Radiation-sensitive composition, cured film, and display element

Abstract

The present invention provides a radiation-sensitive composition, a cured film, and a display element with good storage stability. The radiation-sensitive composition includes: an alkali-soluble resin, a radiation-sensitive compound, propylene glycol monomethyl ether acetate, and allyl methyl ether.

Description

Technical Field

[0001] The present invention relates to a radiation-sensitive composition, a cured film, and a display element. Background Art

[0002] Hitherto, radiation-sensitive compositions have been used to form cured films of display elements, such as patterned cured films such as interlayer insulating films, protective films, and spacers (for example, refer to Patent Document 1).

[0003] [Prior Art Documents]

[0004] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-159601 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] According to the research of the present inventors, when existing radiation-sensitive compositions are formed in the form of liquid compositions, sometimes the storage stability is not good. The subject of the present invention is to provide a radiation-sensitive composition with good storage stability.

[0008] Technical Means for Solving the Problems

[0009] The present inventors made diligent studies to solve the above problems, and as a result, found that the above problems can be solved by a radiation-sensitive composition having the following composition, thereby completing the present invention. That is, the present invention relates to the following [1] to [9].

[0010] [1] A radiation-sensitive composition comprising: an alkali-soluble resin, a radiation-sensitive compound, propylene glycol monomethyl ether acetate, and allyl methyl ether.

[0011] [2] The radiation-sensitive composition according to [1] above, which contains the allyl methyl ether in the range of 10 wtppm to 50000 wtppm.

[0012] [3] The radiation-sensitive composition according to [1] or [2] above, wherein the weight average molecular weight (Mw) in terms of polystyrene of the alkali-soluble resin obtained by gel permeation chromatography is 1,000 to 100,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.0 to 5.0.

[0013] [4]The radiation-sensitive composition according to any one of [1] to [3] above, wherein 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.

[0014] [5]The radiation-sensitive composition according to any one of [1] to [4] above, further comprising a polymerizable compound having at least one ethylenically unsaturated double bond.

[0015] [6]The radiation-sensitive composition according to any one of [1] to [5] above, which is used to form a cured film as an interlayer insulating film, a protective film, or a spacer.

[0016] [7]A cured film formed from the radiation-sensitive composition according to [6] above and serving as an interlayer insulating film, a protective film, or a spacer.

[0017] [8]A display element having the cured film according to [7] above.

[0018] [9]A radiation-sensitive composition comprising: an alkali-soluble resin; a radiation-sensitive compound; and at least one compound selected from 1-methoxy-1-(2-methoxyethoxy)ethane, 1,3-dimethoxy-2,2-dimethylpropane, 4,4,6-trimethyl-1,3-dioxane, and 1-penten-3-ol.

[0019] Effects of the Invention

[0020] According to the present invention, a radiation-sensitive composition with good storage stability can be provided. Detailed Description of the Invention

[0021] In this specification, the upper limit values and lower limit values preferred in the content ratios of the respective components are separately described, and the numerical ranges defined by any combination of the described upper limit values and lower limit values are also described in this specification.

[0022] Hereinafter, the 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.

[0023] [Radiation-Sensitive Composition]

[0024] The first radiation-sensitive composition of the present invention comprises: an alkali-soluble resin, a radiation-sensitive compound, propylene glycol monomethyl ether acetate, and allyl methyl ether.

[0025] The second radiation-sensitive composition of the present invention contains: an alkali-soluble resin; a radiation-sensitive compound; and at least one compound selected from 1-methoxy-1-(2-methoxyethoxy)ethane, 1,3-dimethoxy-2,2-dimethylpropane, 4,4,6-trimethyl-1,3-dioxane, and 1-penten-3-ol.

[0026] Hereinafter, the first radiation-sensitive composition of the present invention will also be referred to as "the first composition of the present invention", the second radiation-sensitive composition of the present invention will also be referred to as "the second composition of the present invention", the common case of these first composition and second composition will be collectively referred to as "the composition of the present invention", the alkali-soluble resin will be referred to as "alkali-soluble resin (A)" or "resin (A)", and the radiation-sensitive compound will be referred to as "radiation-sensitive compound (B)".

[0027] In addition, propylene glycol monomethyl ether acetate will also be referred to as "PGMEA". At least one compound selected from 1-methoxy-1-(2-methoxyethoxy)ethane, 1,3-dimethoxy-2,2-dimethylpropane, 4,4,6-trimethyl-1,3-dioxane, and 1-penten-3-ol will also be referred to as "specific solvent".

[0028] [Chemical formula 1]

[0029]

[0030] The composition of the present invention is usually prepared as a liquid composition by formulating a solvent.

[0031] 〔First composition〕

[0032] The first composition of the present invention contains PEMEA as a solvent.

[0033] The alkali-soluble resin (A) and the radiation-sensitive compound (B) in the first composition have high solubility in PGMEA, so the first composition can use at least PGMEA as a solvent.

[0034] The first composition of the present invention contains allyl methyl ether.

