JP2019086559A - Resin composition for negative photoresist and cured film - Google Patents

Abstract

To provide a resin composition for negative photoresist which has no corrosion of a member by a residual acid, and has no problem in lowering transparency by degradation of a resin.SOLUTION: A resin composition for negative photoresist contains a component (A) formed of an acid generator containing an onium gallate salt represented by general formula (1), a component (B) that is an alkali-soluble resin having a protonic polar group, and a crosslinking agent component (C). In the formula (1), Rto Reach independently represents an alkyl group having 1 to 18 carbon atoms or Ar, but at least one of them is Ar, Ar is an aryl group having 6 to 14 carbon atoms (excluding carbon number of substituent), a part of hydrogen atoms in the aryl group may be substituted by alkyl groups each having 1 to 18 carbon atoms, E represents an element of a valence n of the group 15 to the group 17 (IUPAC expression), n is an integer of 1 to 3, and Ris an organic group bonded to E.SELECTED DRAWING: None

Description

The present invention relates to a chemically amplified negative photoresist resin composition and a cured film for a member that is required to have an optical property containing an onium gallate salt having a specific structure.

In general, a protective film for preventing deterioration or damage to an electronic component such as a semiconductor integrated circuit or a flat panel display (FPD), a planarizing film for planarizing the surface of the element, and insulation between wirings arranged in layers An interlayer insulating film is provided, and a photosensitive resin composition (hereinafter, also referred to as "resin composition for photoresist") has been used for the formation. Above all, not only insulation but also transparency is important for the interlayer insulating film used to improve the display quality of FPD, and resistance to discoloration by such heat or chemical treatment during the process is also important. Furthermore, in order to meet the requirements such as high resolution and high definition, high resolution and high sensitivity are also required.

In the conventional interlayer insulating film, a positive photosensitive resin composition comprising a binder resin, a photosensitive agent, a solvent and the like is used, and an acrylic resin has been mainly used as the binder resin (see, for example, Patent Document 1). . However, in the case of acrylic resin, coloring is observed by heat treatment, leaving a problem from the viewpoint of transmittance.
In addition, a negative photosensitive resin composition containing a polyfunctional acrylic compound having an ethylenically unsaturated bond is used as a resist film for overcoating as a protective film and a resist resin for color filters (for example, Patent Document 2) There is room for improvement in resolution and sensitivity as well as heat shrinkage after curing. Furthermore, a cured product obtained by irradiating and curing an active energy ray on a negative type photoresist composed of an acid generator, a resin and a crosslinking agent causes corrosion of the base, deterioration of the resin and the like, and coloring due to the remaining strong acid. There was a problem that transparency decreased.

Japanese Patent Application Laid-Open No. 2003-076012 Revised 2011/129210

An object of the present invention is to provide a resin composition for negative photoresist, which is suitable as a resin composition used for an interlayer insulating film, a resist for overcoat, and a resist for color filter.

The present inventors have found a resin composition for negative photoresist suitable for the above purpose.
That is, according to the present invention, a component (A) comprising an acid generator containing an onium gallate salt represented by the following general formula (1), a component (B) which is an alkali-soluble resin having a protic polar group, and It is a resin composition for negative type photoresists containing the agent component (C).

[In formula (1), R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 18 carbon atoms or Ar, provided that at least one is Ar,
Ar is an aryl group having 6 to 14 carbon atoms (not including the carbon number of the following substituents), and a part of hydrogen atoms in the aryl group is an alkyl group having 1 to 18 carbon atoms, a halogen atom is A substituted alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an alkynyl group of 2 to 18 carbon atoms, an aryl group of 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, -OR ⁶ Alkoxy group or aryloxy group represented, acyl group represented by R ⁷ CO-, acyloxy group represented by R ⁸ COO-, alkylthio group or arylthio group represented by -SR ⁹ , -NR ¹⁰ R ¹¹ And may be substituted with an amino group represented by or a halogen atom,
R ^{6 to} R ^{9 each} represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
R ¹⁰ and R ^{11 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms;
E represents an element of valence n of 15 to 17 groups (IUPAC notation),
n is an integer of 1 to 3,
R ⁵ is an organic group bonded to E, the number of R ⁵ is n + 1, and (n + 1) R ⁵ may be identical to or different from each other, and two or more of R ⁵ may be directly to each other or -O -, - S -, - SO -, - SO 2 -, - NH -, - CO -, - COO -, - CONH-, ring structure containing an element E through an alkylene group or a phenylene group You may form ]

