 to 30 parts by weight, and more preferably 5 to 25 parts by weight, with respect to 100 parts by weight of the total amount of monomers as a raw material for the polymer (A) containing fluorine. preferable.

  Moreover, in order to adjust the molecular weight of the polymer (A) containing fluorine, a chain transfer agent such as thioglycolic acid may be added. The addition amount of the chain transfer agent is preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the total amount of monomers as a raw material for the polymer (A) containing fluorine, and 0.005 to 0.03. More preferably, it is part by weight.

  The weight average molecular weight of the fluorine-containing polymer (A) varies depending on the type of raw material monomer, but is preferably 2,000 to 50,000 as a guide. Moreover, it is preferable that Mw / Mn of the polymer (A) containing fluorine is 1.5 to 3.5 as a standard.

  The weight average molecular weight (Mw) and number average molecular weight (Mn) of the fluorine-containing polymer (A) can be determined by GPC analysis using polyethylene oxide as a standard. For example, the molecular weight is 1,000 to 510,000. In a GPC analysis under the condition that a polyethylene oxide (for example, TSK standard manufactured by Tosoh Corporation) is used as a standard polyethylene oxide, Shodex KD-806M (Showa Denko Co., Ltd.) is used as a column, and DMF is used as a mobile phase. Can be measured.

  The monomer of the polymer (A) containing fluorine can be estimated by measuring a gas generated by pyrolysis by GC-MS when the polymer (A) containing fluorine is pyrolyzed.

  Since the polymer (A) containing fluorine contains fluorine, it can impart water repellency and / or oil repellency to the film formed from the photocurable polymer composition of the present invention. Moreover, if the radically polymerizable monomer (a-3) contains a crosslinkable functional group, the crosslinkable functional group is introduced into the fluorine-containing polymer (A), whereby the photosensitive composition of the present invention. The chemical resistance of the formed cured film is further improved.

1-2.1,2-quinonediazide compound (B)
As the 1,2-quinonediazide compound (B), for example, a compound used as a photosensitizer in the resist field can be used. Examples of the 1,2-quinonediazide compound (B) include, for example, an ester of a phenol compound and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid, and a phenol compound and 1,2 -Naphthoquinonediazide-4-sulfonic acid or ester with 1,2-naphthoquinonediazide-5-sulfonic acid, sulfonamide of a compound in which the hydroxyl group of the phenol compound is replaced with an amino acid and 1,2-sulfonic acid, hydroxyl group of the phenolic compound And a sulfonamide of 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid.

  Examples of the phenol compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,3 ′, 4. -Tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1 , 1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3- Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1 [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl -1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol and 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan .

  The 1,2-quinonediazide compound (B) is an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-4-sulfonic acid, 2,3,4-trihydroxybenzophenone and 1,2,4. -Esters with naphthoquinonediazide-5-sulfonic acid, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide Esters with -4-sulfonic acid, or 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5 -It is one or more selected from the group consisting of esters with sulfonic acid, from the viewpoint of increasing the transparency of the photosensitive composition Masui.

  The photosensitive composition of the present invention may further contain other components other than the polymer (A) containing fluorine and the 1,2-quinonediazide compound (B) described above. Examples of such other components include an alkali-soluble polymer (C), a solvent, an additive, and a polyvalent carboxylic acid.

1-3. Alkali-soluble polymer (C)
The alkali-soluble polymer (C) is used from the viewpoint of further improving characteristics such as developability of the photosensitive composition of the present invention. The alkali-soluble polymer (C) has the alkali-soluble functional group. The alkali-soluble in the alkali-soluble polymer (C) is the thickness formed by spin coating of the solution of the alkali-soluble polymer (C) and heating at 120 ° C. for 30 minutes, as in the case of the alkali-soluble of the photosensitive composition described above. This means that when a film of 0.01 to 100 μm is immersed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at about 25 ° C. for 5 minutes and rinsed with pure water, the film does not remain. . The alkali-soluble polymer (C) may be one type or two or more types.