[0035] [Chemical formula 2]

[0036] allyl methyl ether

[0037] Allyl methyl ether has free radical scavenging properties. Therefore, during storage as a liquid composition, for example, in the case where the first composition is negative type, it can inhibit the polymerization of the polymerizable compound (E) described later, and in the case of positive type, it can inhibit deterioration such as the decomposition of the alkali-soluble resin (A). Thus, the storage stability of the first composition is improved. In addition, allyl methyl ether has a low boiling point, so it is removed by pre-baking after coating the first composition, and the influence on radiation sensitivity is also small.

[0038] The upper limit of the content ratio of allyl methyl ether in the first composition is preferably 50000 wtppm, more preferably 10000 wtppm, still more preferably 7500 wtppm, and particularly preferably 5000 wtppm. If the content ratio of allyl methyl ether is below the upper limit value, it is preferable from the viewpoints of the coatability and radiation sensitivity of the first composition. In addition, it can suppress the surface roughness of the coating film formed from the first composition and can suppress the whitening of the cured film obtained therefrom, so it is preferable.

[0039] In addition, the lower limit of the content ratio of allyl methyl ether in the first composition is preferably 10 wtppm, more preferably 50 wtppm. If the content ratio of allyl methyl ether is above the lower limit value, it is preferable from the viewpoint of the storage stability of the first composition. In addition, the content ratio of allyl methyl ether can be measured by gas chromatography.

[0040] In the first composition of the present invention, as a solvent, in addition to PGMEA, other solvents (1) that disperse or dissolve the components constituting the first composition, do not react with these components, and have appropriate volatility may be further contained.

[0041] Examples of other solvents (1) include:

[0042] 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 monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, 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 monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate (excluding PGMEA);

[0043] alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol, propylene glycol, and tetrahydrofurfuryl alcohol;

[0044] Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate; aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate; other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, and ethyl pyruvate;

[0045] Ketone solvents such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; amide solvents such as N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone;

[0046] Aromatic hydrocarbon solvents such as toluene and xylene.

[0047] The other solvents (1) can be used alone or in combination of two or more.

[0048] 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, and still more preferably 85% by mass; the lower limit is preferably 50% by mass, more preferably 60% by mass, and still more preferably 65% by mass.

[0049] In addition, the upper limit 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; the lower limit is preferably 5% by mass, more preferably 10% by mass, and still 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 arbitrarily added components.

[0050] The liquid composition prepared in the above manner can be used, for example, after being filtered using a filter having pores with a diameter of about 0.2 μm.

[0051] [Second Composition]

[0052] The second composition of the present invention contains the specific solvent.

[0053] The alkali-soluble resin (A) and the radiation-sensitive compound (B) in the second composition have high solubility in the specific solvent, so the second composition can use at least the specific solvent as a solvent.

[0054] The storage stability of the second composition containing the specific solvent is excellent. In addition, as the storage stability improves, the exposure margin also improves. Details regarding the exposure margin are described in the Examples section.

[0055] In the second composition of the present invention, as the solvent, in addition to the specific solvent, other solvents (2) that can disperse or dissolve the components constituting the radiation-sensitive composition, do not react with these components, and have moderate volatility may also be contained. As the other solvents (2), the above-described other solvents (1) (excluding the specific solvent) and PGMEA can be cited.

[0056] The other solvents (2) can be used alone or in combination of two or more.

[0057] 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; the lower limit is preferably 50% by mass, more preferably 60% by mass, and still more preferably 65% by mass.

[0058] In addition, the upper limit 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; the lower limit is preferably 5% by mass, more preferably 10% by mass, and still 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 optionally added.

[0059] The liquid composition prepared in the above-described manner can, for example, also be filtered using a filter having pores of about 0.2 μm in diameter and then used.

[0060] Hereinafter, each component other than the solvent will be described.

[0061] <Alkali-soluble resin (A)>

[0062] As the alkali-soluble resin (A), for example, a polymer having acidic functional groups such as a carboxyl group, a phenolic hydroxyl group, and a fluorinated hydroxyalkyl group is preferred. An 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.

[0063] A fluorinated hydroxyalkyl group is a hydroxyalkyl group in which a part of the hydrogen atoms bonded to a carbon atom is substituted with a fluorine atom, for example, a group represented by -C(R a1 )(R a2 )OH. In the above 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.

[0064] Examples of the polymer having an acidic functional group include polymers having phenolic hydroxyl groups such as novolak resin, phenol-dimethylolxylene condensate resin, cresol-dimethylolxylene condensate resin, phenol-dicyclopentadiene condensate resin, polybenzoxazole precursor, polyhydroxystyrene, and copolymer of hydroxystyrene and styrene; and polymers having a carboxyl group such as carboxyl group-containing epoxy (meth)acrylate resin having a novolak-type skeleton in the main chain and polyamic acid.

[0065] Examples of the polymer having an acidic functional group further include a copolymer of an ethylenically unsaturated monomer having one or more acidic functional groups (hereinafter also referred to as "unsaturated monomer (a1)") and another ethylenically unsaturated monomer copolymerizable with the (a1) (hereinafter also referred to as "unsaturated monomer (a2)"). A (meth)acrylic polymer having an acidic functional group is particularly preferred.