  The resin composition for negative photoresists of the present invention is free from corrosion of members due to residual acid, and there is no problem that the transparency is deteriorated due to the deterioration of the resin.

  Hereinafter, embodiments of the present invention will be described in detail.

In the above general formula (1), as the alkyl group having 1 to 18 carbon atoms in R ^{1 to} R ⁴ , a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- Octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl etc., branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl etc., cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl and pinanyl etc.).
From the viewpoint of the catalytic activity in the cationic polymerization reaction, those substituted with a halogen atom, a nitro group or a cyano group are preferable, and those substituted with a fluorine atom are more preferable.

The aryl group of 6 to 14 carbon atoms (not including the carbon number of the following substituents) in R ^{1 to} R ⁴ in the above general formula (1) is a monocyclic aryl group (such as phenyl), condensation Polycyclic aryl groups (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl and naphthoquinolyl, etc.) and aromatic heterocyclic hydrocarbon groups (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl etc.) And indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, tianthrenyl, phenoxazinyl, phenoxaxil; Ynyl, chromanyl, isochromanyl, coumarinyl, dibenzothienyl, Kisantoniru, Chiokisantoniru, dibenzofuranyl, etc. fused polycyclic heterocyclic ring).
As the aryl group, in addition to the above, a part of hydrogen atoms in the aryl group is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms in which a halogen atom is substituted, an alkenyl having 2 to 18 carbon atoms Group, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group or aryloxy group represented by -OR ⁶ , or R ⁷ CO- It may be substituted by an acyl group, an acyloxy group represented by R ⁸ COO-, an alkylthio group or arylthio group represented by -SR ⁹ , an amino group represented by -NR ¹⁰ R ¹¹ or a halogen atom.

In the above substituents, examples of the alkenyl group having 2 to 18 carbon atoms include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1- Methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl etc., cycloalkenyl groups (eg 2-cyclohexenyl and 3-cyclohexenyl) and And arylalkenyl groups such as styryl and cinnamyl.

In the above substituents, examples of the alkynyl group having 2 to 18 carbon atoms include a linear or branched alkynyl group (ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl- 2-propynyl, 1,1-dimethyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 3-methyl-1-butynyl, 1-decynyl And 2-decynyl, 8-decynyl, 1-dodecynyl, 2-dodecynyl and 10-dodecynyl and the like) and arylalkynyl groups (phenylethynyl and the like).

In the above substituents, examples of the alkyl group having 1 to 8 carbon atoms substituted with a halogen atom include linear alkyl groups (trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trichloroethyl, 2,2, 2-trifluoroethyl, 1,1-difluoroethyl, heptafluoro-n-propyl, 1,1-difluoro-n-propyl, 3,3,3-trifluoro-n-propyl, nonafluoro-n-butyl, 3 , 3,4,4,4-pentafluoro-n-butyl, perfluoro-n-pentyl, perfluoro-n-octyl etc., branched alkyl group (hexafluoroisopropyl, hexachloroisopropyl, hexafluoroisobutyl, nonafluoro- tert-butyl etc.), cycloalkyl group (pentafluorocyclopropyl, nonaf Orosi black butyl, perfluorocyclopentyl and perfluorocyclohexyl, etc.) and bridged cyclic alkyl group (perfluoro adamantyl, etc.).