The alkali-soluble polymer (C) is preferably a radical polymer of a monomer containing the radical polymerizable monomer (a-2) from the viewpoint of controlling alkali solubility of the alkali-soluble polymer (C). In the alkali-soluble polymer (C), the alkali polymerizable monomer (a-2) can be used from the same viewpoint as the use in the polymer (A) containing fluorine.

  As the monomer of the alkali-soluble polymer (C), it is possible to further use one or both of a radical polymerizable monomer containing N-substituted maleimide and a radical polymerizable monomer containing dicyclopentanyl. From the viewpoint of further improving the properties and the low dielectric constant. The amount of these radically polymerizable monomers used is preferably 20 to 50 parts by weight and more preferably 25 to 45 parts by weight with respect to 100 parts by weight of the monomer that forms the alkali-soluble polymer (C). Preferably, the amount is 30 to 40 parts by weight.

  Examples of the radical polymerizable monomer containing N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- (4- Acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N- (1-anilinonaphthyl-4) maleimide, N- [ 4- (2-Benzoxazolyl) phenyl] maleimide and N- (9-acridinyl) maleimide.

  Examples of the radical polymerizable monomer containing dicyclopentanyl include dicyclopentanyl acrylate and dicyclopentanyl methacrylate.

  The monomer of the alkali-soluble polymer (C) may further contain the radical polymerizable monomer (a-3) as long as the effects of the present invention are not impaired. The radical polymerizable monomer for the alkali-soluble polymer (C) is the same as the monomer contained in the fluorine-containing polymer (A), except for the radical polymerizable monomer (a-1). It may be different or different. The alkali-soluble polymer (C) can be produced in the same manner as the polymer (A) containing fluorine.

  The monomer of the alkali-soluble polymer (C) is measured by GC-MS, for example, when the alkali-soluble polymer is pyrolyzed, as in the polymer (A) containing fluorine. Can be estimated.

  Further, the weight average molecular weight of the alkali-soluble polymer (C) is preferably 2,000 to 50,000 as a standard, as in the polymer (A) containing fluorine, and Mw / Mn is a standard. It is preferably 1.5 to 3.5.

  In the photosensitive composition of the present invention, further containing the alkali-soluble polymer (C) is preferable from the viewpoint of high solubility in an alkaline aqueous solution, that is, high developability and easily obtaining a patterned transparent film. In addition, it is preferable from the viewpoint of further improving various characteristics of the photoresist film such as low dielectric constant, solvent resistance, high water resistance, high acid resistance, high alkali resistance, and high heat resistance.

1-4. Solvent The solvent is a solvent that dissolves solids in the photosensitive composition such as the fluorine-containing polymer (A), 1,2-quinonediazide compound (B), and alkali-soluble polymer (C). Preferably there is. The solvent may be one type or two or more types. The solvent is preferably a solvent having a boiling point of 100 ° C to 300 ° C.

  Examples of the solvent having a boiling point of 100 ° C. to 300 ° C. include water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropion acid Chill, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate Ethyl acetate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, di Propylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether Acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ-butyrolactone, and N, N-dimethyl Acetamide, and the like.

  The solvent may be a mixed solvent containing 20% by weight or more of a solvent having a boiling point of 100 to 300 ° C. As the solvent other than the solvent having a boiling point of 100 to 300 ° C. in the mixed solvent, one or more known solvents can be used.

  The solvent is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, One or more selected from the group consisting of diethylene glycol methyl ethyl ether, ethyl lactate and butyl acetate is preferable from the viewpoint of improving the coating uniformity of the photosensitive composition. Furthermore, the solvent is one or more selected from the group consisting of propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, ethyl lactate, and butyl acetate. Is more preferable from the viewpoint of safety.

1-5. Additive The additive is used from the viewpoint of further improving desired characteristics among various characteristics such as resolution, coating uniformity, developability, and adhesiveness in the photosensitive composition. The additive may be one type or two or more types. Examples of such additives include acrylic, styrene, polyethyleneimine, or urethane polymer dispersants, anionic, cationic, nonionic, or fluorine surfactants, and improved silicone resin coating properties. Agents, adhesion improvers such as silane coupling agents, ultraviolet absorbers such as alkoxybenzophenones, aggregation inhibitors such as sodium polyacrylate, thermal crosslinking agents such as epoxy compounds, melamine compounds or bisazide compounds, organic carboxylic acids, etc. And an alkali solubility promoter.

