TW201940973A - Radiation-sensitive composition, hardened film, and display element having good storage stability - Google Patents

Abstract

The invention provides a radiation-sensitive composition with good storage stability. The radiation-sensitive composition comprises alkali-soluble resin, a radiation-sensitive compound, propylene glycol monomethyl ether acetate, and allyl methyl ether.

Description

Radiation-sensitive composition, cured film and display element

The present invention relates to a radiation-sensitive composition.

In the past, the radiation-sensitive composition has been used to form a cured film of a display element. The cured film is a patterned cured film such as an interlayer insulating film, a protective film, and a spacer (for example, refer to Patent Document 1). .
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-275463

[Problems to be Solved by the Invention]
According to the study by the present inventors, when the conventional radiation-sensitive composition is configured as a liquid composition, the storage stability may not be good. An object of the present invention is to provide a radiation-sensitive composition with good storage stability.
[Technical means to solve the problem]

The present inventors conducted diligent research in order to solve the problems, and as a result, they found that the problems can be solved by a radiation-sensitive composition having the following composition, and thus completed the present invention. That is, this invention relates to the following [1]-[9].

[1] A radiation-sensitive composition comprising: an alkali-soluble resin, a radiation-sensitive compound, propylene glycol monomethyl ether acetate, and allyl methyl ether.
[2] The radiation-sensitive composition according to the above [1], which contains the allyl methyl ether in a range of 10 wtppm to 50000 wtppm.
[3] The radiation-sensitive composition according to the above [1] or [2], wherein the weight-average molecular weight (Mw) of the polystyrene-equivalent alkali-soluble resin obtained by gel permeation chromatography is 1,000 The weight average molecular weight (Mw) / number average molecular weight (Mn) in terms of polystyrene is 1.0 to 5.0.
[4] The radiation-sensitive composition according to any one of the above [1] to [3], wherein the alkali-soluble resin is an ethylenically unsaturated monomer having one or more acidic functional groups and is capable of reacting with A copolymer of other ethylenically unsaturated monomers copolymerized with the monomer.
[5] The radiation-sensitive composition according to any one of the above [1] to [4], further comprising a polymerizable compound having at least one ethylenically unsaturated double bond.
[6] The radiation-sensitive composition according to any one of the above [1] to [5], for forming a cured film as an interlayer insulating film, a protective film, or a separator.
[7] A cured film formed from the radiation-sensitive composition according to the above [6], and used as an interlayer insulating film, a protective film, or a separator.
[8] A display element having a cured film according to the above [7].
[9] A radiation-sensitive composition comprising: an alkali-soluble resin; a radiation-sensitive compound; and selected from 1-methoxy-1- (2-methoxyethoxy) ethane, 1,3- At least one compound among dimethoxy-2,2-dimethylpropane, 4,4,6-trimethyl-1,3-dioxane, and 1-penten-3-ol.
[Effect of the invention]

According to the present invention, a radiation-sensitive composition having good storage stability can be provided.

Preferred upper limit values and lower limit values among the content ratios of the components and the like are described in this specification, and numerical ranges specified by any combination of the described upper limit and lower limit values are also described in this specification.

Hereinafter, the mode for implementing this invention is demonstrated. These problems can be solved by the first radiation-sensitive composition and the second radiation-sensitive composition of the present invention described below.

[Radiosensitive composition]
The first radiation-sensitive composition of the present invention includes an alkali-soluble resin, a radiation-sensitive compound, propylene glycol monomethyl ether acetate, and allyl methyl ether.

The second radiation-sensitive composition of the present invention includes: an alkali-soluble resin; a radiation-sensitive compound; and a compound selected from 1-methoxy-1- (2-methoxyethoxy) ethane, 1,3-di At least one of methoxy-2,2-dimethylpropane, 4,4,6-trimethyl-1,3-dioxane, and 1-penten-3-ol.

Hereinafter, the first radiation-sensitive composition of the present invention is also referred to as "the first composition of the present invention", and the second radiation-sensitive composition of the present invention is also referred to as the "second composition of the present invention", The case where these first and second compositions are common is also collectively referred to as "the composition of the present invention", and the alkali-soluble resin is also referred to as "alkali-soluble resin (A)" or "resin (A)", and The radiation-sensitive compound is called "radiation-sensitive compound (B)".

In addition, propylene glycol monomethyl ether acetate is also called "PGMEA". Also selected from 1-methoxy-1- (2-methoxyethoxy) ethane, 1,3-dimethoxy-2,2-dimethylpropane, 4,4,6-tri At least one of methyl-1,3-dioxane and 1-penten-3-ol is called a "specific solvent".

[Chemical 1]
1-methoxy-1- (2-methoxyethoxy) ethane
1,3-dimethoxy-2,2-dimethyl-propane

4,4,6-trimethyl-1,3-dioxane
1-pentene-3-ol The composition of the present invention is usually prepared as a liquid composition by formulating a solvent.

[First composition]
The first composition of the present invention contains PEMEA as a solvent.
Since the alkali-soluble resin (A) and the radiation-sensitive compound (B) in the first composition have high solubility in PGMEA, the first composition can use at least PGMEA as a solvent.
The first composition of the present invention contains allyl methyl ether.

[Chemical 2]

Allyl methyl ether

Since allyl methyl ether has a radical trapping property, for example, when the first composition is a negative type, the polymerization of the polymerizable compound (E) described below can be inhibited during storage as a liquid composition. For example, in the case of a positive type, degradation such as decomposition of the alkali-soluble resin (A) can be suppressed, whereby the storage stability of the first composition is improved. In addition, since the allyl methyl ether has a low boiling point, the allyl methyl ether is removed by pre-baking after the first composition is applied, and the effect on the radiation sensitivity is also small.