[0066] Examples of the unsaturated monomer (a1) include carboxyl group-containing unsaturated monomers such as (meth)acrylic acid, maleic acid, maleic anhydride, monomethyl [2-(meth)acryloyloxyethyl] succinate, ω-carboxypolycaprolactone mono(meth)acrylate, and p-vinylbenzoic acid; phenolic hydroxyl group-containing unsaturated monomers such as hydroxystyrene, p-isopropenylphenol, hydroxyphenyl acrylate, and hydroxyphenyl acrylamide; and fluorinated hydroxyalkyl group-containing unsaturated monomers such as 4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)styrene. Among these, from the viewpoint of polymerizability, it is preferable to use at least (meth)acrylic acid.

[0067] The unsaturated monomer (a1) can be used alone or in combination of two or more.

[0068] Examples of the unsaturated monomer (a2) include N-position substituted maleimides such as N-arylmaleimide, N-alkylmaleimide, and N-cycloalkylmaleimide; aromatic vinyl compounds such as styrene and its derivatives; (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alicyclic esters, (meth)acrylic acid aromatic ring-containing esters, (meth)acrylic acid esters having a cyclic ether ring such as oxirane ring, oxetane ring, and oxolane ring; aromatic ring-containing silane compounds such as styryl group-containing silane compounds; vinyl ethers such as alicyclic vinyl ethers; and macromonomers having a mono(meth)acryloyl group at the end of a polymer molecule chain such as a polymer chain of an aromatic vinyl compound, a polymer chain of a (meth)acrylic acid ester, and a polysiloxane molecular chain. Among these, from the viewpoint of imparting a crosslinkable functional group to the alkali-soluble resin, it is preferable to use at least one selected from (meth)acrylic acid esters having an oxirane ring and (meth)acrylic acid esters having an oxetane ring.

[0069] More specifically, monomers described in

[0060] to

[0062] of Japanese Patent Laid-Open No. 2015-004968,

[0036] to

[0045] of Japanese Patent Laid-Open No. 2008-233346, and

[0013] to

[0021] of Japanese Patent Laid-Open No. 2009-229567 can be cited.

[0070] The unsaturated monomer (a2) can be used alone or in combination of two or more.

[0071] Specific examples of the copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2) include, for example, copolymers disclosed in Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 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. 2017-173376, etc.

[0072] In addition, as disclosed in, 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, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 2008-181095, etc., a carboxyl group-containing (meth)acrylic polymer having a polymerizable unsaturated bond such as (meth)acryloyl group in the side chain can also be used.

[0073] 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.

[0074] In one embodiment, the copolymer of (a1) and (a2) is preferably a copolymer of an unsaturated monomer (a1) and at least one selected from (meth)acrylates having an oxirane ring and (meth)acrylates having an oxetane ring. In the copolymer, unsaturated monomers (a2) other than these may also be copolymerized. For example, at least one selected from aromatic vinyl compounds, (meth)acrylates containing an aromatic ring, (meth)acrylic acid alkyl esters, N-substituted maleimides, and styryl group-containing silane compounds may be further copolymerized.

[0075] In the copolymer of (a1) and (a2), the upper limit of the content ratio of the structural unit derived from at least one selected from (meth)acrylates having an oxirane ring and (meth)acrylates having an oxetane ring is preferably 50% by mass, more preferably 40% by mass; the lower limit is preferably 5% by mass, more preferably 10% by mass, and still more preferably 15% by mass.

[0076] The copolymer of (a1) and (a2) can be produced by a known method. For example, its structure, weight average molecular weight, and molecular weight distribution can also be controlled by the methods disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 2007 / 029871, etc.

[0077] In addition, as the alkali-soluble resin (A), alkali-soluble polysiloxane, polyimide, or polybenzoxazole can also be cited.

[0078] As specific examples of the polysiloxane, for example, the copolymers disclosed in 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, Japanese Patent Application Laid-Open No. 2010-32977, etc. can be cited.

[0079] As specific examples of the polyimide or polybenzoxazole, for example, the copolymers disclosed in 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 Application Laid-Open No. 2015-114355, Japanese Patent Application Laid-Open No. 2013-164432, Japanese Patent Application Laid-Open No. 2010-72143, etc. can be cited.

[0080] 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 ratio (molecular weight distribution: Mw / Mn) of the number average molecular weight (Mn) to the weight average molecular weight (Mw) of the alkali-soluble resin (A) has an upper limit of usually 5.0, preferably 3.0; the lower limit is usually 1.0, preferably 1.1. Mw and Mn are values in terms of polystyrene measured by gel permeation chromatography (hereinafter also referred to as "GPC").

[0081] The resin (A) can be used alone or in combination of two or more.

[0082] In the composition of the present invention, in 100% by mass of all components other than the solvent of the composition, the upper limit of the content ratio of the alkali-soluble resin (A) is preferably 99% by mass, more preferably 95% by mass, still more preferably 90% by mass, and particularly preferably 85% by mass; the lower limit is preferably 40% by mass, more preferably 50% by mass, still more preferably 60% by mass.