  Examples of the additive include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trade names, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 , Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346 (all are trade names, manufactured by BYK Japan KK), KP-341, KP-358, KP-368, KF-96-50CS KF-50-100CS (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all trade names, Seimi Chemical Co., Ltd.) Manufactured), aftergent 222F, aftergent 251, FTX-218 (all are trade names, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF- 802 (all are trade names, manufactured by Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-475, Megafuck R-08, Megafuck R-30 (all are trade names) , Manufactured by Dainippon Ink & Chemicals, Inc.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, digly Phosphorus tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, Polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan Laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, Vitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate Can be mentioned.

  The additive is more preferably one or both of a fluorine-based surfactant and a silicone resin-based coatability improver from the viewpoint of improving the coating uniformity of the photosensitive composition. More specifically, the additive includes fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis ( Fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, BYK306, BYK344, BYK346, KP-341, KP-358, and one or more selected from the group consisting of KP-368 Is more preferable from the viewpoint of improving the coating uniformity of the photosensitive composition.

1-6. Polyvalent carboxylic acid The polyvalent carboxylic acid is used to increase the heat resistance and chemical resistance of the cured film formed from a photosensitive composition having an epoxy, and the 1,2-quinonediazide compound (B) during storage. From the viewpoint of preventing coloring of the photosensitive composition due to decomposition of the. The polyvalent carboxylic acid reacts with the epoxy in the photosensitive composition having an epoxy by heating. The polyvalent carboxylic acid may be one kind or two or more kinds. Examples of the polyvalent carboxylic acid include trimellitic anhydride, phthalic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride. Of the polyvalent carboxylic acids, trimellitic anhydride is preferable.

1-7. Content of each component in photosensitive composition Content of the said polymer (A) containing the fluorine in the said photosensitive composition is 10 to 90 weight% from a viewpoint of expressing the liquid repellency in a cured film. It is preferably 20 to 80% by weight, more preferably 30 to 70% by weight.

  The content of the 1,2-quinonediazide compound (B) in the photosensitive composition is based on 100 parts by weight of the total amount of the polymer (A) containing the siloxane structure and the alkali-soluble polymer (C). From the viewpoint of forming a fine pattern in the cured film, it is preferably 5 to 30 parts by weight, more preferably 7 to 25 parts by weight, and even more preferably 10 to 20 parts by weight.

  Content of the said alkali-soluble polymer (C) in the said photosensitive composition is 10-100 with respect to content of the said polymer (A) containing a fluorine from a viewpoint of fully expressing the alkali-soluble improvement effect. % By weight, preferably 20 to 90% by weight, more preferably 30 to 80% by weight.

  The content of the solvent in the photosensitive composition is such that the total solid content in the photosensitive composition is 5 to 50% by weight, which improves the coating uniformity of the photosensitive composition. From the viewpoint of safety and safety to the human body, the amount is preferably 10 to 45% by weight, more preferably 15 to 40% by weight.

  The content of the additive in the photosensitive composition is the sum of the fluorine-containing polymer (A) and the alkali-soluble polymer (C) from the viewpoint of imparting and improving the characteristics of the photosensitive composition and the cured film. The amount is preferably 0.05 to 2 parts by weight, more preferably 0.07 to 1.5 parts by weight, and still more preferably 0.1 to 1 part by weight with respect to 100 parts by weight. .

  The content of the polyvalent carboxylic acid in the photosensitive composition is selected from the viewpoints of improving the properties of the cured film and preventing the coloring of the photosensitive composition, and the fluorine-containing polymer (A) and the alkali-soluble polymer. It is preferable that it is 1-30 weight part with respect to 100 weight part of total amounts of (C), It is more preferable that it is 2-20 weight part, It is further more preferable that it is 3-15 weight part.