In the above substituents, an alkoxy group represented by -OR ⁶ , an acyl group represented by R ⁷ CO-, an acyloxy group represented by R ⁸ COO-, an alkylthio group represented by -SR ⁹ , -NR ¹⁰ Examples of R ^{6 to} R ^{11 in the} amino group represented by R ¹ include alkyl groups having 1 to 8 carbon atoms, and specific examples include alkyl groups having 1 to 8 carbon atoms among the above alkyl groups. .

In the above substituents, an aryloxy group represented by -OR ¹⁶ , an acyl group represented by R ⁷ CO-, an acyloxy group represented by R ⁸ COO-, an arylthio group represented by -SR ⁹ , -NR Examples of R ^{6 to} R ¹¹ of the amino group represented by ¹⁰ R ¹¹ include aryl groups having 6 to 14 carbon atoms, and specific examples include the above-mentioned aryl groups having 6 to 14 carbon atoms.

Examples of the alkoxy group represented by —OR ⁶ include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and 2- Methyl butoxy etc. are mentioned.
Examples of the aryloxy group represented by —OR ⁶ include phenoxy, naphthoxy and the like.
The acyl group represented by R ⁷ CO— includes acetyl, propanoyl, butanoyl, pivaloyl and benzoyl.
Examples of the acyloxy group represented by R ⁸ COO- include acetoxy, butanoyloxy and benzoyloxy.
Examples of the alkylthio group represented by -SR ⁹ include methylthio, ethylthio, butylthio, hexylthio and cyclohexylthio.
The arylthio group represented by -SR ⁹ includes phenylthio, naphthylthio and the like.
Examples of the amino group represented by -NR ¹⁰ R ¹¹ include methylamino, ethylamino, propylamino, dimethylamino, diethylamino, methylethylamino, dipropylamino, dipropylamino and piperidino.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Among these substituents, from the viewpoint of catalytic activity in the cationic polymerization reaction, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, a halogen atom, a nitro group and a cyano group are preferable, and a carbon atom having 1 to 8 carbon atoms substituted More preferred are an alkyl group and a fluorine atom.

R ⁵ in the above general formula (1) represents an organic group bonded to E, and may be the same or different. Examples of R ⁵ include aryl groups having 6 to 14 carbon atoms, alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, and alkynyl groups having 2 to 18 carbon atoms, and aryl groups further have carbon atoms An alkoxy represented by an alkyl group of 1 to 18, an alkenyl group of 2 to 18 carbon atoms, an alkynyl group of 2 to 18 carbon atoms, an aryl group of 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group and -OR ⁶ Group or aryloxy group, an acyl group represented by R ⁷ CO-, an acyloxy group represented by R ⁸ COO-, an alkylthio group or arylthio group represented by -SR ⁹ or -NR ¹⁰ R ¹¹ It may be substituted by an amino group or a halogen atom.

The aryl group having 6 to 14 carbon atoms, the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms and the alkynyl group having 2 to 18 carbon atoms of the above organic group are exemplified by R in General Formula (1) ^The same ones as described in ^{1 to} R ⁴ can be mentioned.

The two or more ^{R 5} may bond directly or -O -, - S -, - SO -, - SO 2 -, - NH -, - CO -, - COO -, - CONH-, an alkylene group or a phenylene group A ring structure containing the element L may be formed via

E in the above general formula (1) represents an element of valence n of groups 15 to 17 (IUPAC notation), and combines with an organic group R ⁵ to form an onium ion [E ⁺ ]. Among the Group 15 to 17 elements, preferred are O (oxygen), N (nitrogen), P (phosphorus), S (sulfur) or I (iodine), and the corresponding onium ions are oxonium, ammonium, Phosphonium, sulfonium and iodonium. Among them, ammonium, phosphonium, sulfonium and iodonium which are stable and easy to handle are preferable, and sulfonium and iodonium which are excellent in cationic polymerization performance and crosslinking reaction performance are more preferable.
n represents the valence of the element E and is an integer of 1 to 3.

