JP7010093B2 - Radiation-sensitive composition - Google Patents

Description

The present invention relates to a radiation sensitive composition.

The radiation-sensitive composition is conventionally a cured film possessed by a display element, and has been used to form a patterned cured film such as an interlayer insulating film, a protective film, and a spacer (see, for example, Patent Document 1). ).

Japanese Unexamined Patent Publication No. 2012-159601

According to the studies by the present inventors, the conventional radiation-sensitive composition may not have good storage stability when it is configured as a liquid composition. An object of the present invention is to provide a radiation-sensitive composition having good storage stability.

As a result of studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a radiation-sensitive composition having the following composition, and have completed the present invention. That is, the present invention relates to the following [1] to [9].

[1] A radiation-sensitive composition containing 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 the range of 10 wtppm to 50,000 wtppm.
[3] The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin by gel permeation chromatography is 1,000 to 1,000,000 , and the polystyrene-equivalent weight average molecular weight (Mw) / number average molecular weight (Mn). The radiosensitive composition according to the above [1] or [2], wherein) is 1.0 to 5.0.
[4] The alkali-soluble resin is a copolymer of an ethylenically unsaturated monomer having one or more acidic functional groups and another ethylenically unsaturated monomer copolymerizable with the monomer. The radiation-sensitive composition according to any one of the above [1] to [3].
[5] The radiation-sensitive composition according to any one of the above [1] to [4], which further contains a polymerizable compound having at least one ethylenically unsaturated double bond.
[6] The radiation-sensitive composition according to any one of [1] to [5] above, which is used for forming a cured film as an interlayer insulating film, a protective film or a spacer.
[7] A cured film as an interlayer insulating film, a protective film or a spacer, which is formed from the radiation-sensitive composition according to the above [6].
[8] A display element having the cured film according to the above [7].
[9] Alkali-soluble resin, radiation-sensitive compound, 1-methoxy-1- (2-methoxyethoxy) ethane, 1,3-dimethoxy-2,2-dimethylpropane, 4,4,6-trimethyl-1 , 3-Dioxane, and a radiosensitive composition containing at least one compound selected from 1-pentene-3-ol.

According to the present invention, it is possible to provide a radiation-sensitive composition having good storage stability.

In the present specification, preferable upper limit values and lower limit values are described in terms of the content ratio of each component, respectively, but a numerical range defined from any combination of the described upper limit value and the lower limit value is also described in the present specification. It is assumed that it is.

Hereinafter, embodiments for carrying out the present invention will be described. The above problems can be solved by the first radiation-sensitive composition and the second radiation-sensitive composition of the present invention described below.

[Radiation-sensitive composition]
The first radiation-sensitive composition of the present invention contains 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 comprises an alkali-soluble resin, a radiation-sensitive compound, 1-methoxy-1- (2-methoxyethoxy) ethane, 1,3-dimethoxy-2,2-dimethylpropane. , 4,4,6-trimethyl-1,3-dioxane, and at least one compound selected from 1-pentene-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". When these first and second compositions are common, they are 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)". The radiation-sensitive compound is also referred to as “radiation-sensitive compound (B)”.

Further, propylene glycol monomethyl ether acetate is also referred to as "PGMEA". From 1-methoxy-1- (2-methoxyethoxy) ethane, 1,3-dimethoxy-2,2-dimethylpropane, 4,4,6-trimethyl-1,3-dioxane, and 1-pentene-3-ol At least one compound selected is also referred to as a "specific solvent".

本発明の組成物は、通常、溶媒を配合して液状組成物として調製される。

The composition of the present invention is usually prepared as a liquid composition by blending a solvent.

