JP7201034B2 - Radiation sensitive composition - Google Patents

Description

The present invention relates to radiation sensitive compositions.

Radiation-sensitive compositions have conventionally been used to form patterned cured films such as interlayer insulating films, protective films and spacers, which are cured films possessed by display devices (see, for example, Patent Document 1). ).

JP 2012-159601 A

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

The inventors of the present invention have conducted studies to solve the above problems, and have found that the above 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 [1] above, containing 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 measured by gel permeation chromatography is 1,000 to 100,000, and the polystyrene-equivalent weight-average molecular weight (Mw)/number-average molecular weight (Mn) is 1.0 to 5.0, the radiation-sensitive composition according to [1] or [2].
[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 [1] to [3] above.
[5] The radiation-sensitive composition according to any one of [1] to [4], further containing a polymerizable compound having at least one ethylenically unsaturated double bond.
[6] The radiation-sensitive composition according to any one of [1] to [5], 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, formed from the radiation-sensitive composition according to [6] above.
[8] A display device having the cured film according to [7] above.
[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 at least one compound selected from 1-penten-3-ol.

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

In this specification, preferred upper and lower limits are described for the content ratio of each component, etc., but the numerical range defined by any combination of the upper and lower limits described is also described in this specification. shall be

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated. 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]
A 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, and 1,3-dimethoxy-2,2-dimethylpropane. , 4,4,6-trimethyl-1,3-dioxane, and at least one compound selected from 1-penten-3-ol.

Hereinafter, the first radiation-sensitive composition of the present invention is also referred to as "the first composition of the present invention", and the second radiation-sensitive composition of the present invention is also referred to as "the second composition of the present invention". When these first composition and second composition 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)".

Propylene glycol monomethyl ether acetate is also called "PGMEA". 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 At least one selected compound 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 a solvent in the first composition.
A first composition of the present invention contains allyl methyl 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 allyl methyl ether has a radical trapping property, during storage as a liquid composition, for example, when the first composition is negative, polymerization of the polymerizable compound (E) described below can be suppressed, and positive 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. Moreover, since the boiling point of allyl methyl ether is low, allyl methyl ether is removed by pre-baking after applying the first composition, and the effect on radiation sensitivity is small.

The upper limit of the allyl methyl ether content in the first composition is preferably 50000 wtppm, more preferably 10000 wtppm, even more preferably 7500 wtppm, and particularly preferably 5000 wtppm. When the content of allyl methyl ether is equal to or less than the upper limit, it is preferable from the viewpoint of the applicability 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 whitening of the resulting cured film can be suppressed.

The lower limit of the allyl methyl ether content in the first composition is preferably 10 wtppm, more preferably 50 wtppm. It is preferable from the viewpoint of storage stability of the first composition that the content of allyl methyl ether is equal to or higher than the lower limit. The content of allyl methyl ether can be measured by gas chromatography.

In the first composition of the present invention, as a solvent, other than PGMEA, other solvents that disperse or dissolve the components constituting the first composition, do not react with these components, and have moderate volatility ( 1) can be further included.

Other solvents (1) include, 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 monobutyl ether acetate and other propylene glycol monoalkyl ether acetates (excluding PGMEA);
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol, propylene glycol, tetrahydrofurfuryl alcohol;
Lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, propionate Aliphatic 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, pyruvic acid other esters such as ethyl;
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; Lactones such as γ-butyrolactone solvent;
aromatic hydrocarbon solvents such as toluene and xylene;

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

The upper limit of the content 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 mass %, more preferably 10 mass %, still more preferably 15 mass %. All components other than the solvent are, for example, alkali-soluble resin (A), radiation-sensitive compound (B), allyl methyl ether, and optionally added other components.
The liquid composition thus prepared can be used after being filtered using, for example, a filter having pores with 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 has excellent storage stability. In addition, the exposure margin is improved as the storage stability is improved. Details of the exposure margin are described in the Examples section.

In the second composition of the present invention, in addition to the specific solvent, other solvents that disperse or dissolve the components constituting the radiation-sensitive composition, do not react with these components, and have appropriate volatility are used as the solvent. A solvent (2) may be further included. Examples of the other solvent (2) include the other solvent (1) described above (excluding the specific solvent) and PGMEA.