Specific examples of the oxonium ion include oxonium such as trimethyloxonium, diethylmethyloxonium, triethyloxonium, tetramethylenemethyloxonium and the like; 4-methylpyrilinium, 2,4,6-trimethylpyrilinium, 2,6 -Pyririnium such as di-tert-butylpyrilinium and 2,6-diphenylpyrilinium; and chromenium and isochromium such as 2,4-dimethylchromium, 1,3-dimethylisochromium and the like.

Specific examples of the ammonium ion include tetraalkyl ammonium such as tetramethyl ammonium, ethyl trimethyl ammonium, diethyl dimethyl ammonium, triethyl methyl ammonium, tetraethyl ammonium and the like; N, N-dimethyl pyrrolidinium, N-ethyl-N-methyl pyrrolidine Pyrrolidinium such as N, N, N-diethylpyrrolidinium; N, N'-dimethylimidazolinium, N, N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3, Imidazolinium such as 4-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidinium such as N, N'-dimethyltetrahydropyrimidinium; N, N'-dimethyl mole Holinium and other Piperidinium such as N, N'-diethylpiperidinium; pyridinium such as N-methyl pyridinium, N-benzyl pyridinium, N-phenacyl pyridinium; imidazolium such as N, N'-dimethyl imidazolium; N -Quinolium such as methylquinolium, N-benzylquinolium, N-phenacylquinolium; isoquinolium such as N-methylisoquinolium; thiazonium such as benzylbenzothiazonium, phenacylbenzothiazonium; benzylacridium And acridium such as phenacil acridium.

Specific examples of the phosphonium ion include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, tetrakis (4-methoxyphenyl) phosphonium and the like. Triaryl phosphoniums such as triphenyl benzyl phosphonium, triphenyl phenacyl phosphonium, triphenyl methyl phosphonium, triphenyl butyl phosphonium, etc .; triethyl benzyl phosphonium, tributyl benzyl phosphonium, tetraethyl phosphonium, tetrabutyl phosphonium, tetrahexyl phosphonium, triethyl phenacil phosphonium Tetraalkyl such as tributylphenacyl phosphonium Suhoniumu and the like.

Specific examples of the sulfonium ion include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris (4 (4) -Fluorophenyl) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-tolylthio) phenyldi-p-tolyl Sulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenylthio) pheny Bis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, [4- (2-thioxanthone) Ruthio) phenyl] diphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis ( 4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methoxyphenyl) sulfonio] phenyl} sulfide, 4- (4 4-Benzoyl-2-chlorophenylthio) phenylbis (4-fluoro) Phenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenyl Sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2 -Yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- (9-oxo-9H-thioxanthen-2-yl) thiophenyl-9-oxo -9H-thioxanthen-2-yl fe Nylsulfonium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyl di-p-tolylsulfonium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (4- Benzoylphenylthio)] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthiaanthrenium, 5-tolylthia Triarylsulfonium such as anthrenium, 5- (4-ethoxyphenyl) thiaanthrenium, 5- (2,4,6-trimethylphenyl) thiaanthrenium; diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenyl Benzyl sul Sodium, diarylsulfonium such as diphenylmethylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetoxycarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl (2-naphthylmethyl (2-naphthylmethyl) ) Methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4- Acetcarbonyloxyphenyl methyl phenacyl sulfonium, 2-naphthyl methyl phenacyl sulfo Monoarylsulfonium such as sodium, 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium, etc .; dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphena And trialkylsulfonium such as silsulfonium.

Specific examples of the iodonium ion include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4- Iodonium ions such as decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium and 4-isobutylphenyl (p-tolyl) iodonium.

As an anion structure of the acid generator represented by said General formula (1), what is represented with following Chemical formula (a-1)-(a-9) can be illustrated preferably.