[0083] <Radiation-sensitive compound (B)>

[0084] Examples of the radiation-sensitive compound (B) include a radiation-sensitive radical polymerization initiator (B1) and a radiation-sensitive acid generator (B2).

[0085] 《Radiation-sensitive radical polymerization initiator (B1)》

[0086] The radiation-sensitive radical polymerization initiator (B1) (hereinafter also referred to as "component (B1)") is a compound that generates radicals upon irradiation with radiation. If the composition of the present invention contains component (B1), it can function as a radiation-curable resin composition, and through the generated radicals, the alkali-soluble resin (A), the polymerizable compound (E) described later, etc. are polymerized, thereby exhibiting negative radiation-sensitive properties. By containing component (B1) in the composition of the present invention, the radiation sensitivity can be further improved.

[0087] Examples of component (B1) include: O-acyl oxime compounds, acetophenone compounds, biimidazole compounds, thioxanthone compounds.

[0088] As O-acyl oxime compounds, examples include: 1-[4-(phenylthio)-2-(O-benzoyl oxime)], 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)], acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazol-3-yl]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate.

[0089] As acetophenone compounds, examples include α-amino ketone compounds and α-hydroxy ketone compounds. As α-amino ketone compounds, examples include: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. As α-hydroxy ketone compounds, examples include: 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone.

[0090] As benzimidazole compounds, examples include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-benzimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-benzimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-benzimidazole, preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-benzimidazole.

[0091] As thioxanthone compounds, examples include: thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone.

[0092] Among these, O-acyl oxime compounds, acetophenone compounds, and thioxanthone compounds are preferred, O-acyl oxime compounds, α-amino ketone compounds, and thioxanthone compounds are more preferred, and 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)], acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2,4-diethyl thioxanthone are even more preferred.

[0093] When using the component (B1) as the radiation-sensitive compound (B), in the composition of the present invention, with respect to 100 parts by mass of the alkali-soluble resin (A), the upper limit of the content of the component (B1) is preferably 30 parts by mass, more preferably 25 parts by mass, and even more preferably 20 parts by mass; the lower limit is preferably 1 part by mass, more preferably 3 parts by mass, and even more preferably 6 parts by mass. In this way, the adhesion of the cured film formed from the composition of the present invention can be further improved, and in addition, the radiation sensitivity of the composition of the present invention can be further improved.

[0094] 《Radiation-sensitive acid generator (B2)》

[0095] 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, the radiation sensitivity can be further improved.

[0096] Examples of the acid generator (B2) include: quinone diazide compounds, oxime sulfonate compounds, onium salts, sulfimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, and carboxylate compounds.

[0097] The quinone diazide compound is a compound that generates a carboxylic acid upon irradiation with radiation. By containing the quinone diazide compound as the acid generator (B2) in the composition of the present invention, the solubility of the generated carboxylic acid in the alkali developer for the irradiated portion of the radiation is improved, and thus the positive-type radiation-sensitive characteristics can be exhibited.

[0098] As the quinone diazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as "parent nucleus") and 1,2-naphthoquinone diazide sulfonyl halide can be used.

[0099] Examples of the parent nucleus include: trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, and other parent nuclei.

[0100] As trihydroxybenzophenone, examples include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.

[0101] As tetrahydroxybenzophenone, examples include: 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methyldibenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxydibenzophenone.

[0102] As pentahydroxybenzophenone, an example is 2,3,4,2',6'-pentahydroxybenzophenone.

[0103] As hexahydroxybenzophenone, examples include 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.

[0104] As (polyhydroxyphenyl)alkane, examples 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.

[0105] As other parent nuclei, examples include: 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.

[0106] As 1,2-naphthoquinone diazide sulfonyl halide, 1,2-naphthoquinone diazide sulfonyl chloride is preferred. As 1,2-naphthoquinone diazide sulfonyl chloride, examples include 1,2-naphthoquinone diazide-4-sulfonyl chloride and 1,2-naphthoquinone diazide-5-sulfonyl chloride. Among these, 1,2-naphthoquinone diazide-5-sulfonyl chloride is preferred.

[0107] The synthesis of the quinone diazide compound can be carried out by a known condensation reaction. In the said condensation reaction, relative to the number of OH groups in the phenolic compound or alcoholic compound, 1,2-naphthoquinone diazide sulfonyl halide equivalent to preferably 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol% can be used.

[0108] As the acid generator, known compounds such as oxime sulfonate compounds, onium salts, sulfimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, and carboxylate compounds can be used. If specific examples of sulfimide compounds are listed, N-sulfonyloxyimide compounds can be listed. Specifically, N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, and N-(trifluoromethylsulfonyloxy)naphthalimide can be listed.