Other solvent (2) can be used alone or in combination of two or more.
The upper limit of the content 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. % by mass, more preferably 60% by mass, and even more preferably 65% by mass.

The upper limit of the content 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 mass %, more preferably 10 mass %, still more preferably 15 mass %. All components other than the solvent are, for example, alkali-soluble resin (A), radiation-sensitive compound (B), and optionally added other components.

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

<Alkali-soluble resin (A)>
As the alkali-soluble resin (A), for example, polymers having acidic functional groups such as carboxy groups, phenolic hydroxyl groups and fluorinated hydroxyalkyl groups are preferred. The alkali-soluble resin means that the resin can be dissolved or swelled in an alkali developer such as a 2.38 mass % concentration tetramethylammonium hydroxide aqueous solution.

A fluorinated hydroxyalkyl group is a hydroxyalkyl group in which some of the hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms, 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. is a modified alkyl group.

Examples of polymers having acidic functional groups include novolak resins, phenol-xylylene glycol condensed resins, cresol-xylylene glycol condensed resins, phenol-dicyclopentadiene condensed resins, polybenzoxazole precursors, polyhydroxystyrene, hydroxy Polymers having phenolic hydroxyl groups, such as copolymers of styrene and styrene; Polymers having carboxy groups, such as carboxy group-containing epoxy (meth)acrylate resins containing a novolak skeleton in the main chain, polyamic acid, etc. be done.

As the polymer having an acidic functional group, an ethylenically unsaturated monomer having one or more acidic functional groups (hereinafter also referred to as "unsaturated monomer (a1)"), and (a1) Examples thereof include copolymers with other copolymerizable ethylenically unsaturated monomers (hereinafter also referred to as “unsaturated monomer (a2)”). A (meth)acrylic polymer having an acidic functional group is particularly preferred.

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

The unsaturated monomers (a1) can be used alone or in combination of two or more.
The unsaturated monomer (a2) includes, for example, N-substituted maleimides such as N-arylmaleimide, N-alkylmaleimide and N-cycloalkylmaleimide; aromatic vinyl compounds such as styrene and derivatives thereof; Having a cyclic ether ring such as an alkyl acrylate, a hydroxyalkyl (meth)acrylate, an alicyclic (meth)acrylate, an aromatic (meth)acrylate, an oxirane ring, an oxetane ring, or an oxolane ring ( (Meth)acrylic acid esters such as meth)acrylic acid esters; Aromatic ring-containing silane compounds such as styryl group-containing silane compounds; Vinyl ethers such as alicyclic-containing vinyl ethers; Polymer chains of aromatic vinyl compounds, (meth)acrylic acid esters and macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain such as polysiloxane molecular chain. Among these, from the viewpoint of imparting a crosslinkable functional group to the alkali-soluble resin, it is possible to use at least one selected from (meth)acrylic acid esters having an oxirane ring and (meth)acrylic acid esters having an oxetane ring. preferable.

More specifically, [0060] to [0062] of JP 2015-004968, [0036] to [0045] of JP 2008-233346, [0013] to of JP 2009-229567 [0021].

The unsaturated monomers (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, for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308 Publications, 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 publications, etc., 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 of structural units 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) comprises an unsaturated monomer (a1), a (meth)acrylic acid ester having an oxirane ring and a (meth)acrylic acid having an oxetane ring A copolymer with at least one selected from esters is preferred. In this copolymer, an unsaturated monomer (a2) other than these may be copolymerized. For example, at least one selected from aromatic vinyl compounds, (meth)acrylic acid aromatic ring-containing esters, (meth)acrylic acid alkyl esters, N-position substituted maleimides and styryl group-containing silane compounds may be further copolymerized. good.

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

The copolymer of (a1) and (a2) can be produced by a known method. The structure, weight average molecular weight, and molecular weight distribution can be controlled by the method disclosed in No.

The alkali-soluble resin (A) also includes alkali-soluble polysiloxane, polyimide or polybenzoxazole.
Specific examples of polysiloxane include, for example, WO 2017/188047, WO 2017/169763, WO 2017/159876, JP 2013-114238, JP 2012-53381, Examples thereof include copolymers disclosed in JP-A-2010-32977.