The upper limit value of the content ratio of the allyl methyl ether in the first composition is preferably 50,000 wtppm, more preferably 10,000 wtppm, even more preferably 7500 wtppm, and particularly preferably 5000 wtppm. When the content ratio of allyl methyl ether is equal to or less than the upper limit value, it is preferable from the viewpoint of coatability and radiation sensitivity of the first composition, and formation of the first composition can be suppressed. The surface of the coating film is rough, and whitening of the cured film thus obtained can be suppressed, which is preferable.

The lower limit of the content ratio of allyl methyl ether in the first composition is preferably 10 wtppm, and more preferably 50 wtppm. If the content ratio of allyl methyl ether is more than the said lower limit, it is preferable from the viewpoint of the storage stability of the said 1st composition. The content ratio of allyl methyl ether can be measured by gas chromatography.

The first composition of the present invention may contain, in addition to PGMEA, as a solvent, other solvents that disperse or dissolve the components constituting the first composition, do not react with these components, and have moderate volatility ( 1).

Examples of other solvents (1) include:
Ethylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; ethylene glycol monomethyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate ; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether ; Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate (except PGMEA);
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol, propylene glycol, tetrahydrofurfuryl alcohol;
Methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate and other lactates; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate , Aliphatic carboxylic acid esters such as isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate and other esters;
Ketone solvents such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, Solvent solvents such as N-methylpyrrolidone; lactone solvents such as γ-butyrolactone;
Aromatic hydrocarbon solvents such as toluene and xylene.

Other solvents (1) can be used alone or in combination of two or more.
The upper limit of the content ratio of PGMEA in the first composition of the present invention is preferably 95% by mass, more preferably 90% by mass, even more preferably 85% by mass; and the lower limit is preferably 50% by mass, more It is preferably 60% by mass, and even more preferably 65% by mass.

In addition, the upper limit value of the content ratio of all components other than the solvent in the first composition of the present invention is preferably 50% by mass, more preferably 40% by mass, and still more preferably 35% by mass; and the lower limit is preferably It is 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass. All components other than the solvent are, for example, an alkali-soluble resin (A), a radiation-sensitive compound (B), allyl methyl ether, and other components added arbitrarily.
The liquid composition prepared as described above can be used after being filtered, for example, using a filter having a pore size of about 0.2 μm, or the like.

[Second composition]
The second composition of the present invention contains the specific solvent.
Since the alkali-soluble resin (A) and the radiation-sensitive compound (B) in the second composition have high solubility in the specific solvent, the second composition can use at least the specific solvent as a solvent.

The second composition containing the specific solvent is excellent in storage stability. In addition, as storage stability improves, exposure margins also increase. Details of the exposure margin are described in the column of Examples.

The second composition of the present invention may contain, as a solvent, other than the specific solvent described above, a component which disperses or dissolves the components constituting the radiation-sensitive composition, does not react with these components, and has a moderate volatility. Solvent (2). Examples of the other solvent (2) include the above-mentioned other solvent (1) (excluding the specific solvent) and PGMEA.

Other solvents (2) can be used alone or in combination of two or more.
The upper limit of the content ratio of the specific solvent in the second composition of the present invention is preferably 95% by mass, more preferably 90% by mass, and still more preferably 85% by mass; and the lower limit is preferably 50% by mass. %, More preferably 60% by mass, and even more preferably 65% by mass.

In addition, the upper limit value of the content ratio of all components other than the solvent in the second composition of the present invention is preferably 50% by mass, more preferably 40% by mass, and still more preferably 35% by mass; and the lower limit is preferably It is 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass. All components other than the solvent are, for example, an alkali-soluble resin (A), a radiation-sensitive compound (B), and other components added arbitrarily.

The liquid composition prepared as described above may be used after being filtered, for example, using a filter having a pore size of about 0.2 μm, or the like.
Hereinafter, each component other than the said solvent is demonstrated.

<Alkali soluble resin (A)>
As the alkali-soluble resin (A), for example, a polymer having an acidic functional group such as a carboxyl group, a phenolic hydroxyl group, and a fluorinated hydroxyalkyl group is preferable. The alkali-soluble resin means that the resin is soluble or swellable in an alkaline developer such as a tetramethylammonium hydroxide aqueous solution having a concentration of 2.38% by mass.

The fluorinated hydroxyalkyl group is a hydroxyalkyl group in which a part of hydrogen atoms bonded to a carbon atom is substituted with a fluorine atom, and is, for example, a group represented by -C (R ^a1 ) (R ^a2 ) OH. In the formula, R ^a1 is a hydrogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms, and R ^a2 is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms. .

Examples of the polymer having an acidic functional group include a novolac resin, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, a phenol-dicyclopentadiene condensation resin, Polymers with phenolic hydroxyl groups, such as polybenzoxazole precursors, polyhydroxystyrene, copolymers of hydroxystyrene and styrene; carboxyl-containing epoxy (meth) acrylates with a novolak-type skeleton in the main chain Polymers having a carboxyl group, such as resin and polyamic acid.