1-8. Storage of Photosensitive Composition The photosensitive composition is preferably stored while being shielded from light in the temperature range of −30 ° C. to 25 ° C. from the viewpoint of stably storing the photosensitive composition, and the storage temperature is −20. From the viewpoint of preventing the generation of precipitates, it is more preferable that the temperature is 10 ° C to 10 ° C.

2. Cured film of the present invention The cured film of the present invention is obtained by firing the film of the photosensitive composition of the present invention described above. The photosensitive composition is suitable for forming a transparent cured film. Since the resolution at the time of patterning is relatively high, it is suitable for forming an insulating film having a small hole of 10 μm or less. Here, the insulating film refers to, for example, a film (interlayer insulating film) provided to insulate wirings arranged in layers.

  The cured film such as the transparent film and the insulating film can be formed by an ordinary method of forming a cured film in the resist field, and is formed as follows, for example.

  First, a film of the photosensitive composition is formed. The film of the photosensitive composition is formed by applying the photosensitive composition on a substrate such as glass by a known method. Examples of preferable known coating methods include spin coating, roll coating, and slit coating. Examples of substrates include transparent glass substrates such as white plate glass, blue plate glass, and silica coated blue plate glass, synthetic resins such as polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, and polyimide. Examples thereof include a metal substrate such as a sheet, a film or a substrate, an aluminum plate, a copper plate, a nickel plate, and a stainless plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. If necessary, these substrates can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like.

  Next, the film of the photosensitive composition is dried. The photosensitive composition film is dried, for example, by heating the substrate having the photosensitive composition film in a hot plate or oven. Usually, it is dried at 60 to 120 ° C. for 1 to 5 minutes.

Next, the dried film of the photosensitive composition is irradiated with radiation such as ultraviolet rays through a mask having a desired pattern shape. Irradiation conditions depend on the type of the photosensitive agent in the positive photosensitive composition. For example, since the photosensitive composition contains the 1,2-quinonediazide compound (B), 5 to 1, 000 mJ / cm ² is suitable. In addition, when forming the cured film which does not have a pattern, this radiation irradiation process is unnecessary.

  Subsequently, the film of the photosensitive composition irradiated with radiation is washed with a developer and developed. The 1,2-quinonediazide compound (B) in the film of the photosensitive composition irradiated with the radiation becomes indenecarboxylic acid and quickly dissolves in the developer. By this development, the portion of the film irradiated with radiation is quickly dissolved in the developer. The development method is not particularly limited, and any of known methods such as dip development, paddle development, and shower development can be used.

  The developer is preferably an alkaline solution. As the developer, an aqueous alkali solution is preferably used. Examples of the alkali contained in the alkali solution include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and sodium hydroxide. , And potassium hydroxide. More preferable examples of the developer include organic alkalis such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and 2-hydroxyethyltrimethylammonium hydroxide, and sodium carbonate, sodium hydroxide, or water. An aqueous solution of inorganic alkalis such as potassium oxide can be used.

  Methanol, ethanol, or a surfactant may be added to the developer for the purpose of reducing development residue and optimizing the pattern shape. As the surfactant, for example, a surfactant selected from anionic, cationic, and nonionic surfactants can be used. Among these, it is particularly preferable to add nonionic polyoxyethylene alkyl ether from the viewpoint of increasing the resolution.

  Next, the developed film is washed. The cleaning of the film is performed, for example, by sufficiently rinsing the film together with pure water with pure water.

Then, the front surface of the cleaned film is irradiated with radiation. The remaining 1,2-quinonediazide compound (B) is deactivated by irradiation with this radiation. For example, when the radiation is ultraviolet rays, the irradiation of the radiation is performed by irradiating the film with ultraviolet rays having an intensity of 100 to 1,000 mJ / cm ² .

  Next, the film irradiated with radiation is baked to obtain a cured film. This film is baked, for example, by heating the substrate having the film at 180 to 250 ° C. for 10 to 120 minutes. According to such a step, the cured film is obtained as a desired patterned transparent film.

  The patterned transparent film thus obtained can also be used as a patterned insulating film. The shape of the hole formed in the insulating film is preferably a square, a rectangle, a circle or an ellipse when viewed from directly above. Furthermore, a transparent electrode may be formed over the insulating film, and after patterning by etching, a film for performing an alignment process may be formed. Since the insulating film has high sputtering resistance, wrinkles are not generated in the insulating film even when a transparent electrode is formed, and high transparency can be maintained.