Specific examples of polyimide or polybenzoxazole include, for example, WO2017/169763, WO2017/159876, WO2017/057281, WO2017/159476, WO2017/ 073481, International Publication No. 2017/038828, International Publication No. 2016/148176, JP 2015-114355, JP 2013-164432, JP 2010-72143, etc. Copolymers disclosed in 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 of the number average molecular weight (Mn) to the weight average molecular weight (Mw) of the alkali-soluble resin (A) (molecular weight distribution: Mw/Mn) 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 of the alkali-soluble resin (A) in 100% by mass of all components other than the solvent of the composition is preferably 99% by mass, more preferably 95% by mass, and even more preferably 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 radiation-sensitive radical polymerization initiators (B1) and radiation-sensitive acid generators (B2).

<<Radiation-sensitive radical polymerization initiator (B1)>>
The radiation-sensitive radical polymerization initiator (B1) (hereinafter also referred to as “component (B1)”) is a compound that generates radicals upon exposure to radiation. When the composition of the present invention contains the component (B1), it can function as a radiation-curable resin composition, and the generated radicals polymerize the alkali-soluble resin (A), the polymerizable compound (E) described later, and the like. By doing so, a negative type radiation sensitive property is exhibited. The radiation sensitivity of the composition of the present invention can be further enhanced by containing the component (B1).

Examples of component (B1) include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and thioxanthone compounds.
Examples of O-acyloxime compounds include 1-[4-(phenylthio)-2-(O-benzoyloxime)], 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-[9-ethyl-6-benzoyl -9. H. -carbazol-3-yl]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9. H. -carbazol-3-yl]-ethan-1-one oxime-O-benzoate.

Acetophenone compounds include, for example, α-aminoketone compounds and α-hydroxyketone compounds. Examples of α-aminoketone compounds 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. Examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, , 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenylketone.

Examples of biimidazole compounds include 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 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′-biimidazole Imidazole is preferred.

Thioxanthone compounds include, for example, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

Among these, O-acyloxime compounds, acetophenone compounds and thioxanthone compounds are preferred, O-acyloxime compounds, α-aminoketone compounds and thioxanthone compounds are more preferred, and 1,2-octanedione 1-[4-(phenylthio)- 2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-methyl- More preferred are 1-(4-methylthiophenyl)-2-morpholinopropan-1-one and 2,4-diethylthioxanthone.

When the component (B1) is used as the radiation-sensitive compound (B), 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 is preferably The lower limit is preferably 1 part by mass, more preferably 3 parts by mass, and even more preferably 6 parts by mass. In such an embodiment, the adhesiveness 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 upon exposure to radiation. The radiation sensitivity of the composition of the present invention can be further enhanced 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, sulfonate compounds, and carboxylate compounds.

A quinonediazide compound is a compound that generates a carboxylic acid upon exposure to radiation. Since the composition of the present invention contains a quinonediazide compound as the acid generator (B2), the generated carboxylic acid enhances the solubility of the radiation-irradiated portion in an alkaline developer, resulting in positive radiation sensitivity. can be demonstrated.

As the quinonediazide compound, for example, a condensate of a phenolic compound or alcoholic compound (hereinafter also referred to as “mother nucleus”) and 1,2-naphthoquinonediazide sulfonic acid halide can be used.

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

Trihydroxybenzophenones include, for example, 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.
Examples of tetrahydroxybenzophenone include 2,2′,4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2, 3,4,2'-tetrahydroxy-4'-methylbenzophenone and 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone.

Examples of pentahydroxybenzophenone include 2,3,4,2',6'-pentahydroxybenzophenone.
Hexahydroxybenzophenones include, for example, 2,4,6,3',4',5'-hexahydroxybenzophenone and 3,4,5,3',4',5'-hexahydroxybenzophenone.

(Polyhydroxyphenyl)alkanes include, for example, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tri(p- hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl -4-hydroxyphenyl)-3-phenylpropane.

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-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferred. Examples of 1,2-naphthoquinonediazide sulfonyl chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. Among these, 1,2-naphthoquinonediazide-5-sulfonyl chloride is preferred.

A quinonediazide compound can be synthesized by a known condensation reaction. In this condensation reaction, 1,2-naphthoquinonediazide sulfonic acid halide is used in an amount of preferably 30 to 85 mol%, more preferably 50 to 70 mol%, based on the number of OH groups in the phenolic compound or alcoholic compound. be able to.