[0109] When a quinone diazide compound is used as the radiation-sensitive compound (B), in the composition of the present invention, with respect to 100 parts by mass of the alkali-soluble resin (A), the upper limit of the content of the quinone diazide compound is preferably 40 parts by mass, more preferably 35 parts by mass, and still more preferably 30 parts by mass; the lower limit is preferably 5 parts by mass, more preferably 10 parts by mass, and still more preferably 15 parts by mass. In this way, the adhesion of the cured film formed from the composition of the present invention can be further improved, and in addition, the radiation sensitivity of the composition of the present invention can be further improved.

[0110] When an acid generator (B2) other than the quinone diazide compound is used as the radiation-sensitive compound (B), in the composition of the present invention, with respect to 100 parts by mass of the alkali-soluble resin (A), the upper limit of the content of the acid generator (B2) is preferably 20 parts by mass, more preferably 15 parts by mass, and still more preferably 10 parts by mass; the lower limit is preferably 1 part by mass, more preferably 2 parts by mass, and still more preferably 3 parts by mass.

[0111] <Other Components>

[0112] The composition of the present invention contains an alkali-soluble resin (A) and a radiation-sensitive compound (B) as essential components, and may contain at least one selected from an adhesion aid (C), a surfactant (D), 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-generating compound (G) as other components as needed.

[0113] In order to improve the adhesion between the substrate and the coating film, the composition of the present invention may contain an adhesion aid (C). As the adhesion aid (C), for example, functional silane coupling agents such as silane coupling agents having reactive functional groups such as carboxyl group, methacryloyl group, vinyl group, isocyanate group, epoxy group, and amino group can be cited. Specifically, the following can be cited: trimethoxysilylbenzoic acid, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. As the adhesion aid (C), for example, the compounds described in Japanese Patent Application Laid-Open No. 2006-126397 and Japanese Patent Application Laid-Open No. 2009-204865 can also be used. The adhesion aid (C) can be used alone or in combination of two or more.

[0114] With respect to 100 parts by mass of the alkali-soluble resin (A), the composition of the present invention preferably contains the adhesion aid (C) in an amount of 20 parts by mass or less, more preferably 10 parts by mass or less.

[0115] The composition of the present invention may contain a surfactant (D) in order to improve its coatability. As the surfactant (D), for example, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants can be cited. The surfactant (D) can be used alone or in combination of two or more.

[0116] With respect to 100 parts by mass of the alkali-soluble resin (A), the composition of the present invention preferably contains the surfactant (D) in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less.

[0117] 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-type or to improve the heat resistance and hardness of the cured film. As the polymerizable compound (E), for example, (meth)acrylates such as monofunctional (meth)acrylate, difunctional (meth)acrylate, and trifunctional or higher (meth)acrylate can be cited. The number of (meth)acryloyl groups in the (meth)acrylate is preferably 2 to 6. Among these, trifunctional or higher (meth)acrylates are preferred, and for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate can be cited. The polymerizable compound (E) can be used alone or in combination of two or more.

[0118] With respect to 100 parts by mass of the alkali-soluble resin (A), the composition of the present invention may preferably contain the polymerizable compound (E) in an amount of 100 parts by mass or less, more preferably 75 parts by mass or less.

[0119] 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). In addition, the alkali-soluble resin (A) also contains a compound that can be called an "epoxy resin", but it is different from the epoxy resin (F) in terms of having alkali solubility. The epoxy resin (F) here is alkali-insoluble.

[0120] The epoxy resin (F) is not particularly limited as long as the compatibility is not affected. For example, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, and a resin obtained by (co)polymerizing glycidyl methacrylate can be mentioned. Among these, bisphenol A type epoxy resin, cresol novolak type epoxy resin, and glycidyl ester type epoxy resin are preferred. The epoxy resin (F) can be used alone or in combination of two or more.

[0121] With respect to 100 parts by mass of the alkali-soluble resin (A), the composition of the present invention may preferably contain the epoxy resin (F) in an amount of 50 parts by mass or less.

[0122] In order to improve the heat resistance and hardness of the cured film, the composition of the present invention may contain a heat-sensitive acid-generating compound (G). Examples of the heat-sensitive acid-generating compound (G) include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. The heat-sensitive acid-generating compound (G) can be used alone or in combination of two or more.

[0123] With respect to 100 parts by mass of the alkali-soluble resin (A), the composition of the present invention may preferably contain the heat-sensitive acid-generating compound (G) in an amount of 20 parts by mass or less, more preferably 10 parts by mass or less.

[0124] The composition of the present invention described above can be suitably used as a cured film such as an interlayer insulating film, a protective film, and a spacer; a forming material for a cured film included in a display element, etc.

[0125] [Cured Film and Its Manufacturing Method]

[0126] A method for manufacturing the cured film of the present invention using the radiation-sensitive composition of the present invention is 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 μm to 6 μm. The cured film of the present invention has high hardness, excellent heat resistance, and solvent resistance.

[0127] 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), irradiating at least a part of the coating film with radiation; step (3), developing the coating film after the radiation irradiation; and step (4), heating the developed coating film to obtain a cured film.

[0128] <Step (1)>

[0129] In step (1), the composition of the present invention is coated on a substrate, and preferably pre-baked to remove the solvent and form a coating film of the radiation-sensitive composition.