Examples of the polymer having an acidic functional group include an ethylenically unsaturated monomer (hereinafter also referred to as an "unsaturated monomer (a1)") having one or more acidic functional groups, and a polymer capable of reacting with (a1) Copolymer of other copolymerized ethylenic unsaturated monomer (hereinafter also referred to as "unsaturated monomer (a2)"). A (meth) acrylic polymer having an acidic functional group is particularly preferred.

Examples of the unsaturated monomer (a1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinate mono [2- (meth) acryloxyethyl] ester, and ω-carboxyl. Polycaprolactone mono (meth) acrylate, p-vinylbenzoic acid and other unsaturated monomers containing carboxyl groups; hydroxystyrene, p-isopropenylphenol, hydroxyphenylacrylate, hydroxyphenylacrylamide, etc. Unsaturated monomers with phenolic hydroxyl groups; unsaturated monomers containing fluorinated hydroxyalkyl groups such as 4- (1,1,1,3,3,3-hexafluoro-2-hydroxypropane-2-yl) styrene . Among these, at least (meth) acrylic acid is preferably used from the viewpoint of polymerizability.

The unsaturated monomer (a1) may be used alone or in combination of two or more.
Examples of the unsaturated monomer (a2) include N-substituted maleates such as N-arylmaleimide, N-alkylmaleimide, and N-cycloalkylmaleimide. Ammonium imine; aromatic vinyl compounds such as styrene and its derivatives; alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, alicyclic esters of (meth) acrylic acid, (methyl ) (Meth) acrylic acid esters (meth) acrylic acid esters having cyclic ether rings, such as acrylic acid esters containing aromatic rings, oxetane ring, oxetane ring, oxetane ring, etc .; containing benzene Silane compounds containing aromatic rings such as vinyl silane compounds; vinyl ethers such as alicyclic vinyl ethers; polymer chains of aromatic vinyl compounds, polymer chains of (meth) acrylates, polysiloxanes A macromonomer having a mono (meth) acrylfluorene group at the end of a polymer molecular chain such as an alkane molecular chain. Among these, from the viewpoint of imparting a cross-linkable functional group to an alkali-soluble resin, it is preferred to use a member selected from a (meth) acrylate having an oxetane ring and a (methyl) having an oxetane ring. At least one of acrylates.

More specifically, [0060] to [0062] of Japanese Patent Laid-Open No. 2015-004968, [0036] to [0045] of Japanese Patent Laid-Open No. 2008-233346, and Japanese Patent Laid-Open No. 2009-229567 Monomers described in [0013] to [0021] of the publication.

The unsaturated monomer (a2) may be used alone or in combination of two or more.
Specific examples of the copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2) include, for example, Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, and Japanese Patent Laid-Open Gazette No. 10-31308, Gazette No. 10-300922, Gazette No. 11-174224, Gazette No. 11-258415, Gazette No. 2000-56118, Gazette No. 2000-56118 2004-101728, Japanese Patent Laid-Open No. 2006-201549, Japanese Patent Laid-Open No. 2007-128062, Japanese Patent Laid-Open No. 2008-233563, Japanese Patent Laid-Open No. 2017-181928, Japanese Patent Laid-Open No. Copolymer disclosed in 2017-173376 and the like.

For example, Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 9-325494, and Japanese Patent Laid-Open No. 11- As disclosed in Japanese Unexamined Patent Publication No. 140144 and Japanese Patent Laid-Open No. 2008-181095, a carboxyl group-containing (meth) acrylic polymer having a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group in a side chain can also be used.

In the copolymer (a1) and (a2), the upper limit value of the content ratio of the structural unit derived from the unsaturated monomer (a1) is preferably 50% by mass, more preferably 40% by mass; and the lower limit value is preferably It is 5% by mass, and more preferably 10% by mass.

In one embodiment, the copolymer of (a1) and (a2) is preferably an unsaturated monomer (a1), and is selected from a (meth) acrylate having an oxetane ring and an oxetane Copolymer of at least one of cyclic (meth) acrylates. In the copolymer, an unsaturated monomer (a2) other than these may be copolymerized. For example, it may be further copolymerized with an aromatic vinyl compound, an aromatic ring-containing ester of (meth) acrylic acid, an alkyl (meth) acrylate, an N-substituted maleimide, and a styryl-containing silane. At least one of the compounds.

The copolymer of (a1) and (a2) is derived from at least one selected from a (meth) acrylate having an oxepane ring and a (meth) acrylate having an oxetane The upper limit of the content ratio of the structural unit is preferably 50% by mass, more preferably 40% by mass; the lower limit is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass.

The copolymer of (a1) and (a2) can be produced by a known method. For example, it can be produced by Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006-259680, and International Publication No. 2007 / The method disclosed in 029871 and the like is used to control the structure or weight average molecular weight and molecular weight distribution.

Further, examples of the alkali-soluble resin (A) include alkali-soluble polysiloxane, polyimide, and polybenzoxazole.
Specific examples of the polysiloxane include International Publication No. 2017/188047, International Publication No. 2017/169763, International Publication No. 2017/159876, Japanese Patent Laid-Open No. 2013-114238, and Japanese Patent Laid-Open No. Copolymers disclosed in 2012-53381, Japanese Patent Laid-Open No. 2010-32977, and the like.

Specific examples of polyimide or polybenzoxazole include International Publication No. 2017/169763, International Publication No. 2017/159876, International Publication No. 2017/057281, International Publication No. 2017/159476, International Publication No. 2017/073481, International Publication No. 2017/038828, International Publication No. 2016/148176, Japanese Patent Laid-Open No. 2015-114355, Japanese Patent Laid-Open No. 2013-164432, Japanese Patent Laid-Open No. 2010- Copolymer disclosed in Japanese Patent No. 72143 and the like.