The resin composition for negative photoresist of the present invention is an alkali-soluble resin having a component (A) comprising an acid generator containing an onium gallate salt represented by the above general formula (1), and a protic polar group. It is characterized by comprising the component (B) and the crosslinker component (C).

  In the resin composition for negative photoresists of the present invention, the component (A) may be used in combination with other known acid generators. Other acid generators include, for example, onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfoneimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, nitrobenzyl compounds Besides, organic halides, disulfone and the like can be mentioned.

  As another acid generator conventionally known, preferably, one or more selected from the group of an onium compound, a sulfone imide compound, a diazomethane compound and an oxime sulfonate compound are preferable.

  When such conventionally known other acid generators are used in combination, their use ratio may be arbitrary, but usually 10 to 900 parts by weight of the other acid generator to 100 parts by weight of the acid generator of the present invention , Preferably 25 to 400 parts by weight.

  The content of the component (A) is preferably 0.01 to 10% by weight in the solid content of the negative photoresist resin composition.

Alkali-soluble resin having protic polar group (B)
The alkali-soluble resin having a protic polar group is not particularly limited as long as it is a resin having a protic polar group. For example, novolak resin, polyhydroxystyrene, copolymer of hydroxystyrene, copolymer of hydroxystyrene and styrene , Copolymers of hydroxystyrene, styrene and (meth) acrylic acid derivatives, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, polyimide containing a phenolic hydroxyl group, polyamic acid containing a phenolic hydroxyl group, Copolymers (copolymers) such as phenol-dicyclopentadiene condensation resin and cycloolefin resin, homopolymers and the like are used. Among these, novolak resin, polyhydroxystyrene, copolymer of polyhydroxystyrene, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene, styrene and (meth) acrylic acid derivative, phenol-xylylene glycol Preferred are copolymers (copolymers) and homopolymers such as condensation resins and cycloolefin resins. These alkali-soluble resins (B) having a protic polar group may be used alone or in combination of two or more.

  Here, the protic polar group means a group including an atom in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or Group 16 of the periodic table. Among the atoms belonging to Group 15 or Group 16 of the Periodic Table, atoms belonging to the first or second period of Group 15 or Group 16 of the periodic table are preferable, and more preferably an oxygen atom, a nitrogen atom or sulfur It is an atom, particularly preferably an oxygen atom.

Specific examples of such a protic polar group include polar groups having an oxygen atom such as hydroxyl group, carboxy group (hydroxycarbonyl group), sulfonic acid group, phosphoric acid group, etc .; primary amino group, secondary amino group And polar groups having a nitrogen atom such as primary amide group and secondary amide group (imide group); polar groups having a sulfur atom such as thiol group; and the like. Among these, those having an oxygen atom are preferable, and more preferably a hydroxyl group or a carboxy group.
In the present invention, the number of protic polar groups bonded to the alkali-soluble resin having a protic polar group is not particularly limited, and different types of protic polar groups may be contained.

The above novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.

Examples of the above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like can be mentioned.

Moreover, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde etc. are mentioned as said aldehydes.

Specific examples of the novolak resin include phenol / formaldehyde condensation novolac resin, cresol / formaldehyde condensation novolac resin, phenol-naphthol / formaldehyde condensation novolac resin, and the like.

The alkaline soluble resin (B) having a protic polar group may contain a phenolic low molecular weight compound as a part of the component.

Examples of the above-mentioned low molecular weight phenolic compound include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl) -1-one. Phenylethane, tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1 -Methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4 -[1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane, 1,1,2,2-tetra (4-hydro) Shifeniru) ethane, 4,4 '- {1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene} bisphenol and the like. These low molecular weight phenolic compounds may be used alone or in combination of two or more.

The content of the low molecular weight phenolic compound in the alkali-soluble resin (B) having a protic polar group is 40% by weight or less based on 100% by weight of the alkali-soluble resin (B) having a protic polar group. It is preferably 1 to 30% by weight.