3. Display element of the present invention The display element of the present invention has the above-described cured film of the present invention. Examples of the use of the cured film in the display element include a transparent film, an insulating film, and a bulk film for preventing liquid from adhering to the periphery of the pattern.

  The display element has the same configuration as that of a known display element except that the cured film is used for the above application, and can be manufactured in the same manner as the known display element. The display element is, for example, bonded by pressure-bonding an element substrate having a cured film patterned on the substrate as described above and a color filter substrate, which is a counter substrate, with the pixel positions aligned, and then heat-treating the display element. A liquid crystal display element is manufactured by curing the agent, injecting liquid crystal between opposing substrates, sealing the injection port, and combining with a polarizing plate or the like.

  In the manufacture of the liquid crystal display element, the liquid crystal can be sealed by spraying the liquid crystal on the element substrate, and then superimposing the element substrate and the color filter substrate and sealing the liquid crystal to prevent leakage. . The display element may be a liquid crystal display element manufactured in this way.

  The liquid crystal, that is, the liquid crystal compound and the composition containing the liquid crystal are not particularly limited, and any liquid crystal compound and liquid crystal composition can be used.

  The photosensitive composition of the present invention has, for example, high solvent resistance, high water resistance, high acid resistance, high alkali resistance, high heat resistance, and high transparency generally required for patterning transparent films and insulating films. In addition, it is possible to form a cured film having various properties such as properties and adhesion to the base and excellent liquid repellency.

  Since the cured film of the present invention is formed from the photosensitive composition, surface roughness is unlikely to occur even when subjected to treatments such as immersion, contact, and heat treatment in a solvent, acid, alkali solution or the like. Therefore, the display element of the present invention has a high light transmittance in the cured film and can provide a high display quality.

In addition, since the cured film of the present invention is formed from the photosensitive composition, it has excellent liquid repellency, and is a liquid that is supplied to the pattern (opening) of the cured film in the process of manufacturing a display element. Even if the material adheres to the vicinity of the opening, the formed droplet can be easily moved to the opening. Therefore, the display element of the present invention can eliminate the use of materials required for the display element in order to prevent adhesion of the droplets to areas other than the openings in the display element manufacturing and to prevent problems caused by the adhesion. In addition, contamination by the element material on the cured film can be prevented.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.

[Synthesis Example 1] Synthesis of Fluorine-Containing Polymer (A1) In a four-necked flask equipped with a stirrer, ethylene glycol methyl ethyl ether as a polymerization solvent and γ-methacryloxypropyl hepta as a radical polymerizable monomer (a-1) (Trifluoropropyl) -T8-silsesquioxane, radical polymerizable monomer (a-2) as 4-hydroxyphenyl vinyl ketone, radical polymerizable monomer (a-3) as glycidyl methacrylate, (3-ethyl- 3-Oxetanyl) methyl acrylate and dimethyl 2,2′-azobis (2-methylpropionate) as a polymerization initiator were charged in the following weight, and polymerization was performed by heating at a polymerization temperature of 90 ° C. for 2 hours.
Ethylene glycol methyl ethyl ether 54.0g
Glycidyl methacrylate 10.8g
γ-methacryloxypropylhepta (trifluoropropyl) -T8-silsesquioxane 2.7 g
4-hydroxyphenyl vinyl ketone 2.7 g
(3-Ethyl-3-oxetanyl) methyl acrylate 10.8 g
2,2′-Azobis (2-methylpropionate) 4.05 g

  The obtained reaction liquid was cooled to room temperature to obtain a 33.3% by weight solution of a polymer (A1) containing fluorine.

  A part of the obtained reaction solution was sampled, and the weight average molecular weight of the polymer (A1) containing fluorine was measured by GPC analysis (polyethylene oxide standard). As a result, the polymer (A1) containing fluorine had a weight average molecular weight of 2,100.