Known compounds can be used as oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds as acid generators. Specific examples of sulfonimide compounds include N-sulfonyloxyimide compounds, specifically N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-( trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthyl imides.

When a quinonediazide compound is used as the radiation-sensitive compound (B), the upper limit of the content of the quinonediazide 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 adhesiveness 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 a quinonediazide compound is used as the radiation-sensitive compound (B), the acid generator (B2) is added to 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; the lower limit is preferably 1 part by mass, more preferably 2 parts by mass, more preferably 3 parts by mass part by mass.

<Other ingredients>
The composition of the present invention contains an alkali-soluble resin (A) and a radiation-sensitive compound (B) as essential components. D), at least one 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) can contain one.

The composition of the present invention can contain an adhesion promoter (C) in order to improve the adhesion between the substrate and the coating film. Examples of adhesion aids (C) include functional silane coupling agents such as silane coupling agents having a reactive functional group such as a carboxy group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, and an amino group. be done. Specifically, trimethoxysilylbenzoic 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)- 3-aminopropyltrimethoxysilane can be mentioned. As the adhesion aid (C), for example, 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 an amount of preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin (A). .

The composition of the present invention can contain a surfactant (D) in order to improve its coatability. Surfactants (D) include, for example, fluorine-based surfactants, silicone-based surfactants and nonionic surfactants. A surfactant (D) can be used individually or in combination of 2 or more types.

The composition of the present invention can contain the surfactant (D) in an amount of preferably 5 parts by mass or less, more preferably 2 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin (A). .

The composition of the present invention contains a polymerizable compound (E) having at least one ethylenically unsaturated double bond in order to make the composition negative or to improve the heat resistance and hardness of the cured film. can contain. Examples of the polymerizable compound (E) include (meth)acrylates such as monofunctional (meth)acrylates, bifunctional (meth)acrylates, and tri- or higher functional (meth)acrylates. The number of (meth)acryloyl groups in the (meth)acrylate is preferably 2-6. Among these, tri- or more functional (meth)acrylates are preferred, and examples thereof include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Polymerizable compounds (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 an amount of preferably 100 parts by mass or less, more preferably 75 parts by mass or less, relative to 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. Although the alkali-soluble resin (A) also includes what can be called an "epoxy resin", it differs from the epoxy resin (F) in that it is alkali-soluble. The epoxy resin (F) here is alkali-insoluble.

The epoxy resin (F) is not limited as long as it does not affect the compatibility. type epoxy resins, glycidylamine type epoxy resins, heterocyclic epoxy resins, and resins obtained by (co)polymerizing glycidyl methacrylate. Among these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, and glycidyl ester type epoxy resins are preferred. Epoxy resin (F) can be used individually or in combination of 2 or more types.

The composition of the present invention can contain the epoxy resin (F) in an amount of preferably 50 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 a heat-sensitive acid-generating compound (G) in order to improve the heat resistance and hardness of the cured film. Examples of the heat-sensitive acid-generating compound (G) include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts. The heat-sensitive acid-generating compound (G) can be used alone or in combination of two or more.

The composition of the present invention preferably contains 20 parts by mass or less, more preferably 10 parts by mass or less of the heat-sensitive acid-generating compound (G) per 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 cured films of display elements, such as cured films such as interlayer insulating films, protective films and spacers.

[Cured film and its manufacturing method]
A method for producing the 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 interlayer insulating films, protective films, and spacers. The thickness of the cured film is usually 0.5 to 6 μm. The cured film of the present invention has high hardness and excellent heat resistance and solvent resistance.

The cured film of the present invention can be produced by, for example, the step (1) of forming a coating film of the radiation-sensitive composition of the present invention on a substrate, the step (2) of irradiating at least part of the coating film with radiation, and the It can be formed by a production method comprising the step (3) of developing the coating film after development and the step (4) of heating the coating film after development to obtain a cured film.

<Step (1)>
In step (1), the composition of the present invention is applied onto a substrate, and the solvent is removed, preferably by pre-baking, to form a coating film of the radiation-sensitive composition.
Examples of substrates include glass substrates, silicon substrates, and substrates having various metal members formed thereon.