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

アリルメチルエーテルはラジカルトラップ性を有することから、液状組成物として保存中に、例えば、前記第１組成物がネガ型の場合には後述する重合性化合物（Ｅ）の重合を抑制でき、またポジ型の場合にはアルカリ可溶性樹脂（Ａ）の分解等の劣化を抑制でき、よって、前記第１組成物の保存安定性が向上する。また、アリルメチルエーテルの沸点は低いことから、前記第１組成物を塗布した後のプレベークによりアリルメチルエーテルは除去され、放射線感度への影響も小さい。

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

The upper limit of the content ratio of allylmethyl ether in the first composition is preferably 50,000 wtppm, more preferably 10,000 wtppm, still more preferably 7500 wtppm, and particularly preferably 5000 wtppm. When the content ratio of allylmethyl ether is not more than the upper limit, it is preferable from the viewpoint of the coatability and radiation sensitivity of the first composition, and the surface roughness of the coating film formed from the first composition can be suppressed. Therefore, it is preferable because the whitening of the obtained cured film can be suppressed.

The lower limit of the content ratio of allylmethyl ether in the first composition is preferably 10 wtppm, more preferably 50 wtppm. When the content ratio of allylmethyl ether is at least the lower limit value, it is preferable from the viewpoint of storage stability of the first composition. The content ratio of allyl methyl ether can be measured by gas chromatography.

In the first composition of the present invention, in addition to PGMEA, another solvent that disperses or dissolves the components constituting the first composition, does not react with these components, and has appropriate volatility (as a solvent). 1) can be further contained.

As another solvent (1), for example,
Ethylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monoalkyl ethers such as propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; propylene glycol monoethyl ether acetate. , Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Monoalkyl Ether Acetate, etc. (excluding PGMEA);
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol, propylene glycol, tetrahydrofurfuryl alcohol;
Lactates such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, propion Aliup carboxylic acid esters such as n-butyl acid and isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, pyruvate Other esters such as ethyl;
Ketone solvents such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; amide solvents such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactones such as γ-butyrolactone. solvent;
Aromatic hydrocarbon solvents such as toluene and xylene;
Can be mentioned.

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

Further, the upper limit of the content ratio of all the components other than the solvent in the first composition of the present invention is preferably 50% by mass, more preferably 40% by mass, still more preferably 35% by mass; the lower limit is It is preferably 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), allylmethyl ether, and other components optionally added.
The liquid composition thus prepared can also be used after being filtered using, for example, a filter having pores having a pore size of about 0.2 μm.

[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, at least the specific solvent is used as the solvent in the second composition.

The second composition containing the specific solvent is excellent in storage stability. Further, as the storage stability is improved, the exposure margin is also improved. Details of the exposure margin will be described in the Example column.

In the second composition of the present invention, other than the specific solvent, other components constituting the radiation-sensitive composition are dispersed or dissolved, and the components do not react with these components and have appropriate volatility. The solvent (2) can be further contained. Examples of the other solvent (2) include the above-mentioned other solvent (1) (however, excluding the specific solvent) and PGMEA.

The other solvent (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, still more preferably 85% by mass; the lower limit is preferably 50. It is by mass, more preferably 60% by mass, still more preferably 65% by mass.

Further, the upper limit of the content ratio of all the components other than the solvent in the second composition of the present invention is preferably 50% by mass, more preferably 40% by mass, still more preferably 35% by mass; the lower limit is It is preferably 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 optionally other components.

The liquid composition thus prepared can also be used after being filtered using, for example, a filter having pores having a pore size of about 0.2 μm.
Hereinafter, each component other than the solvent will be described.

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

A fluorinated hydroxyalkyl group is a hydroxyalkyl group in which a part of a hydrogen atom bonded to a carbon atom is replaced with a fluorine atom, for example, a group represented by −C (R ^a1 ) (R ^a2 ) OH. In the above formula, R ^a1 is a fluorine 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 fluorine having 1 to 4 carbon atoms. It is an alkylated group.

Examples of the polymer having an acidic functional group include novolak resin, phenol-xylylene glycol condensed resin, cresol-xylylene glycol condensed resin, phenol-dicyclopentadiene condensed resin, polybenzoxazole precursor, polyhydroxystyrene, and hydroxy. Polymers having a phenolic hydroxyl group such as a copolymer of styrene and styrene; polymers having a carboxy group such as a carboxy group-containing epoxy (meth) acrylate resin having a novolak-type skeleton in the main chain and polyamic acid can be mentioned. Be done.