[Synthesis Example 2] Synthesis of Fluorine-Containing Polymer (A2) In the same manner as in Synthesis Example 1, the following components were charged in the following weights and polymerized.
Ethylene glycol methyl ethyl ether 54.0g
Glycidyl methacrylate 12.15g
γ-methacryloxypropylhepta (trifluoropropyl) -T8-silsesquioxane 1.35 g
4-hydroxyphenyl vinyl ketone 2.7 g
(3-Ethyl-3-oxetanyl) methyl acrylate 10.8 g
2,2′-Azobis (2-methylpropionate) 4.05 g

  The obtained reaction liquid was cooled to room temperature to obtain a 33.3% by weight solution of a polymer (A2) containing fluorine.

  A part of the obtained reaction solution was sampled, and the weight average molecular weight of the polymer (A2) containing fluorine was measured by GPC analysis (polyethylene oxide standard). As a result, the polymer (A2) containing fluorine had a weight average molecular weight of 2,100.

[Synthesis Example 3] Synthesis of Alkali-Soluble Polymer (C1) The following components were charged at the following weights in the same manner as in Synthesis Example 1 except that the polymerization was performed at a polymerization temperature of 110 ° C, and polymerization was performed.
Ethylene glycol methyl ethyl ether 54.0g
6.21 g of N-cyclohexylmaleimide
Methoxypolyethylene glycol # 400 methacrylate 0.54g
Dicyclopentanyl methacrylate 13.5g
Methacrylic acid 6.75g
2,2′-Azobis (2-methylpropionate) 4.05 g

  The obtained reaction liquid was cooled to room temperature to obtain a 33.3% by weight solution of the alkali-soluble polymer (C1).

  A part of the obtained reaction solution was sampled, and the weight average molecular weight of the alkali-soluble polymer (C1) was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C1) was 3,100.

[Synthesis Example 4] Synthesis of Alkali-Soluble Polymer (C2) The following components were charged at the following weights in the same manner as in Synthesis Example 1 except that the polymerization was performed at a polymerization temperature of 110 ° C, and polymerization was performed.
Ethylene glycol methyl ethyl ether 54.0g
9.45 g of N-cyclohexylmaleimide
Dicyclopentanyl methacrylate 10.8g
Methacrylic acid 6.75g
2,2′-Azobis (2-methylpropionate) 4.05 g

  The obtained reaction liquid was cooled to room temperature to obtain a 33.3% by weight solution of the alkali-soluble polymer (C2).

  A part of the obtained reaction solution was sampled, and the weight average molecular weight of the alkali-soluble polymer (C2) was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C2) was 3,800.

[Synthesis Example 5] Synthesis of Comparative Polymer (D1) In the same manner as in Synthesis Example 1, the following components were charged in the following weights and polymerized.
Ethylene glycol methyl ethyl ether 54.0g
Glycidyl methacrylate 10.8g
γ-methacryloxypropylheptacyclopentyl-T8-silsesquioxane
2.7g
4-hydroxyphenyl vinyl ketone 2.7 g
(3-Ethyl-3-oxetanyl) methyl acrylate 10.8 g
2,2′-Azobis (2-methylpropionate) 4.05 g

  The obtained reaction liquid was cooled to room temperature to obtain a 33.3% by weight solution of the comparative polymer (D1).

  A part of the obtained reaction solution was sampled, and the weight average molecular weight of the comparative polymer (D1) was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight of the comparative polymer (D1) was 2,100.

[Example 1]
The fluorine-containing polymer (A1) obtained in Synthesis Example 1, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl], which is a 1,2-quinonediazide compound [Phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid chloride condensate (average esterification rate 58%, hereinafter referred to as “PAD”), silicon surfactant byk344 (product) Name: Big Chemie Japan Co., Ltd., hereinafter abbreviated as “byk344”), diethylene glycol methyl ethyl ether as a solvent was mixed and dissolved in the following weight to obtain photosensitive composition 1.
Diethylene glycol methyl ethyl ether 1.34g
3.00 g of a 33.3% by weight polymer (A1) solution
PAD 0.30g
Byk344 0.01g

The photosensitive composition 1 was spin-coated at 600 rpm for 10 seconds on a glass substrate, and dried on a hot plate at 100 ° C. for 2 minutes. This substrate is passed through a mask for hole pattern formation in air using a proximity exposure machine TME-150PRC manufactured by Topcon Co., Ltd., and the light of 350 nm or less is cut through a wavelength cut filter to obtain g, h, i lines. Was taken out and exposed with an exposure gap of 100 μm. The exposure amount was 150 mJ / cm ² . The exposure amount was measured with an integrated light meter UIT-102 and a photoreceiver UVD-365PD manufactured by USHIO INC.