The cycloolefin resin is, for example, a homopolymer or copolymer of a cycloolefin monomer having a cyclic structure (alicyclic or aromatic ring) of a cycloolefin monomer unit in the main chain, and is a protic polar Having a group.

  As such cycloolefin resin, a polymer of one or more cycloolefin monomers, or a copolymer of one or more cycloolefin monomers and a monomer copolymerizable therewith. In the present invention, at least a protic polar group is contained in the cycloolefin monomer (b) or the copolymerizable monomer as a monomer for forming the cycloolefin resin, although the combination includes coalescence. is necessary.

  Specific examples of the cycloolefin monomer (b) (hereinafter, appropriately referred to as “monomer (b)”) include bicyclo [2.2.1] hept-2-ene, 2-hydroxycarbonylbicyclo [2 .2.1] Hept-5-ene, 2-methyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-hydroxycarbonyl-2-methoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo [2.2.1] hept- 5-ene, 2-hydroxycarbonyl-2-propoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-b Xylcarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-pentyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-hexyl Oxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-cyclohexyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-phenoxy Carbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-naphthyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-biphenyloxy Carbonylmethylbicyclo [2.2.1] hept-5-ene, -Hydroxycarbonyl-2-benzyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-hydroxyethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2 , 3-Dihydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-methoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-ethoxy Carbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-butoxycarbonylbicyclo [2 .2.1] Hept-5-ene, 2-hydroxycarbonyl-3-pentylo Xylcarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-hexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-cyclohexyloxycarbonyl Bicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-phenoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo [2 .2.1] Hept-5-ene, 2-hydroxycarbonyl-3-biphenyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbonylbicyclo [2.2 .1] Hept-5-ene, 2-hydroxycarbonyl-3-hydroxyeth Cyclocarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 3-methyl-2-hydroxycarbonylbicyclo [2 2.2.1] Hept-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyltricyclo [5.2.1.02, 6] deca-3,8-diene, 4-hydroxycarbonyltetracyclo [6.2.1.13, 6.2, 7] dodec-9-ene, 4-methyl-4-hydroxycarbonyltetracyclo [6. 2.1.13, 6. 02, 7] dodec-9-ene, 4, 5-dihydroxycarbonyltetracyclo [6.2.1.13, 6.02, 7] dodeca-9 En, (4-exo-5-endo-4,5-dihydroxycarbonyltetracyclo [6.2.1.13,6.20,7] dodec-9-ene), 4-carboxymethyl-4-hydroxycarbonyl Tetracyclo [6.2.1.13,6.02,7] dodec-9-ene, N- (hydroxycarbonylmethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide, N- (hydroxycarbonylethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylpentyl) bicyclo [2.2.1] hept-5- Ene-2,3-dicarboximide, N- (dihydroxycarbonylethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (dihydroxyki) (Cycarbonylpropyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylphenethyl) bicyclo [2.2.1] hept-5-ene-2,3 N- (2- (4-hydroxyphenyl) -1- (hydroxycarbonyl) ethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- Carboxy group-containing cycloolefins such as hydroxycarbonylphenyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide; 2- (4-hydroxyphenyl) bicyclo [2.2.1] hept -5-ene, 2-methyl-2- (4-hydroxyphenyl) bicyclo [2.2.1] hept-5-ene, 4- (4-hydroxyphenyl) tetra Chromo [6.2.1.13,6.02,7] dodec-9-ene, 4-methyl-4- (4-hydroxyphenyl) tetracyclo [6.2.1.13,6.02,7] Dodec-9-ene, 2-hydroxybicyclo [2.2.1] hept-5-ene, 2-hydroxymethylbicyclo [2.2.1] hept-5-ene, 2-hydroxyethylbicyclo [2.2 .1] Hept-5-ene, 2-methyl-2-hydroxymethylbicyclo [2.2.1] hept-5-ene, 2,3-dihydroxymethylbicyclo [2.2.1] hept-5-ene , 2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2- ( 1-hydroxy-1- Fluoromethyl-2,2,2-trifluoroethyl) bicyclo [2.2.1] hept-5-ene, 2- (2-hydroxy-2-trifluoromethyl-3,3,3-trifluoropropyl) ) Bicyclo [2.2.1] hept-5-ene, 3-hydroxytricyclo [5.2.1.02,6] deca-4,8-diene, 3-hydroxymethyltricyclo [5.2. 1.02,6] deca-4,8-diene, 4-hydroxytetracyclo [6.2.1.13,6.02,7] dodeca-9-ene, 4-hydroxymethyltetracyclo [6.2 1.1. 3,6. 02, 7] dodec-9-ene, 4, 5-dihydroxymethyl tetracyclo [6.2.1. 36, 6. 02, 7] dodeca-9-ene, 4- (hydroxy Ethoxycarbonyl) tetracyclo [6.2. 1.13.6. 02, 7] dodec-9-ene, 4-methyl-4- (hydroxyethoxycarbonyl) tetracyclo [6.2.1.13, 6.2.7, 7] dodeca-9-ene, N -(Hydroxyethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxyphenyl) bicyclo [2.2.1] hept-5-ene-2,3 -A hydroxyl group-containing cycloolefin such as dicarboximide and the like, and the like can be mentioned. Further, as a cycloolefin monomer (b) having a protic polar group, 4-diethylaminotetracyclo [6.2.1.13,60.2,7] dodeca-9-ene, 4-dimethylaminotetracyclo An amino group-containing cycloolefin such as [6.2.1.1 3, 6. 02, 7] dodec-9-ene can be used. These monomers (b) may be used alone or in combination of two or more.