Examples of the polymer having an acidic functional group include an ethylenically unsaturated monomer having one or more acidic functional groups (hereinafter, also referred to as “unsaturated monomer (a1)”) and the above-mentioned (a1). Examples thereof include a copolymer with another copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as “unsaturated monomer (a2)”). In particular, a (meth) acrylic polymer having an acidic functional group is preferable.

Examples of the unsaturated monomer (a1) include (meth) acrylic acid, maleic acid, maleic anhydride, monosuccinic acid [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Carboxy group-containing unsaturated monomers such as acrylate and p-vinylbenzoic acid; phenolic hydroxyl group-containing unsaturated monomers such as hydroxystyrene, p-isopropenylphenol, hydroxyphenyl acrylate and hydroxyphenylacrylamide; 4- (1) , 1,1,3,3,3-hexafluoro-2-hydroxypropane-2-yl) Examples thereof include fluorinated hydroxyalkyl group-containing unsaturated monomers such as styrene. Among these, it is preferable to use at least (meth) acrylic acid from the viewpoint of polymerizable property.

The unsaturated monomer (a1) can be used alone or in combination of two or more.
Examples of the unsaturated monomer (a2) include N-substituted maleimides such as N-arylmaleimide, N-alkylmaleimide, and N-cycloalkylmaleimide; aromatic vinyl compounds such as styrene and derivatives thereof; (meth). It has a cyclic ether ring such as an acrylic acid alkyl ester, a (meth) acrylic acid hydroxyalkyl ester, a (meth) acrylic acid alicyclic-containing ester, a (meth) acrylic acid aromatic ring-containing ester, an oxylan ring, an oxetan ring, and an oxolan ring (. (Meta) acrylic acid ester such as meta) acrylic acid ester; Aromatic ring-containing silane compound such as styryl group-containing silane compound; Vinyl ether such as alicyclic-containing vinyl ether; Polymer chain of aromatic vinyl compound, (meth) acrylic acid ester Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as a polymer chain and a polysiloxane molecular chain. Among these, at least one selected from a (meth) acrylic acid ester having an oxylan ring and a (meth) acrylic acid ester having an oxetane ring can be used from the viewpoint of imparting a crosslinkable functional group to the alkali-soluble resin. preferable.

More specifically, Japanese Patent Laid-Open Nos. 2015-004968 [0060] to [0062], Japanese Patent Laid-Open Nos. 2008-233346 [0036] to [0045], and Japanese Patent Laid-Open Nos. 2009-229567 [0013] to [0013] to Examples thereof include the monomers described in [0021].

The unsaturated monomer (a2) can 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 JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, JP-A-2006-201549. , JP-A-2007-128062, JP-A-2008-233563, JP-A-2017-181928, JP-A-2017-173376 and the like.

Further, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, JP-A-2008-181095. As disclosed in Japanese publications and the like, a carboxy group-containing (meth) acrylic polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used.

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

In one embodiment, the copolymer of (a1) and (a2) has an unsaturated monomer (a1), a (meth) acrylic acid ester having an oxylan ring, and a (meth) acrylic acid having an oxetane ring. A copolymer with at least one selected from esters is preferred. In this copolymer, unsaturated monomers (a2) other than these may be copolymerized. For example, even if at least one selected from an aromatic vinyl compound, a (meth) acrylic acid aromatic ring-containing ester, a (meth) acrylic acid alkyl ester, an N-position substituted maleimide and a styryl group-containing silane compound is further copolymerized. good.

In the copolymer of (a1) and (a2), the content ratio of the structural unit derived from at least one selected from the (meth) acrylic acid ester having an oxylan ring and the (meth) acrylic acid ester having an oxetane ring. The upper limit of the above value is preferably 50% by mass, more preferably 40% by mass; and the lower limit value is preferably 5% by mass, more preferably 10% by mass, still more preferably 15% by mass.

The copolymer of (a1) and (a2) can be produced by a known method, and for example, Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 2007/029871. The structure, weight average molecular weight, and molecular weight distribution can also be controlled by the method disclosed in No. and the like.