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

<Step (2)>
In step (2), at least part of the coating film formed in step (1) is irradiated with radiation. For example, the coating film is irradiated with radiation through a mask having a predetermined pattern.
Examples of radiation include visible light, ultraviolet rays, X-rays, and charged particle beams. Examples of 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). . X-rays include, for example, synchrotron radiation. Examples of charged particle beams include electron beams. Among these, visible light and ultraviolet light are preferred, and radiation containing at least one selected from g-line, h-line, i-line and KrF excimer laser light is particularly preferred.
The exposure dose is usually 5-1000 mJ/cm ² .

<Step (3)>
In step (3), the coated film after irradiation is subjected to development treatment using a developing solution to remove the portion irradiated with radiation. Thereby, a patterned coating film can be obtained.
For the development processing, an alkaline developer is usually used, for example, an aqueous solution of an alkaline compound (basic compound). Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, 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-nonane. The concentration of the alkaline compound in the alkaline developer is usually 0.1-10% 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.

The developing method includes, for example, a liquid immersion method, a dipping method, a swinging immersion 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 with running water, for example.

In addition, decomposition treatment of the compound (B) remaining in the coating film can be performed by irradiating the entire surface of the patterned coating film with radiation (post-exposure). The exposure dose in the post-exposure is usually 200-500 mJ/cm ² .

<Step (4)>
In step (4), the coating film obtained in step (3), specifically, the patterned coating film is heated (post-baking treatment) to obtain a cured film.
A heating device such as a hot plate or an oven can be used for heating in the curing treatment of the coating film. The heating temperature in the curing treatment is usually 120-250°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 heat treatment is performed on a hot plate, and 30 to 100 minutes when heat treatment is performed in an oven. At this time, a step baking method in which the heating process is performed two or more times can also be used.
A cured film can be obtained as described above. In one embodiment, for example, a desired interlayer insulating film, a protective film and a cured film as spacers can be formed on the substrate.

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

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

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

[Synthesis of alkali-soluble resin]
[Synthesis Example 1] (Synthesis of polymer (A-1))
A flask equipped with a condenser and 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-epoxycyclohexylmethyl methacrylate, and 40 parts of styrene were charged, and after nitrogen substitution, the temperature of the solution was raised to 70°C while gently stirring, Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution containing the polymer (A-1), which is an alkali-soluble resin. The resulting polymer solution was reprecipitated in hexane, filtered, and purified by vacuum drying. Polymer (A-1) was dissolved in PGMEA to prepare a solution with 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), respectively, in the same manner as in Synthesis Example 1 except that each component of the type and amount (parts 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: methacrylic acid AA: acrylic acid HS: hydroxystyrene FHST: 4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)styrene GMA: glycidyl methacrylate OXMA: (3 -ethyloxetan-3-yl)methyl methacrylate EPMA: 3,4-epoxycyclohexylmethyl methacrylate ST: styrene BzMA: benzyl methacrylate MMA: methyl methacrylate PM: phenylmaleimide STMS: styryltrimethoxysilane ADVN: 2,2'-azobis ( 2,4-dimethylvaleronitrile)
S-1 to S-5: described later

[Components contained in the radiation-sensitive composition]
Alkali-soluble resin (A), radiation-sensitive compound (B), adhesion aid (C), surfactant (D), polymerizable compound (E ) and 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-methacryloxypropyltrimethoxysilane
<<Surfactant (D)>>
D-1: SH8700 (manufactured by Dow Corning Toray)
<<polymerizable compound (E)>>
E-1: Dipentaerythritol hexaacrylate (DPHA)
<<Solvent (S)>>
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: 1-methoxy-1-(2-methoxyethoxy)ethane S-3: 1,3-dimethoxy-2,2-dimethylpropane S-4: 4,4,6-trimethyl-1,3-dioxane S-5: 1-penten-3-ol

[Evaluation of Radiation-Sensitive Composition]
The following items were evaluated for the radiation-sensitive compositions of Examples and Comparative Examples.
<Applicability>
After applying the radiation-sensitive composition onto a silicon substrate using a spinner, it was pre-baked on a hot plate at 90° C. for 2 minutes to form a coating film having an average thickness of 3.0 μm. Then, the surface of this coating film was observed for repelling using an optical microscope. At this time, it can be evaluated that the coating property is good when repelling does not occur, and the coating property is poor when repelling occurs.