The exposed glass substrate was dip-developed with an aqueous tetramethylammonium hydroxide solution for 60 seconds to remove the photosensitive composition 1 in the exposed area. The substrate after development was washed with pure water for 60 seconds and then dried on a hot plate at 100 ° C. for 2 minutes. The entire surface of the substrate was exposed at an exposure amount of 300 mJ / cm ² without using a mask with the exposure machine, and then post-baked in an oven at 230 ° C. for 30 minutes to form a patterned transparent film having a thickness of 3 μm.

  The film thickness was defined as an average value of three measured values measured using a stylus type film thickness meter α step 200 manufactured by KLA-Tencor Japan.

[Evaluation Method for Photosensitive Composition and Patterned Transparent Film]
1) Residual film ratio after development The film thickness was measured before and after development and calculated from the following formula.
(Film thickness after development / film thickness before development) x 100 (%)

2) Resolution The substrate of the obtained patterned transparent film was observed at 400 times with an optical microscope, and the mask size with the glass surface exposed at the bottom of the hole pattern was confirmed. When a hole pattern was not formed, it was judged as defective (NG: No Good).

3) Adhesiveness The obtained pattern-like transparent film was evaluated by a cross-cut peel test (cross cut test). The evaluation was represented by the number of remaining grids after peeling the tape in 100 1 mm square grids.

4) Contact angle The contact angle of pure water on the film after firing was measured at 25 ° C. with a DropMaster 500 manufactured by Kyowa Interface Chemical Co., Ltd. The value 1 second after the pure water landing (2 μL) was taken as the contact angle value.

  The results obtained by the above evaluation method for the resin composition 1 are shown in Table 1.

[Example 2]
The photosensitive composition was the same as in Example 1, except that the fluorine-containing polymer (A2) obtained in Synthesis Example 2 was used instead of the fluorine-containing polymer (A1) used in Example 1. 2 was obtained and evaluated. The results are shown in Table 1.

[Example 3]
Instead of the fluorine-containing polymer (A1) used in Example 1, the fluorine-containing polymer (A1) obtained in Synthesis Example 1 and the alkali-soluble polymer (C1) obtained in Synthesis Example 3 A photosensitive composition 3 was obtained in the same manner as in Example 1 except that a 1: 1 mixture (by weight) was used, and this was evaluated. The results are shown in Table 1.

[Example 4]
Instead of the fluorine-containing polymer (A1) used in Example 1, the fluorine-containing polymer (A1) obtained in Synthesis Example 1 and the alkali-soluble polymer (C2) obtained in Synthesis Example 4 A photosensitive composition 4 was obtained in the same manner as in Example 1 except that a 1: 1 mixture (by weight) was used, and this was evaluated. The results are shown in Table 1.

[Comparative Example 1]
Photosensitive composition 5 was obtained in the same manner as in Example 1 except that the comparative polymer (D1) obtained in Synthesis Example 5 was used instead of the fluorine-containing polymer (A1) used in Example 1. And evaluated this. The results are shown in Table 1.

[Comparative Example 2]
Instead of the fluorine-containing polymer (A1) used in Example 1, the comparative polymer (D1) obtained in Synthesis Example 5 and the alkali-soluble polymer (C2) obtained in Synthesis Example 4 A photosensitive composition 6 was obtained in the same manner as in Example 1 except that a 1: 1 mixture (weight ratio) was used, and this was evaluated. The results are shown in Table 1.

  The photosensitive composition of this invention can be used for a liquid crystal display element, for example.