Further, examples of the alkali-soluble resin (A) include alkali-soluble polysiloxane, polyimide or polybenzoxazole.
Specific examples of the polysiloxane include, for example, International Publication No. 2017/188047, International Publication No. 2017/169763, International Publication No. 2017/159876, Japanese Patent Application Laid-Open No. 2013-114238, Japanese Patent Application Laid-Open No. 2012-53381. Examples thereof include copolymers disclosed in JP-A-2010-32977.

Specific examples of the polyimide or polybenzoxazole include, for example, International Publication No. 2017/169763, International Publication No. 2017/159876, International Publication No. 2017/052781, International Publication No. 2017/159476, International Publication No. 2017/ Coweight disclosed in 073481, International Publication No. 2017/038882, International Publication No. 2016/148176, JP-A-2015-114355, JP-A-2013-164432, JP-A-2010-72143, etc. Coalescence is mentioned.

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

The resin (A) can be used alone or in combination of two or more.
In the composition of the present invention, the upper limit of the content ratio of the alkali-soluble resin (A) in 100% by mass of all the components other than the solvent of the composition is preferably 99% by mass, more preferably 95% by mass, still more preferable. Is 90% by mass, particularly preferably 85% by mass; the lower limit is preferably 40% by mass, more preferably 50% by mass, still more preferably 60% by mass.

<Radiation-sensitive 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 by irradiation with radiation. When the composition of the present invention contains the component (B1), it can function as a radiation-curable resin composition, and the generated radical polymerizes the alkali-soluble resin (A), the polymerizable compound (E) described later, and the like. By doing so, it exhibits negative radiation-sensitive characteristics. The composition of the present invention can further enhance the radiation sensitivity by containing the component (B1).

Examples of the component (B1) include an O-acyloxime compound, an acetophenone compound, a biimidazole compound, and a thioxanthone compound.
Examples of the O-acyloxime compound include 1- [4- (phenylthio) -2- (O-benzoyloxime)] and 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyl). Oxime)], Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl] -9. H. -Carbazole-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate can be mentioned.

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-morpholinophenyl) -butane-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4). -Morphorin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one can be mentioned. Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-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-trichlorophenyl) -4,4', 5, 5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-bi Imidazole is preferred.

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

Among these, O-acyloxime compounds, acetophenone compounds, and thioxanthone compounds are preferable, O-acyloxime compounds, α-aminoketone compounds, and thioxanthone compounds are more preferable, and 1,2-octanedione 1- [4- (phenylthio)-. 2- (O-benzoyloxime)], etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 2-methyl- 1- (4-Methylthiophenyl) -2-morpholinopropane-1-one, 2,4-diethylthioxanthone are more preferred.

When the component (B1) is used as the radiation-sensitive compound (B), the upper limit of the content of the component (B1) is preferably the upper limit of the content of the component (B1) with respect to 100 parts by mass of the alkali-soluble resin (A) in the composition of the present invention. It is 30 parts by mass, more preferably 25 parts by mass, still more preferably 20 parts by mass; the lower limit is preferably 1 part by mass, more preferably 3 parts by mass, still more preferably 6 parts by mass. In such an embodiment, the adhesion of the cured film formed from the composition of the present invention can be further enhanced, and the radiation sensitivity of the composition of the present invention can be further enhanced.

<< 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 by irradiation with radiation. The composition of the present invention can further enhance the radiation sensitivity by containing the acid generator (B2).

Examples of the acid generator (B2) include quinonediazide compounds, oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds.

The quinonediazide compound is a compound that generates a carboxylic acid by irradiation with radiation. The composition of the present invention contains a quinonediazide compound as an acid generator (B2), so that the generated carboxylic acid enhances the solubility of the irradiated portion in an alkaline developer, and thus has positive radiation-sensitive characteristics. Can be demonstrated.

As the quinone diazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter, also referred to as “matrix”) and a 1,2-naphthoquinone diazide sulfonic acid halide can be used.

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

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'-tetrahydroxybenzophenone, 2, Examples thereof include 3,4,2'-tetrahydroxy-4'-methylbenzophenone and 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone.

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'-hexahydroxybenzophenone and the like.

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

Other mother nuclei include, for example, 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, 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-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] benzene.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazido sulfonic acid chloride is preferable. Examples of the 1,2-naphthoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferable.