The upper limit of the weight-average molecular weight (Mw) of the alkali-soluble resin (A) is usually 100,000, preferably 50,000, and the lower limit is usually 1,000, preferably 5,000. The upper limit of the ratio (molecular weight distribution: Mw / Mn) of the number-average molecular weight (Mn) of the alkali-soluble resin (A) to the weight-average molecular weight (Mw) is usually 5.0, preferably 3.0; the lower limit is usually 1.0, preferably Is 1.1. Mw and Mn are polystyrene-equivalent values measured by Gel Penetration Chromatography (hereinafter also referred to as "GPC").

The resin (A) may be used alone or in combination of two or more.
In the composition of the present invention, the upper limit value of the content ratio of the alkali-soluble resin (A) in 100% by mass of all components except the solvent of the composition is preferably 99% by mass, more preferably 95% by mass, and even more preferably It is preferably 90% by mass, particularly preferably 85% by mass; the lower limit value is preferably 40% by mass, more preferably 50% by mass, and even more preferably 60% by mass.

＜ Radiosensitive compound (B) ＞
Examples of the radiation-sensitive compound (B) include a radiation-sensitive radical polymerization initiator (B1) and a radiation-sensitive acid generator (B2).

"Radiation-sensitive Radical Polymerization Initiator (B1)"
The radiation-sensitive radical polymerization initiator (B1) (hereinafter also referred to as "component (B1)") is a compound that generates radicals upon irradiation with radiation. When the composition of the present invention contains the component (B1), it can function as a radiation-curable resin composition, and by using generated radicals, an alkali-soluble resin (A), a polymerizable compound (E) described later, and the like Polymerization thereby exerts negative radiation-sensitive characteristics. By containing the component (B1), the composition of the present invention can further improve radiation sensitivity.

Examples of the component (B1) include an O-fluorenyl oxime compound, an acetophenone compound, a biimidazole compound, and a thioxanthone compound.
Examples of O-fluorenyl oxime compounds include 1- [4- (phenylthio) -2- (O-benzylidene oxime)], 1,2-octanedione 1- [4- (benzene Thio) -2- (O-benzylideneoxime)], ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl] -1- (O-ethylamidoxime), 1- [9-ethyl-6-benzylidene-9.H.-oxazol-3-yl] -octanone-1-one oxime-O- Acetate, 1- [9-ethyl-6- (2-methylbenzylidene) -9.H.-oxazol-3-yl] -ethane-1-oneoxime-O-benzyl Acid ester, 1- [9-n-butyl-6- (2-ethylbenzylidene) -9.H.-oxazol-3-yl] -ethane-1-oneoxime-O-benzyl Acid ester.

Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound. Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one and 2-dimethylamino-2 -(4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) 2-morpholinylpropan-1-one. Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'- Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorobenzene) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, preferably 2,2'-bis (2,4-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole.

Examples of the thioxanthone compound include thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Tons of ketones.

Among these, an O-fluorenyl oxime compound, an acetophenone compound, and a thioxanthone compound are preferable, and an O-fluorenyl oxime compound, an α-amino ketone compound, and a thioxanthone compound are more preferable, and 1,2-octane is more preferable. Ketone 1- [4- (phenylthio) -2- (O-benzylideneoxime)], ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H -Oxazol-3-yl] -1- (O-acetamidooxime), 2-methyl-1- (4-methylthiophenyl) -2-morpholinylpropane-1-one, 2 , 4-diethylthioxanthone.

When the component (B1) is used as the radiation-sensitive compound (B), in the composition of the present invention, the upper limit value of the content of the component (B1) is preferably 30 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A). Is more preferably 25 parts by mass, and still more preferably 20 parts by mass; the lower limit value is preferably 1 part by mass, more preferably 3 parts by mass, and even more preferably 6 parts by mass. According to this aspect, the adhesiveness of the cured film formed from the composition of the present invention can be further improved, and the radiation sensitivity of the composition of the present invention can be further improved.

"Radiation-sensitive acid generator (B2)"
The radiation-sensitive acid generator (B2) (hereinafter also referred to as "acid generator (B2)") is a compound that generates an acid upon irradiation with radiation. By containing the acid generator (B2) in the composition of the present invention, radiation sensitivity can be further improved.

Examples of the acid generator (B2) include quinonediazide compounds, oxime sulfonate compounds, onium salts, sulfonylimine compounds, halogen-containing compounds, diazomethane compounds, sulfonium compounds, and sulfonate esters. Compounds, carboxylic acid ester compounds.

A quinonediazide compound is a compound that generates a carboxylic acid by irradiation of radiation. By containing the quinonediazide compound as the acid generator (B2), the composition of the present invention improves the solubility of the alkali developing solution in the radiation-irradiated portion of the generated carboxylic acid, and thereby exerts positive radiation sensitivity. characteristic.

As the quinonediazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as a "mother core") and 1,2-naphthoquinonediazidesulfonium halide can be used.

Examples of the mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother cores.

Examples of the trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.
Examples of the tetrahydroxybenzophenone include 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4 4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxy Benzophenone.

Examples of the pentahydroxybenzophenone include 2,3,4,2 ', 6'-pentahydroxybenzophenone.
Examples of the hexahydroxybenzophenone include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy Benzophenone and so on.

Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1- Tris (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.