  The content ratio of the units of the monomer (b) in the cycloolefin resin is preferably 10 to 90 mol%, more preferably 15 to 80 mol%, still more preferably 20 to 90 mol%, based on all monomer units. It is 70 mol%. If the content ratio of the units of the monomer (b) is too small, the heat resistance may be insufficient. On the other hand, if too large, the solubility of the cycloolefin polymer (A) in the polar solvent is insufficient. May be

  The cycloolefin resin used in the present invention is a copolymer obtained by copolymerizing a cycloolefin monomer (b) having a protic polar group and a monomer copolymerizable therewith. It is also good.

A more specific example of the cycloolefin resin is, for example, a copolymer represented by the following formula (2).

In Formula (2), 1 and m show the molar content rate (mol%) in the polymer of, and are l + m <= 1, 0.1 <= l <= 0.9, 0.1 <= m <= 0.9. n is 0, 1 or 2.
R ^{11, R 12, R 13} and ^{R 14} are each independently hydrogen or an organic group having 1 to 30 carbon atoms. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be identical to each other or different from each other.
Q is a structural unit represented by the following formula (3a), (3b), (3c) or (3d). The copolymer represented by the above formula (2) contains one or more structural units Q selected from the following formulas (3a), (3b), (3c) and (3d). In the present embodiment, it is preferable that at least one or more structural units Q selected from the following formulas (3a), (3b) and (3c) be included. In addition, a polymer may contain other structural units other than the structural unit shown by said Formula (Q).

R < ¹⁵ >, R < ¹⁶ > and R < ¹⁷ > are respectively independently C1-C18 organic groups in Formula (3a) and Formula (3b).

The organic group having 1 to 30 carbon atoms constituting R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may contain one or more selected from O, N, S, P and Si in its structure.