The synthesis of the quinonediazide compound can be carried out by a known condensation reaction. In this condensation reaction, a 1,2-naphthoquinonediazide sulfonic acid halide corresponding to preferably 30 to 85 mol%, more preferably 50 to 70 mol% with respect to the number of OH groups in the phenolic compound or alcoholic compound is used. be able to.

As the oxime sulfonate compound, onium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonic acid ester compound, and carboxylic acid ester compound as the acid generator, known compounds can be used. Specific examples of the sulfoneimide compound include N-sulfonyloxyimide compounds, specifically, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, and N- ( Trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthyl Imide is mentioned.

When the quinone diazide compound is used as the radiation-sensitive compound (B), the upper limit of the content of the quinone diazide compound is preferably 40 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A) in the composition of the present invention. It is more preferably 35 parts by mass, still more preferably 30 parts by mass, and the lower limit is preferably 5 parts by mass, more preferably 10 parts by mass, still more preferably 15 parts by mass. In such an embodiment, the adhesion of the cured film formed from the composition of the present invention can be further enhanced, and the radiation sensitivity of the composition of the present invention can be further enhanced.

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

<Other ingredients>
The composition of the present invention contains an alkali-soluble resin (A) and a radiation-sensitive compound (B) as essential components, but if necessary, as other components, an adhesion aid (C) and a surfactant ( D), at least selected from a polymerizable compound (E) having at least one ethylenically unsaturated double bond, an epoxy resin (F) other than the alkali-soluble resin (A), and a heat-sensitive acid-producing compound (G). It can contain one kind.

The composition of the present invention may contain an adhesion aid (C) in order to improve the adhesion between the substrate and the coating film. Examples of the adhesion aid (C) include functional silane coupling agents such as silane coupling agents having reactive functional groups such as carboxy group, methacryloyl group, vinyl group, isocyanate group, epoxy group and amino group. Be done. Specifically, trimethoxysilyl benzoic acid, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-Epoxycyclohexyl) Ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl)- Examples thereof include 3-aminopropyltrimethoxysilane. As the adhesion aid (C), for example, the compounds described in JP-A-2006-126397 and JP-A-2009-204865 can also be used. The adhesion aid (C) can be used alone or in combination of two or more.

The composition of the present invention can contain the adhesion aid (C) in a range of preferably 20 parts by mass or less, more preferably 10 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 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 can contain the 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 comprises a polymerizable compound (E) having at least one ethylenically unsaturated double bond in order to make the composition a negative type or to improve the heat resistance and hardness of the cured film. Can be contained. Examples of the polymerizable compound (E) include monofunctional (meth) acrylates, bifunctional (meth) acrylates, and (meth) acrylates such as trifunctional or higher functional (meth) acrylates. The number of (meth) acryloyl groups in the (meth) acrylate is preferably 2 to 6. Among these, trifunctional or higher functional (meth) acrylates are preferable, and examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. The polymerizable compound (E) can be used alone or in combination of two or more.

The composition of the present invention can contain the polymerizable compound (E) in a range of preferably 100 parts by mass or less, more preferably 75 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (A). ..

The composition of the present invention can contain an epoxy resin (F) other than the alkali-soluble resin (A) in order to improve the heat resistance and hardness of the cured film. The alkali-soluble resin (A) also contains what 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 alkaline insoluble.

The epoxy resin (F) is not limited as long as it does not affect the compatibility. For example, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cyclic aliphatic epoxy resin, and glycidyl ester. Examples thereof include a type epoxy resin, a glycidylamine type epoxy resin, a heterocyclic epoxy resin, and a resin obtained by (co) polymerizing glycidyl methacrylate. Among these, bisphenol A type epoxy resin, cresol novolac type epoxy resin, and 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 can contain the epoxy resin (F) in a range of preferably 50 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A).
The composition of the present invention can contain a heat-sensitive acid-producing compound (G) in order to improve the heat resistance and hardness of the cured film. Examples of the heat-sensitive acid-producing compound (G) include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts. The heat-sensitive acid-producing compound (G) can be used alone or in combination of two or more.