Examples of other mother cores include 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylene] bisphenol, and 2- Methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methyl (Ethyl) -4,6-dihydroxyphenyl} -1-methylethyl] benzene.

The 1,2-naphthoquinonediazidesulfonium halide is preferably 1,2-naphthoquinonediazidesulfonyl chloride. Examples of 1,2-naphthoquinonediazidesulfonyl chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride, and 1,2-naphthoquinonediazide-5-sulfonyl chloride. Among these, 1,2-naphthoquinonediazide-5-sulfonyl chloride is preferred.

Synthesis of a quinonediazide compound can be performed by a well-known condensation reaction. In the condensation reaction, 1 corresponding to the number of OH groups in the phenolic compound or the alcoholic compound is preferably 30 mol% to 85 mol%, and more preferably 50 mol% to 70 mol%. , 2-naphthoquinonediazidesulfonium halide.

As the acid generator, known compounds can be used as the oxime sulfonate compound, onium salt, sulfonylimine compound, halogen-containing compound, diazomethane compound, sulfonium compound, sulfonate compound, and carboxylate compound. Specific examples of the sulfonimide compound include N-sulfonyloxyfluorenimine compounds, and specific examples include N- (trifluoromethylsulfonyloxy) succinimine, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethyl Sulfofluorenyloxy) bicyclo [2.2.1] hept-5-en-2,3-dicarboxyfluorenimine, N- (trifluoromethylsulfonyloxy) naphthylfluorenimine.

When a quinonediazide compound is used as the radiation-sensitive compound (B), in the composition of the present invention, the upper limit value of the content of the quinonediazide compound is preferably 40 relative to 100 parts by mass of the alkali-soluble resin (A). The mass part is more preferably 35 parts by mass, and still more preferably 30 parts by mass; the lower limit value is preferably 5 parts by mass, more preferably 10 parts by mass, and still more preferably 15 parts by mass. According to this aspect, the adhesiveness of the cured film formed from the composition of the present invention can be further improved, and the radiation sensitivity of the composition of the present invention can be further improved.

When an acid generator (B2) other than the quinonediazide compound is used as the radiation-sensitive compound (B), in the composition of the present invention, the acid generator (B) is 100 parts by mass of the alkali-soluble resin (A). The upper limit of the content of B2) is preferably 20 parts by mass, more preferably 15 parts by mass, and even more preferably 10 parts by mass; the lower limit is preferably 1 part by mass, more preferably 2 parts by mass, and even more preferably 3 Parts by mass.

＜ Other ingredients ＞
The composition of the present invention contains an alkali-soluble resin (A) and a radiation-sensitive compound (B) as essential components, and may optionally contain at least one selected from an adhesion promoter (C), a surfactant (D), and having at least one ethylenic property. At least one of a polymerizable compound (E) having a saturated double bond, an epoxy resin (F) other than the alkali-soluble resin (A), and a thermoacid-generating compound (G) is used as another component.

In order to improve the adhesion between the substrate and the coating film, the composition of the present invention may contain an adhesion assistant (C). Examples of the adhesion assistant (C) include functional silane coupling agents such as silane coupling agents having reactive functional groups such as a carboxyl group, a methacryl group, a vinyl group, an isocyanate group, an epoxy group, and an amino group. Specific examples include trimethoxysilylbenzoic acid, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-isocyanatepropyl. Triethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. As the adhesion promoter (C), for example, compounds described in Japanese Patent Laid-Open No. 2006-126397 and Japanese Patent Laid-Open No. 2009-204865 can also be used. The adhesion promoter (C) may be used alone or in combination of two or more.

The composition of the present invention may contain the adhesion assistant (C) in a range of preferably 20 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A).

The composition of the present invention may contain a surfactant (D) in order to improve its coatability. Examples of the surfactant (D) include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. The surfactant (D) can be used alone or in combination of two or more.

The composition of the present invention may contain a surfactant (D) in a range of preferably 5 parts by mass or less, more preferably 2 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (A).

The composition of the present invention may contain a polymerizable compound (E) having at least one ethylenically unsaturated double bond in order to make the composition negative, or to improve the heat resistance and hardness of the cured film. Examples of the polymerizable compound (E) include (meth) acrylates such as monofunctional (meth) acrylates, difunctional (meth) acrylates, and trifunctional or higher (meth) acrylates. The number of (meth) acrylic acid fluorene groups in the (meth) acrylate is preferably 2 to 6. Among these, trifunctional or higher (meth) acrylates are preferred, and examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. . The polymerizable compound (E) may be used alone or in combination of two or more.

The composition of the present invention may contain the polymerizable compound (E) in a range of preferably 100 parts by mass or less, and more preferably 75 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A).

In order to improve the heat resistance and hardness of the cured film, the composition of the present invention may contain an epoxy resin (F) other than the alkali-soluble resin (A). The alkali-soluble resin (A) also contains a compound that can be called an “epoxy resin”, but is different from the epoxy resin (F) in that it has alkali solubility. The epoxy resin (F) here is alkali-insoluble.

The epoxy resin (F) is not limited as long as it does not affect compatibility, and examples thereof include bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and cyclic Aliphatic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, heterocyclic epoxy resin, and resin obtained by (co) polymerizing glycidyl methacrylate. Among these, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, and a glycidyl ester type epoxy resin are preferable. The epoxy resin (F) can be used alone or in combination of two or more.