[0130] Examples of the substrate include a glass substrate, a silicon substrate, and a substrate having various metal members formed on the surface thereof.

[0131] Examples of the coating method of the composition include: spray method, roll coating method, spin coating method, slot die coating method, bar coating method, inkjet method, and preferably spin coating method and slot die coating method.

[0132] The conditions for pre-baking also vary depending on the types and content ratios of the respective components in the composition of the present invention. For example, it can be set to be carried out at 60°C to 110°C for about 30 seconds to 15 minutes.

[0133] The film thickness of the coating film of the radiation-sensitive composition after pre-baking is usually 0.5 μm to 6 μm.

[0134] <Step (2)>

[0135] 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.

[0136] Examples of the radiation include: visible light, ultraviolet light, X-rays, charged particle beams. Examples of the visible light and ultraviolet light include: g-ray (wavelength 436 nm), h-ray (wavelength 405 nm), i-ray (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm). Examples of the X-rays include synchrotron radiation. Examples of the charged particle beams include electron beams. Among these, visible light and ultraviolet light are preferred, and radiation containing at least one selected from g-ray, h-ray, i-ray, and KrF excimer laser is particularly preferred.

[0137] The exposure dose is usually 5 mJ / cm 2 ~1000 mJ / cm 2 .

[0138] <Process (3)>

[0139] In process (3), the irradiated film after radiation is developed using developability to remove the irradiated portion of the radiation. Thus, a patterned film can be obtained.

[0140] An alkaline developer is usually used in the development process. For example, an aqueous solution of an alkaline compound (alkaline compound) can be cited. As the alkaline compound, for example, 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, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene can be cited. The concentration of the alkaline compound in the alkaline developer is usually 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 that dissolve the composition of the present invention can be used as the developer.

[0141] As the development method, for example, dipping method, immersion method, rocking immersion method, spraying method can be cited. The development time varies depending on the composition of the composition and can be set to, for example, 30 seconds to 120 seconds. In addition, a rinsing treatment such as rinsing with running water can be performed on the patterned film.

[0142] In addition, the compound (B) remaining in the film can be decomposed by irradiating the entire surface of the patterned film with radiation (post-exposure). The exposure dose in the post-exposure is usually 200 mJ / cm 2 ~500 mJ / cm 2 .

[0143] <Process (4)>

[0144] In process (4), the film obtained in process (3), specifically the patterned film, is heated (post-baking treatment) to obtain a hardened film.

[0145] Regarding the heating in the hardening treatment of the 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 treatment varies depending on the type of heating machine. For example, when heating on a hot plate, it is 5 minutes to 30 minutes, and when heating in an oven, it is 30 minutes to 100 minutes. At this time, a stepwise baking method with two or more heating steps can also be used.

[0146] A cured film can be obtained in the above manner. In one embodiment, for example, a cured film can be formed on a substrate as a target interlayer insulating film, protective film, and spacer.

[0147] [Display element]

[0148] The display element of the present invention has the cured film of the present invention described above. The cured film is, for example, a protective film or an interlayer insulating film for a thin film transistor (TFT) in a display element. The display element of the present invention is, for example, a liquid crystal display or an organic electroluminescence (EL) display element.

[0149] [Examples]

[0150] 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" is described as "parts" unless otherwise specified.

[0151] <Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn)>

[0152] For the alkali-soluble resin (A), Mw and Mn are measured by gel permeation chromatography (GPC) under the following conditions. In addition, the molecular weight distribution (Mw / Mn) is calculated from the obtained Mw and Mn.

[0153] Apparatus: "GPC-101" (manufactured by Showa Denko KK)

[0154] GPC column: Combining GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 (manufactured by Shimadzu GLC Co., Ltd.)

[0155] Mobile phase: Tetrahydrofuran

[0156] Column temperature: 40°C

[0157] Flow rate: 1.0 mL / min

[0158] Sample concentration: 1.0 mass%

[0159] Sample injection volume: 100 μL

[0160] Detector: Differential refractometer

[0161] Standard substance: Monodisperse polystyrene

[0162] [Synthesis of alkali-soluble resin]

[0163] [Synthesis Example 1] (Synthesis of polymer (A-1))

[0164] Into a flask including a cooling tube and a stirrer, 10 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate (PGMEA) were charged. Subsequently, 20 parts of methacrylic acid, 20 parts of glycidyl methacrylate, 20 parts of 3,4-epoxycyclohexylmethyl methacrylate, and 40 parts of styrene were charged. After nitrogen replacement, stirring was carried out slowly, and the temperature of the solution was raised to 70 °C and maintained at this temperature for 5 hours for polymerization, thereby obtaining a polymer solution containing a polymer (A-1) as an alkali-soluble resin. The obtained polymer solution was reprecipitated in hexane and filtered, purified by vacuum drying, and the polymer (A-1) was dissolved in PGMEA to prepare a 30 mass% solution of the polymer concentration. The weight average molecular weight (Mw) of the polymer (A-1) was 10,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.3.