The composition of the present invention contains the heat-sensitive acid-producing compound (G) in a range of preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (A). Can be done.
The composition of the present invention described above can be suitably used as a material for forming a cured film of a display element, such as an interlayer insulating film, a protective film, and a cured film such as a spacer.

[Cured film and its manufacturing method]
A method for producing a cured film of the present invention using the radiation-sensitive composition of the present invention will be described. Examples of the cured film of the present invention include an interlayer insulating film, a protective film, and a spacer. The film thickness of the cured film is usually 0.5 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 is, for example, a step of forming a coating film of the radiation-sensitive composition of the present invention on a substrate (1), a step of irradiating at least a part of the coating film with radiation (2), and irradiation. It can be formed by a production method comprising a step (3) of developing a subsequent coating film and a step (4) of heating the developed coating film to obtain a cured film.

<Process (1)>
In step (1), the composition of the present invention is applied onto a substrate, and the solvent is preferably removed by prebaking to form a coating film of a radiation-sensitive composition.
Examples of the substrate include a glass substrate, a silicon substrate, and a substrate on which various metal members are formed on the surface thereof.

Examples of the coating method of the composition include a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method, and a spin coating method and a slit die coating method. Is preferable.
The prebaking conditions also differ depending on the type, content ratio, etc. of each component in the composition of the present invention. For example, it can be set to about 30 seconds to 15 minutes at 60 to 110 ° C.
The film thickness of the coating film of the radiation-sensitive composition after prebaking is usually 0.5 to 6 μm.

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

<Process (3)>
In the step (3), the coating film after irradiation is subjected to a developing process using a developing solution to remove the irradiated portion. Thereby, a patterned coating film can be obtained.
An alkaline developer is usually used for the development treatment, and examples thereof include an aqueous solution of an alkaline compound (basic compound). Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, and methyl. Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4. 3.0] -5-Nonan can be mentioned. The concentration of the alkaline compound in the alkaline developer is usually 0.1 to 10% by mass. Further, 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 for dissolving the composition of the present invention can be used as a developing solution.

Examples of the developing method include a liquid filling method, a dipping method, a rocking dipping method, and a shower method. The development time varies depending on the composition of the composition, but can be, for example, 30 to 120 seconds. The patterned coating film can be rinsed, for example, by washing with running water.

Further, by irradiating the patterned coating film on the entire surface (post-exposure), the compound (B) remaining in the coating film can be decomposed. The exposure amount in the post-exposure is usually 200 to 500 mJ / cm ² .

<Process (4)>
In the step (4), the coating film obtained in the step (3), specifically, the patterned coating film is heated (post-baked) to obtain a cured film.
For heating in the curing 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 curing treatment is usually 120 to 250 ° C. The heating time in the curing treatment varies depending on the type of heating equipment, but is, for example, 5 to 30 minutes when the heat treatment is performed on a hot plate and 30 to 100 minutes when the heat treatment is performed in an oven. At this time, a step baking method in which two or more heating steps are performed can also be used.
As described above, a cured film can be obtained. In one embodiment, for example, a desired interlayer insulating film, a protective film, and a cured film which is a spacer can be formed on the substrate.

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

Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following examples. In the following description, "parts by mass" will be referred to as "parts" unless otherwise specified.

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

[Synthesis of alkali-soluble resin]
[Synthesis Example 1] (Synthesis of polymer (A-1))
A flask equipped with a condenser 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). Subsequently, 20 parts of methacrylic acid, 20 parts of glycidyl methacrylate, 20 parts of 3,4-epoxycyclohexylmethylmethacrylate and 40 parts of styrene were charged, substituted with nitrogen, and then the temperature of the solution was raised to 70 ° C. with gentle stirring. By maintaining this temperature for 5 hours and polymerizing, a polymer solution containing the polymer (A-1) which is an alkali-soluble resin was obtained. The obtained polymer solution was reprecipitated in hexane, purified by filtration and vacuum drying, and the polymer (A-1) was dissolved in PGMEA to obtain a polymer concentration of 30% by mass. The weight average molecular weight (Mw) of this polymer (A-1) was 10,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.3.