The composition of the present invention may preferably contain the epoxy resin (F) in an amount of 50 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A).
In order to improve the heat resistance and hardness of the cured film, the composition of the present invention may contain a thermosensitive acid generating compound (G). Examples of the thermosensitive acid generating compound (G) include onium salts such as a sulfonium salt, a benzothiazolium salt, an ammonium salt, and a sulfonium salt. The thermo-acid-generating compound (G) may be used alone or in combination of two or more.

The composition of the present invention may contain the thermosensitive acid-generating compound (G) in a range of preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A).
The composition of the present invention described above can be suitably used as a cured film and the like of an interlayer insulating film, a protective film, and a separator; a material for forming a cured film included in a display element; and the like.

[Hardened film and manufacturing method thereof]
The method of manufacturing the cured film of this invention using the radiation-sensitive composition of this invention is described. Examples of the cured film of the present invention include an interlayer insulating film, a protective film, and a separator. The film thickness of the cured film is usually 0.5 μm to 6 μm. The cured film of the present invention has high hardness and is excellent in heat resistance and solvent resistance.

The cured film of the present invention can be formed, for example, by a manufacturing method including the following steps: step (1), forming a coating film of the radiation-sensitive composition of the present invention on a substrate; step (2), At least a part is irradiated with radiation; step (3), developing the coating film after radiation irradiation; and step (4), heating the developed coating film to obtain a cured film.

＜ Step (1) ＞
In the step (1), the composition of the present invention is coated on a substrate, and it is preferable to perform pre-baking to remove the solvent to form a coating film of the radiation-sensitive composition.
Examples of the substrate include a glass substrate, a silicon substrate, and a substrate having various metal members formed on its surface.

Examples of the coating method of the composition include a spray method, a roll coating method, a spin coating method (spin coating method), a slot die coating method, a bar coating method, and an inkjet method. The spin coating method and the slot die coating are preferred. law.
The conditions for the pre-baking also differ depending on the kind, content ratio, and the like of each component in the composition of the present invention. For example, it can be performed at 60 to 110 ° C. for about 30 seconds to 15 minutes.
The film thickness of the coating film of the radiation-sensitive composition after pre-baking is usually 0.5 μm to 6 μm.

＜ Step (2) ＞
In step (2), at least a part of the coating film formed in step (1) is irradiated with radiation. For example, the coating film is irradiated with radiation through a mask having a predetermined pattern.
Examples of the radiation include visible rays, ultraviolet rays, X-rays, and charged particle beams. Examples of visible light and ultraviolet rays include g-ray (wavelength 436 nm), h-ray (wavelength 405 nm), i-ray (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (Wavelength 193 nm). Examples of the X-ray include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these, visible rays and ultraviolet rays are preferred, and radiation containing at least one selected from the group consisting of g-rays, h-rays, i-rays, and KrF excimer lasers is particularly preferred.
The exposure amount is usually 5 mJ / cm ² to 1000 mJ / cm ² .

＜ Step (3) ＞
In step (3), the coating film after the radiation irradiation is developed using developability, and the irradiation portion of the radiation is removed. Thereby, a patterned coating film can be obtained.
In the development process, an alkaline developer is usually used, and examples thereof include an aqueous solution of an alkaline compound (basic compound). Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylamine ethanol, di-n-propylamine, Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, pyridine, 1,8-diazabicyclo [5.4.0 ] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene. The concentration of the basic compound in the alkaline developing solution is usually from 0.1% by mass to 10% by mass. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution, or various organic solvents in which the composition of the present invention is dissolved can be used as a developing solution.

Examples of the development method include a liquid coating method, a dipping method, a shaking dipping method, and a shower method. The development time varies depending on the composition of the composition, and it can be set to, for example, 30 seconds to 120 seconds. Further, the patterned coating film may be subjected to a rinsing treatment such as washing with running water.

Further, the entire surface of the patterned coating film may be irradiated with radiation (post-exposure) to perform a decomposition treatment of the compound (B) remaining in the coating film. The exposure amount in the post-exposure is usually 200 mJ / cm ² to 500 mJ / cm ² .

＜ Step (4) ＞
In step (4), the coating film obtained in step (3), specifically, the patterned coating film is heated (post-baking treatment) to obtain a cured film.
Regarding the heating in the hardening treatment of the coating film, for example, a heating device such as a hot plate or an oven can be used. The heating temperature in the hardening treatment is usually 120 ° C to 250 ° C. The heating time in the hardening process varies depending on the type of heating device, for example, when the heat treatment is performed on a hot plate, it is 5 minutes to 30 minutes, and when the heat treatment is performed in an oven, it is 30 minutes to 100 minutes. In this case, a stepwise baking method in which the heating step is performed twice or more may be used.
A cured film can be obtained in the above manner. In one embodiment, for example, a hardened film as a target interlayer insulating film, a protective film, and a spacer can be formed on a substrate.

[Display element]
The display element of the present invention includes the cured film of the present invention as described above. The cured film is, for example, a protective film for thin film transistor (TFT) in a display element or an interlayer insulating film. The display element of the present invention is, for example, a liquid crystal display or an organic electroluminescence (EL) display element.
[Example]

Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples. In the following description, unless otherwise mentioned, "mass part" is described as "part".

<Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn)>
For alkali-soluble resin (A), Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) is calculated from the obtained Mw and Mn.
Device: "GPC-101" (manufactured by Showa Denko)
GPC column: Combination of GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Shimadzu GLC)
Mobile phase: Tetrahydrofuran column temperature: 40 ° C
Flow rate: 1.0 mL / min
Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Reference material: Monodisperse polystyrene

[Synthesis of alkali-soluble resin]
[Synthesis Example 1] (Synthesis of Polymer (A-1))
A flask including a cooling tube and a stirrer was charged with 10 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate (PGMEA). Next, 20 parts of methacrylic acid, 20 parts of glycidyl methacrylate, 20 parts of 3,4-epoxycyclohexylmethyl methacrylate, and 40 parts of styrene were charged, and nitrogen substitution was performed. The polymer solution was gradually stirred and the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to perform polymerization, thereby obtaining a polymer solution containing a polymer (A-1) as an alkali-soluble resin. The obtained polymer solution was reprecipitated in hexane, filtered, and purified by vacuum drying to dissolve the polymer (A-1) in PGMEA to prepare a solution having a polymer concentration of 30% by mass. The polymer (A-1) had a weight average molecular weight (Mw) of 10,000 and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.3.

[Synthesis Example 2 to Synthesis Example 12] (Synthesis of Polymer (A-2) to Polymer (A-12))
A polymer (A-2) to a polymer (A-12) were obtained by the same method as in Synthesis Example 1 except that the components shown in the following Table 1 were used, and each component was prepared by mass (parts by mass). Polymer solution. In Table 1, "-" indicates that no eligible component was used.

[Table 1]

The meaning of each symbol in Table 1 is as follows.
MA: methacrylic acid
AA: Acrylic
HS: hydroxystyrene
FHST: 4- (1,1,1,3,3,3-hexafluoro-2-hydroxypropane-2-yl) styrene
GMA: glycidyl methacrylate
OXMA: (3-ethyloxetane-3-yl) methyl methacrylate
EPMA: 3,4-epoxycyclohexyl methyl methacrylate
ST: styrene
BzMA: benzyl methacrylate
MMA: methyl methacrylate
PM: Phenylmaleimide
STMS: styryltrimethoxysilane
ADVN: 2,2'-azobis (2,4-dimethylvaleronitrile)
S-1 to S-5: described later

[Contained Components of Radiation Sensitive Composition]
The alkali-soluble resin (A), the radiation-sensitive compound (B), the adhesion assistant (C), the surfactant (D), and the polymerization used in the preparation of the radiation-sensitive composition of the examples and comparative examples are shown below Sexual compounds (E) and solvents (S).

"Alkali soluble resin (A)"
A-1 to A-12: polymer (A-1) to polymer (A-12) synthesized in Synthesis Example 1 to Synthesis Example 12
"Radiation Sensitive Compound (B)"
B-1: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol (1.0 mole) with 1,2 -Condensate of Naphthoquinonediazide-5-sulfosulfonyl chloride (2.0 moles)
B-2: Trifluoromethanesulfonic acid-1,8-naphthylimine
B-3: Irgacure OXE-01 (manufactured by BASF)
"Seal Adhesive (C)"
C-1: 3-Glycidoxypropyltrimethoxysilane
C-2: 3-Methacryloxypropyltrimethoxysilane "Surfactant (D)"
D-1: SH8700 (manufactured by Toray Dow Corning)
"Polymerizable Compound (E)"
E-1: Dipentaerythritol hexaacrylate (DPHA)
"Solvent (S)"
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: 1-methoxy-1- (2-methoxyethoxy) ethane
S-3: 1,3-dimethoxy-2,2-dimethylpropane
S-4: 4,4,6-trimethyl-1,3-dioxane
S-5: 1-penten-3-ol

[Evaluation of radiation-sensitive composition]
The following items were evaluated for the radiation-sensitive compositions of the examples and comparative examples.
<Coatability>
After the radiation-sensitive composition was coated on a silicon substrate using a spinner, it was pre-baked at 90 ° C. for 2 minutes on a hot plate to form a coating film having an average film thickness of 3.0 μm. Next, the surface of the coating film was observed for the occurrence of dents using an optical microscope. At this time, those who did not sag could be evaluated as having good coatability, and those who had sags could be evaluated as having poor coatability.

The dent of the coating film refers to a phenomenon in which, after the composition is coated on the substrate and pre-baked, a circular depression is formed on the surface of the coating film, or when the hole of the substrate can be seen when it is noticeable. The sag is caused by various factors, and is considered to be caused by the evaporation of a local volatile component from the wet coating film after coating, the contamination of minute foreign matter, the stain of the substrate, and the like.
A case where the number of depressions per substrate is 0 is evaluated as AA, a case where one or more is less than 10 is evaluated as BB, a case where 10 or more and less than 100 is evaluated as CC, and 100 or more cases were evaluated as DD.

<Radiation sensitivity>
Using a spinner, the radiation-sensitive composition was coated on a silicon substrate treated with hexamethyl disilazane (HMDS) at 60 ° C for 60 seconds, and then pre-baked on a hot plate at 90 ° C. For 2 minutes, a coating film having an average film thickness of 3.0 μm was formed. The coating film was irradiated with a predetermined amount of ultraviolet rays through a pattern mask having a line and a space pattern with a width of 10 μm through a pattern mask. Next, after performing a development process at 25 ° C. for 60 seconds using a developer containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, the solution was washed with ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a line and space pattern with a width of 10 μm was measured. The case where the value is less than 100 mJ / cm ² is determined as AA, the case where the value is 100 mJ / cm ² or more and less than 150 mJ / cm ² is determined as BB, and the case where 150 mJ / cm ² or more is determined as CC. The exposure was measured with a light meter (wavelength 365 nm).