[0165] [Synthesis Examples 2 to 12] (Synthesis of Polymers (A-2) to (A-12))

[0166] Except for using the respective components of the types and blending amounts (parts by mass) shown in Table 1 below, polymer solutions containing polymers (A-2) to (A-12) were obtained by the same method as in Synthesis Example 1. In Table 1, "-" indicates that the component meeting the conditions was not used.

[0167]

[0168] The meanings of the respective notations in Table 1 are as follows.

[0169] MA: Methacrylic acid

[0170] AA: Acrylic acid

[0171] HS: Hydroxystyrene

[0172] FHST: 4-(1,1,1,3,3,3-Hexafluoro-2-hydroxypropan-2-yl)styrene

[0173] GMA: Glycidyl methacrylate

[0174] OXMA: (3-Ethyloxetan-3-yl)methyl methacrylate

[0175] EPMA: 3,4-Epoxycyclohexylmethyl methacrylate

[0176] ST: Styrene

[0177] BzMA: Benzyl methacrylate

[0178] MMA: Methyl methacrylate

[0179] PM: Phenyl maleimide

[0180] STMS: Styryltrimethoxysilane

[0181] ADVN: 2,2'-Azobis(2,4-dimethylvaleronitrile)

[0182] S-1 to S-5: Described below

[0183] [Components contained in the radiation-sensitive composition]

[0184] The alkali-soluble resin (A), radiation-sensitive compound (B), adhesion promoter (C), surfactant (D), polymerizable compound (E), and solvent (S) used in the preparation of the radiation-sensitive compositions of the examples and comparative examples are shown below.

[0185] 《Alkali-soluble resin (A)》

[0186] A-1 to A-12: Polymers (A-1) to (A-12) synthesized in Synthesis Examples 1 to 12

[0187] 《Radiation-sensitive compound (B)》

[0188] B-1: Condensate of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonyl chloride (2.0 mol)

[0189] B-2: 1,8-Naphthalimide trifluoromethanesulfonate

[0190] B-3: Irgacure OXE-01 (manufactured by BASF)

[0191] 《Adhesion promoter (C)》

[0192] C-1: 3-Glycidoxypropyltrimethoxysilane

[0193] C-2: 3-Methacryloxypropyltrimethoxysilane

[0194] 《Surfactant (D)》

[0195] D-1: SH8700 (manufactured by Toray Dow Corning)

[0196] 《Polymerizable compound (E)》

[0197] E-1: Dipentaerythritol hexaacrylate (DPHA)

[0198] 《Solvent (S)》

[0199] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0200] S-2: 1-Methoxy-1-(2-methoxyethoxy)ethane

[0201] S-3: 1,3-Dimethoxy-2,2-dimethylpropane

[0202] S-4: 4,4,6-Trimethyl-1,3-dioxane

[0203] S-5: 1-Penten-3-ol

[0204] [Evaluation of Radiation-Sensitive Composition]

[0205] Evaluate the following items for the radiation-sensitive compositions of the examples and comparative examples.

[0206] <Coatability>

[0207] Using a spinner, coat the radiation-sensitive composition on a silicon substrate, and then pre-bake it on a hot plate at 90 °C for 2 minutes to form a coating film with an average film thickness of 3.0 μm. Then, use an optical microscope to observe the surface of the coating film for the occurrence of dents. At this time, those without dents can be evaluated as having good coatability, and those with dents can be evaluated as having poor coatability.

[0208] The dent in the coating film refers to the following phenomenon, that is, after coating the composition on the substrate and performing pre-baking, circular depressions are formed on the surface of the coating film, or when it is obvious, pores are formed to the extent that the substrate base can be seen. The dent is caused by various factors and is considered to be caused by the evaporation of local volatile components from the wet coating film after coating, contamination by minute foreign matters, stains on the substrate, etc.

[0209] Evaluate the case where the number of dents on each substrate is 0 as AA, the case where it is 1 or more and less than 10 as BB, the case where it is 10 or more and less than 100 as CC, and the case where it is 100 or more as DD.

[0210] <Radiation Sensitivity>

[0211] Using a spinner, a radiation-sensitive composition was coated on a silicon substrate that had been 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 to form a coating film with an average film thickness of 3.0 μm. For the said coating film, a pattern mask with a line and space pattern having a width of 10 μm was interposed, and a specified amount of ultraviolet light was irradiated using a mercury lamp. Subsequently, after developing for 60 seconds at 25°C using a developer containing a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, rinsing with ultrapure water was performed 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. When the said value was less than 100 mJ / cm 2 the case was judged as AA, and when it was 100 mJ / cm 2 or more and less than 150 mJ / cm 2 the case was judged as BB, and when it was 150 mJ / cm 2 or more the case was judged as CC. The exposure amount was measured using an illuminometer (wavelength 365 nm).