[Synthesis Examples 2 to 12] (Synthesis of Polymers (A-2) to (A-12))
Polymers containing polymers (A-2) to (A-12) by the same method as in Synthesis Example 1 except that each component of the type and blending amount (part by mass) shown in Table 1 below was used. A solution was obtained. In Table 1, "-" indicates that the corresponding component was not used.

The meaning of each symbol in Table 1 is as follows.
MA: Methacrylate AA: Acrylic acid HS: Hydroxystyrene FHST: 4- (1,1,1,3,3,3-hexafluoro-2-hydroxypropane-2-yl) Styrene GMA: Glycidyl methacrylate OXMA: (3) -Ethyloxetane-3-yl) Methylmethacrylate EPMA: 3,4-Epoxycyclohexylmethylmethacrylate ST: Styrene BzMA: Benzylmethacrylate MMA: Methylmethacrylate PM: Phenylmaleimide STMS: Styryltrimethoxysilane ADVN: 2,2'-azobis ( 2,4-Dimethylvaleronitrile)
S-1 to S-5: Will be described later.

[Ingredients contained in radiation-sensitive composition]
The alkali-soluble resin (A), the radiation-sensitive compound (B), the adhesion aid (C), the surfactant (D), and the polymerizable compound (E) used in the preparation of the radiation-sensitive compositions of Examples and Comparative Examples. ) And the solvent (S) are shown below.

<< Alkali-soluble resin (A) >>
A-1 to A-12: Polymers (A-1) to (A-12) synthesized in Synthesis Examples 1 to 12
<< Radiation-sensitive compound (B) >>
B-1: 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (2.0 mol) B-2: Trifluoromethanesulfonic acid-1,8-naphthalimide B-3: Irgacure OXE-01 (manufactured by BASF)
<< Adhesion aid (C) >>
C-1: 3-glycidyloxypropyltrimethoxysilane C-2: 3-methacrylicoxypropyltrimethoxysilane
<< 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-Pentene-3-all

[Evaluation of radiation-sensitive composition]
The following items were evaluated for the radiation-sensitive compositions of Examples and Comparative Examples.
<Applicability>
After applying the radiation-sensitive composition on a silicon substrate using a spinner, it was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Next, the occurrence of repellent was observed on the surface of this coating film using an optical microscope. At this time, it can be evaluated that the one without repellency has good coatability and the one with repellency has poor coatability.

The repelling of the coating film is a phenomenon in which after the composition is applied on the substrate and prebaked, a circular dent is formed on the surface of the coating film, and in a remarkable case, a hole is formed so that the substrate of the substrate can be seen. .. The repellent is generated from various factors, but is considered to be caused by local evaporation of volatile components from the wet coating film after coating, contamination of minute foreign substances, contamination of the substrate, and the like.
When the number of repellents per substrate was 0, it was evaluated as AA, when it was 1 or more and less than 10, it was evaluated as BB, when it was 10 or more and less than 100, it was evaluated as CC, and when it was 100 or more, it was evaluated as DD.

<Radiation sensitivity>
3. A radiation-sensitive composition was applied onto a silicon substrate treated with hexamethyldisilazane (HMDS) at 60 ° C. for 60 seconds using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to achieve an average film thickness. A 0 μm coating was formed. The coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, a developing solution consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used to develop the product at 25 ° C. for 60 seconds, and then washed with ultrapure water for 1 minute under running water. At this time, the minimum exposure amount capable of forming a line-and-space pattern having a width of 10 μm was measured. When this value was less than 100 mJ / cm ² , it was determined as AA, when it was 100 mJ / cm ² or more and less than 150 mJ / cm ² , it was determined as BB, and when it was 150 mJ / cm ² or more, it was determined as CC. The exposure amount was measured with an illuminance meter (wavelength 365 nm).

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

<Exposure margin>
After applying the radiation-sensitive composition on a silicon substrate treated with HMDS at 60 ° C for 60 seconds using a spinner, it is prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having an average film thickness of 3.0 μm. did. The coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, a developing solution consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used to develop the product at 25 ° C. for 60 seconds, and then washed with ultrapure water for 1 minute under running water. At this time, the exposure amount capable of forming a line-and-space pattern having a width of 10 μm was measured. Assuming that the maximum value of the exposure amount is D ₁ and the minimum value is D ₂ , the value of 100 (%) × (D ₁ − D ₂ ) / D ₁ is AA, 10% or more when the value is 20% or more and less than 30%. When it was less than 20%, it was judged as BB, and when it was less than 10%, it was judged as CC. "-" Is not evaluated.