＜ Storage stability ＞
The prepared radiation-sensitive composition was sealed in a light-shielding and air-tight container. After 7 days at 25 ° C., the container was opened and the above-mentioned [radiation sensitivity] was measured, and the increase rate of the radiation sensitivity (minimum exposure amount) before and after storage for 7 days was calculated. The case where the value is less than 10% is determined as AA, the case where 10% or more and less than 20% is determined as BB, and the case where 20% or more is determined as CC. When it is AA or BB, it can be evaluated as good storage stability, and when it is CC, it can be evaluated as poor storage stability.

＜ Exposure margin ＞
Using a spinner, the radiation-sensitive composition was coated on a silicon substrate subjected to HMDS treatment at 60 ° C for 60 seconds, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating having an average film thickness of 3.0 μm. membrane. The coating film was irradiated with a predetermined amount of ultraviolet rays through a pattern mask having a line and a space pattern with a width of 10 μm through a pattern mask. Next, after performing a development process at 25 ° C. for 60 seconds using a developer containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, the solution was washed with ultrapure water for 1 minute. At this time, the exposure amount capable of forming a line and space pattern with a width of 10 μm was measured. If the maximum exposure amount is D ₁ and the minimum value is D ₂ , the value of 100 (%) × (D ₁ -D ₂ ) / D ₁ is 20% or more and less than 30%. The case is judged as AA, the case where it is 10% or more and less than 20% is judged as BB, and the case is less than 10% as CC. "-" Means not evaluated.

<Preparation of radiation-sensitive composition 1>
Examples of the first composition of the present invention described above will be described below.
[Example 1]
In the polymer solution containing the polymer (A-1) at a polymer concentration of 30% by mass, 30 parts of the radiation-sensitive compound (B-1) was based on 100 parts of the polymer (A-1). , 1 part of the adhesion promoter (C-1) and 0.05 part of the surfactant (D-1) are mixed, and then a PGMEA solution of allyl methyl ether (AME) is added (the final AME amount is described in Table 2). Furthermore, the obtained mixture was dissolved in the solvent (S-1) (PGMEA) so that the concentration of all components except the solvent became 30% by mass, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive combination. Thing.

[Examples 2 to 15 and Comparative Examples 1 to 4]
A radiation-sensitive composition of Examples 2 to 15 and Comparative Examples 1 to 4 was prepared in the same manner as in Example 1 except that the components of the types shown in Table 2 below were used.
The evaluation results are shown in Table 2.

[Table 2]

As shown in Table 2, it can be seen that each of the radiation-sensitive compositions of the examples has good coatability and storage stability. On the other hand, the radiation-sensitive composition of the comparative example did not have both coatability and storage stability.

<Preparation of radiation-sensitive composition 2>
Examples of the second composition of the present invention described above will be described below.
[Example 21]
In the polymer solution containing the polymer (A-5) at a polymer concentration of 30% by mass, 30 parts of the radiation-sensitive compound (B-1) was based on 100 parts of the polymer (A-5). , 1 part of the adhesion promoter (C-1) and 0.05 part of the surfactant (D-1) are mixed, and the obtained mixture is dissolved in the solvent so that the concentration of all components except the solvent becomes 30% by mass. After (S-2), filtration was performed using a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[Example 22 to Example 28 and Comparative Example 21 to Comparative Example 22]
A radiation-sensitive composition of Examples 22 to 28 and Comparative Examples 21 to 22 was prepared in the same manner as in Example 21 except that the components of the types shown in Table 3 below were used.
The evaluation results are shown in Table 3.

[table 3]

As shown in Table 3, each of the radiation-sensitive compositions of the examples was found to have good coatability, storage stability, and exposure margin. On the other hand, the radiation-sensitive composition of the comparative example does not have all of good coatability, storage stability, and exposure margin.

Claims (9)

A radiation-sensitive composition comprising: Alkali-soluble resin Radioactive compounds Propylene glycol monomethyl ether acetate; and Allyl methyl ether. The radiation-sensitive composition according to item 1 of the patent application scope, wherein the allyl methyl ether is contained in a range of 10 wtppm to 50000 wtppm. The radiation-sensitive composition according to item 1 or item 2 of the scope of patent application, wherein the weight-average molecular weight (Mw) of the polystyrene-equivalent alkali-soluble resin obtained by gel permeation chromatography is 1,000 to The weight average molecular weight (Mw) / number average molecular weight (Mn) in terms of polystyrene is 1.0 to 5.0. The radiation-sensitive composition according to item 1 or item 2 of the patent application scope, wherein the alkali-soluble resin is an ethylenically unsaturated monomer having one or more acidic functional groups, and a monomer capable of interacting with the monomer. Copolymer of other ethylenically unsaturated monomers. The radiation-sensitive composition according to claim 1 or claim 2, further comprising a polymerizable compound having at least one ethylenically unsaturated double bond. The radiation-sensitive composition according to item 1 or item 2 of the scope of patent application, wherein it is used to form a hardened film as an interlayer insulating film, a protective film, or a separator. A hardened film formed of the radiation-sensitive composition according to item 6 of the patent application scope, and used as an interlayer insulating film, a protective film, or a separator. A display element having a cured film as described in item 7 of the scope of patent application. A radiation-sensitive composition comprising: Alkali-soluble resin Radioactive compounds; and Selected from 1-methoxy-1- (2-methoxyethoxy) ethane, 1,3-dimethoxy-2,2-dimethylpropane, 4,4,6-trimethyl At least one compound of -1,3-dioxane and 1-penten-3-ol.