Claims (12)

A photosensitive composition containing a polymer (A) containing fluorine and a 1,2-quinonediazide compound (B),
The photosensitive composition in which the polymer (A) containing the fluorine has a fluorine-containing silsesquioxane group represented by the following formula (I) and an alkali-soluble functional group.

_{- [(R-SiO 1.5)} (Rf-SiO 1.5) n-1] (I)

(In the formula (I),
R represents a single bond or alkylene having 1 to 20 carbon atoms in which arbitrary methylene may be replaced by oxygen, and arbitrary hydrogen may be replaced by fluorine;
Rf is, independently: a) any methylene having 1 to 20 carbon atoms which may be replaced by oxygen fluoroalkyl; b) carbon one or more hydrogens in the aryl is replaced by fluorine or -CF ₃ A fluoroaryl having 6 to 20; c) a fluoroarylalkyl having 7 to 20 carbons in which one or more hydrogens in the aryl are replaced by fluorine or —CF ₃ ; or d) any methylene is replaced by oxygen An alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, an arylalkyl having 7 to 20 carbon atoms in which any methylene may be replaced by oxygen, and one or more of Rf is a) ~ C),
n represents an integer of 4 to 24. However, oxygen does not adjoin in R and Rf. ) The photosensitive composition of Claim 1 in which the said fluorine-containing silsesquioxane group is represented by following formula (II).
(In the formula (II),
R represents a single bond or alkylene having 1 to 20 carbon atoms in which arbitrary methylene may be replaced by oxygen, and arbitrary hydrogen may be replaced by fluorine;
Rf is, independently: a) any methylene having 1 to 20 carbon atoms which may be replaced by oxygen fluoroalkyl; b) carbon one or more hydrogens in the aryl is replaced by fluorine or -CF ₃ A fluoroaryl having 6 to 20; c) a fluoroarylalkyl having 7 to 20 carbons in which one or more hydrogens in the aryl are replaced by fluorine or —CF ₃ ; or d) any methylene is replaced by oxygen An alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, an arylalkyl having 7 to 20 carbon atoms in which any methylene may be replaced by oxygen, and one or more of Rf is a) ~c) Ru der any of the. However, oxygen does not adjoin in R and Rf. )   The photosensitive composition according to claim 1 or 2, wherein the alkali-soluble functional group is one or both of a carboxyl group and a phenolic hydroxyl group. Polymers containing fluorine (A) is, the fluorine-containing silsesquioxane group and a radical polymerizable monomer having a radically polymerizable functional group (a-1), wherein the La radical polymerizable functional groups alkali-soluble functional The photosensitive composition as described in any one of Claims 1-3 which is a radical polymer of the radically polymerizable monomer containing the radically polymerizable monomer (a-2) which has a group. The radical polymerizable functional group is a functional group represented by CH ₂ ═CH—, CH ₂ ═CHO—, CH ₂ ═C (CH ₃ ) —COO—, CH ₂ ═CH—COO— and the following formula (III). The photosensitive composition of Claim 4 which is one or more chosen from the group which consists of groups.
Polymers containing fluorine (A) is, the radical polymerizable monomer (a-1) and the radical polymerization of the radical polymerizable monomer containing (a-2) other than the other radical polymerizable monomer (a-3) in it, photosensitive composition according to claim 4 or 5. The photosensitive composition according to claim 6, wherein the other radical polymerizable monomer (a-3) is one or more selected from the group consisting of a ( meth) acrylic acid derivative and a styrene derivative.   The photosensitive composition as described in any one of Claims 1-7 which further contains an alkali-soluble polymer (C).   The alkali-soluble polymer (C) is selected from the group consisting of a radical polymerizable monomer having an unsaturated carboxylic acid, a radical polymerizable monomer having an unsaturated carboxylic acid anhydride, and a radical polymerizable monomer having a phenolic hydroxyl group. The photosensitive composition of Claim 8 which is a radical polymer of the radically polymerizable monomer containing 1 or more.   The photosensitive composition in any one of Claims 1-9 which further contains a solvent.   The cured film obtained by baking the film | membrane of the photosensitive composition as described in any one of Claims 1-10.   A display element comprising the cured film according to claim 11.