<Preparation of radiation-sensitive composition 1>
Hereinafter, examples of the first composition of the present invention described above will be described.
[Example 1]
30 parts of the radiation-sensitive compound (B-1) is adhered to the polymer solution containing the polymer (A-1) and having a polymer concentration of 30% by mass, based on 100 parts of the polymer (A-1). 1 part of the agent (C-1) and 0.05 part of the surfactant (D-1) were mixed, and a PGMEA solution of allylmethyl ether (AME) was further added (final AME amount is shown in Table 2). ). Further, the obtained mixture is dissolved in a solvent (S-1) (PGMEA) so that the concentration of all components other than the solvent is 30% by mass, and then filtered through a membrane filter having a pore size of 0.2 μm to detect radiation. A sex composition was prepared.

[Examples 2 to 15 and Comparative Examples 1 to 4]
The same procedure as in Example 1 was carried out except that each component of the types shown in Table 2 below was used to prepare radiation-sensitive compositions of Examples 2 to 15 and Comparative Examples 1 to 4.
The above evaluation results are shown in Table 2.

As shown in Table 2, it can be seen that each radiation-sensitive composition of the example has good coatability and storage stability. On the other hand, none of the radiation-sensitive compositions of Comparative Examples had both coatability and storage stability.

<Preparation of radiation-sensitive composition 2>
Hereinafter, examples of the second composition of the present invention described above will be described.
[Example 21]
30 parts of the radiation-sensitive compound (B-1) and 30 parts of the radiation-sensitive compound (B-1) adhere to the polymer solution containing the polymer (A-5) at a polymer concentration of 30% by mass based on 100 parts of the polymer (A-5). 1 part of the agent (C-1) and 0.05 part of the surfactant (D-1) are mixed, and the obtained mixture is further mixed with a solvent (S-) so that the concentration of all components other than the solvent is 30% by mass. After being dissolved in 2), the mixture was filtered through a polymer filter having a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[Examples 22 to 28 and Comparative Examples 21 to 22]
The same procedure as in Example 21 was carried out except that each component of the types shown in Table 3 below was used to prepare radiation-sensitive compositions of Examples 22 to 28 and Comparative Examples 21 to 22.
The above evaluation results are shown in Table 3.

As shown in Table 3, it can be seen that each radiation-sensitive composition of the example has good coatability, storage stability, and exposure margin. On the other hand, none of the radiation-sensitive compositions of Comparative Examples had good coatability, storage stability, and exposure margin.

Claims (8)

Alkaline-soluble resin and
Radiation sensitive compounds and
Propylene glycol monomethyl ether acetate and
With allyl methyl ether,
A radiation-sensitive composition containing. The radiation-sensitive composition according to claim 1, which contains the allyl methyl ether in the range of 10 wtppm to 50,000 wtppm. The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin by gel permeation chromatography is 1,000 to 1,000,000 , and the polystyrene-equivalent weight average molecular weight (Mw) / number average molecular weight (Mn) is 1. The radiation-sensitive composition according to claim 1 or 2, which is 0.0 to 5.0. Claimed that the alkali-soluble resin is a copolymer of an ethylenically unsaturated monomer having one or more acidic functional groups and another ethylenically unsaturated monomer copolymerizable with the monomer. Item 3. The radiation-sensitive composition according to any one of Items 1 to 3. The radiation-sensitive composition according to any one of claims 1 to 4, further comprising a polymerizable compound having at least one ethylenically unsaturated double bond. The radiation-sensitive composition according to any one of claims 1 to 5, which is used for forming a cured film as an interlayer insulating film, a protective film or a spacer. A cured film as an interlayer insulating film, a protective film or a spacer, which is formed from the radiation-sensitive composition according to claim 6. The display element having the cured film according to claim 7.