Repelling of the coating film is a phenomenon in which circular dents are formed on the surface of the coating film after the composition is applied on the substrate and pre-baked, or in extreme cases, holes are formed so that the base material of the substrate can be seen. . The cissing is caused by various factors, but is believed to be caused by local evaporation of volatile components from the wet coating film after coating, contamination by minute foreign matter, contamination of the substrate, and the like.
A case where the number of cissing per substrate was 0 was evaluated as AA, a case where the number was 1 or more and less than 10 was BB, a case where 10 or more and less than 100 was CC, and a case of 100 or more was DD.

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

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

<Exposure Margin>
Using a spinner, a radiation-sensitive composition was applied onto a silicon substrate treated with HMDS at 60° C. for 60 seconds, and then prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with an average thickness of 3.0 μm. bottom. This coating film was irradiated with a predetermined amount of ultraviolet rays from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, using a developer consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was performed at 25° C. for 60 seconds, and then washing was performed with running ultrapure water for 1 minute. At this time, the exposure dose capable of forming a line-and-space pattern with a width of 10 μm was measured. When the maximum value of the exposure dose is D ₁ and the minimum value is D ₂ , 100 (%) × (D ₁ - D ₂ )/D ₁ is AA when the value is 20% or more and less than 30%, and 10% or more. A case of less than 20% was judged to be BB, and a case of less than 10% was judged to be CC. "-" is not evaluated.

<Preparation 1 of Radiation-Sensitive Composition>
Examples of the first composition of the present invention are described below.
[Example 1]
To the polymer solution containing the polymer (A-1) and having a polymer concentration of 30% by mass, 30 parts of the radiation-sensitive compound (B-1), based on 100 parts of the polymer (A-1), and an adhesion promoter 1 part of the agent (C-1) and 0.05 part of the surfactant (D-1) were mixed, and a PGMEA solution of allyl methyl ether (AME) was added (the final amount of AME is shown in Table 2). ). Furthermore, the obtained mixture was dissolved in the solvent (S-1) (PGMEA) so that the concentration of all components other than the solvent was 30% by mass, filtered through a membrane filter with a pore size of 0.2 μm, and exposed to radiation. A sexual composition was prepared.

[Examples 2 to 15 and Comparative Examples 1 to 4]
Radiation-sensitive compositions of Examples 2 to 15 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, except that the components shown in Table 2 below were used.
Table 2 shows the above evaluation results.

As shown in Table 2, it can be seen that each radiation-sensitive composition of Examples 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 2 of radiation sensitive composition>
Examples of the above-described second composition of the present invention are described below.
[Example 21]
To the polymer solution containing the polymer (A-5) and having a polymer concentration of 30% by mass, 30 parts of the radiation-sensitive compound (B-1), an adhesion aid, 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 solvent (S- 2) and filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[Examples 22-28 and Comparative Examples 21-22]
Radiation-sensitive compositions of Examples 22 to 28 and Comparative Examples 21 to 22 were prepared in the same manner as in Example 21 except that the components shown in Table 3 below were used.
Table 3 shows the above evaluation results.

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

Claims (7)

an alkali-soluble resin;
a radiation sensitive compound;
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 and at least one selected compound. The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin measured by gel permeation chromatography is 1,000 to 100,000, and the polystyrene-equivalent weight average molecular weight (Mw)/number average molecular weight (Mn) is 1.5. 2. The radiation-sensitive composition according to claim 1, which is 0 to 5.0. 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 Item 1 or 2. 4. The radiation-sensitive composition according to any one of claims 1 to 3, further comprising a polymerizable compound having at least one ethylenically unsaturated double bond. 5. The radiation-sensitive composition according to any one of claims 1 to 4, which is used for forming a cured film as an interlayer insulating film, a protective film or a spacer. A method for producing a cured film, comprising the step of producing a cured film as an interlayer insulating film, a protective film or a spacer using the radiation-sensitive composition according to claim 5 . A method for producing a display element, comprising a step of producing a display element using the cured film obtained by the method for producing a cured film according to claim 6.