[0212] <Storage Stability>

[0213] The prepared radiation-sensitive composition was sealed in a light-shielding and airtight container. After 7 days at 25°C, the container was opened, the said [radiation sensitivity] was measured, and the increase rate of the radiation sensitivity (minimum exposure amount) before and after storage for 7 days was calculated. When the said value was less than 10%, the case was judged as AA, when it was 10% or more and less than 20%, the case was judged as BB, and when it was 20% or more, the case was judged as CC. When it was AA or BB, the storage stability could be evaluated as good, and when it was CC, the storage stability could be evaluated as poor.

[0214] <Exposure Margin>

[0215] Using a spinner, a radiation-sensitive composition was coated on a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and then pre-baked on a hot plate at 90°C for 2 minutes to form a coating film with an average film thickness of 3.0 μm. For the said coating film, a pattern mask with a line and space pattern having a width of 10 μm was interposed, and a specified amount of ultraviolet light was irradiated using a mercury lamp. Subsequently, after developing for 60 seconds at 25°C using a developer containing a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, rinsing with ultrapure water was performed 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 of the said exposure amount is set as D 1 and the minimum is set as D 2 , then 100(%)×(D 1 -D 2 ) / D 1When the value is 20% or more and less than 30%, it is judged as AA; when it is 10% or more and less than 20%, it is judged as BB; when it is less than 10%, it is judged as CC. "-" means not evaluated.

[0216] <Preparation 1 of the radiation-sensitive composition>

[0217] The following describes the examples of the first composition of the present invention described above.

[0218] [Example 1]

[0219] In the polymer solution having a polymer concentration of 30% by mass containing the polymer (A-1), based on 100 parts of the polymer (A-1), 30 parts of the radiation-sensitive compound (B-1), 1 part of the adhesion promoter (C-1), and 0.05 part of the surfactant (D-1) were mixed. Further, a PGMEA solution of allyl methyl ether (AME) (the final amount of AME is shown in Table 2) was added. Then, 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 with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0220] [Examples 2 to 15 and Comparative Examples 1 to 4]

[0221] Except for using the respective components of the types shown in Table 2 below, the operation was carried out in the same manner as in Example 1 to prepare the radiation-sensitive compositions of Examples 2 to 15 and Comparative Examples 1 to 4.

[0222] The evaluation results are shown in Table 2.

[0223]

[0224] 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, among the radiation-sensitive compositions of the comparative examples, coatability and storage stability are not both achieved.

[0225] <Preparation 2 of the radiation-sensitive composition>

[0226] The following describes the examples of the second composition of the present invention described above.

[0227] [Example 21]

[0228] In the polymer solution with a polymer concentration of 30% by mass containing the polymer (A-5), based on 100 parts of the polymer (A-5), 30 parts of the radiation-sensitive compound (B-1), 1 part of the adhesion promoter (C-1), and 0.05 part of the surfactant (D-1) are mixed. Further, the obtained mixture is dissolved in the solvent (S-2) such that the concentration of all components except the solvent becomes 30% by mass, and then filtered through a membrane filter with a pore size of 0.2 μm to prepare the radiation-sensitive composition.

[0229] [Examples 22 to 28 and Comparative Examples 21 to 22]

[0230] Except for using the respective components of the types shown in Table 3 below, the radiation-sensitive compositions of Examples 22 to 28 and Comparative Examples 21 to 22 were prepared in the same manner as in Example 21.

[0231] The evaluation results are shown in Table 3.

[0232]

[0233] As shown in Table 3, it can be seen that each of the radiation-sensitive compositions of the examples has good coatability, storage stability, and exposure latitude. On the other hand, among the radiation-sensitive compositions of the comparative examples, not all have good coatability, storage stability, and exposure latitude.

Claims

1. A radiation-sensitive composition, characterized in that it comprises: an alkali-soluble resin; a radiation-sensitive compound; propylene glycol monomethyl ether acetate, wherein based on 100% by mass of the radiation-sensitive composition, the content ratio of propylene glycol monomethyl ether acetate is 50% to 95% by mass; and allyl methyl ether, wherein the radiation-sensitive composition contains the allyl methyl ether in a range of 10 wtppm to 10,000 wtppm.

2. The radiation-sensitive composition according to claim 1, characterized in that: the weight-average molecular weight in terms of polystyrene of the alkali-soluble resin obtained by gel permeation chromatography is 1,000 to 100,000, and the weight-average molecular weight / number-average molecular weight in terms of polystyrene is 1.0 to 5.

0.

3. The radiation-sensitive composition according to claim 1 or 2, characterized in that: the alkali-soluble resin is a copolymer of an ethylenically unsaturated monomer having one or more acidic functional groups and other ethylenically unsaturated monomers copolymerizable with the monomer.

4. The radiation-sensitive composition according to claim 1 or 2, characterized in that: it further contains a polymerizable compound having at least one ethylenically unsaturated double bond.

5. The radiation-sensitive composition according to claim 1 or 2, characterized in that: it is used to form a cured film as an interlayer insulating film, a protective film or a spacer.

6. A cured film, characterized in that: it is formed from the radiation-sensitive composition according to claim 5 and serves as an interlayer insulating film, a protective film or a spacer.

7. A display element, characterized in that: it has the cured film according to claim 6.

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