In the present embodiment, the organic group constituting R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is, for example, an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, And heterocyclic groups.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, Examples include octyl group, nonyl group and decyl group. As an alkenyl group, an allyl group, pentenyl group, and a vinyl group are mentioned, for example. The alkynyl group includes an ethynyl group. The alkylidene group includes, for example, a methylidene group and an ethylidene group. As an aryl group, a phenyl group, a naphthyl group, and an anthracenyl group are mentioned, for example. As an aralkyl group, a benzyl group and a phenethyl group are mentioned, for example. Examples of the alkaryl group include tolyl group and xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The heterocyclic group includes, for example, an epoxy group and an oxetanyl group.
Note that by including an alkyl group as R ^{11, R 12,} R ¹³ and R ^14, it is possible to improve the film formability of the film made of negative type photoresist resin composition comprising a polymer. Further, by containing an aryl group as R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , a film made of a resin composition for negative photoresist containing a polymer is developed at the time of development using an alkaline developer in the lithography step. Film loss can be suppressed.

Furthermore, in the above-mentioned alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group and heterocyclic group, one or more hydrogen atoms may be substituted by a halogen atom. Good. The halogen atom includes fluorine, chlorine, bromine and iodine. Among them, a haloalkyl group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom is preferable. When at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a haloalkyl group, when a polymer is used to construct a resin composition for negative photoresist, the resin for negative photoresist The developability of the composition can be improved.
From the viewpoint of enhancing the light transmittance of a film containing a polymer, any one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is preferably hydrogen, and in particular, R ¹¹ , R ¹² , R Preferably, ¹³ and R ¹⁴ are all hydrogen.

The organic group having 1 to 18 carbon atoms constituting R ¹⁵ , R ¹⁶ and R ¹⁷ may contain any one or more of O, N, S, P and Si in its structure.

In this embodiment, examples of the organic group constituting R ¹⁵ , R ¹⁶ and R ¹⁷ include, for example, an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and a heterocyclic ring. Groups are mentioned. Here, examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group Groups, octyl group, nonyl group, and decyl group. As an alkenyl group, an allyl group, pentenyl group, and a vinyl group are mentioned, for example. The alkynyl group includes an ethynyl group. The alkylidene group includes, for example, a methylidene group and an ethylidene group. As an aryl group, a phenyl group, a naphthyl group, and an anthracenyl group are mentioned, for example. As an aralkyl group, a benzyl group and a phenethyl group are mentioned, for example. Examples of the alkaryl group include tolyl group and xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The heterocyclic group includes, for example, an epoxy group and an oxetanyl group.

  Furthermore, in the above-mentioned alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group and heterocyclic group, one or more hydrogen atoms may be substituted by a halogen atom. Good. The halogen atom includes fluorine, chlorine, bromine and iodine. Among them, a haloalkyl group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom is preferable.

The copolymer represented by the above formula (2) is, for example, a repeating unit derived from a norbornene type monomer represented by the following formula (4), and a repeating unit derived from maleic anhydride shown in the following formula (5) It is preferable that it is an alternating copolymer in which is arranged alternately.
The copolymer represented by the above formula (2) may be a random copolymer or a block copolymer.
The repeating unit derived from maleic anhydride shown in the following formula (5) is a structural unit represented by Q in the above formula (2). In addition, the polymer may contain the monomer shown by following formula (4) and (5) as a low molecular weight component.

(In the formula (4), n and R ^{11 to} R ¹⁴ are the same as the above formula (2), that is, n is either 0 or 1 or 2. R ^{11 to} R ¹⁴ are each independently Hydrogen or an organic group having 1 to 30 carbon atoms.In formula (4), R ^{11 to} R ¹⁴ may be the same or different)

The weight average molecular weight of the alkali-soluble resin (B) having a protic polar group is preferably 2000 or more from the viewpoints of resolution of the insulating film to be obtained, thermal shock resistance, heat resistance, residual film ratio, etc. More preferably, it is about 2000 to 20000.

In addition, the content ratio of the alkali-soluble resin (B) having a protic polar group in the resin composition for negative photoresist is 30 to 90% by weight when the entire composition excluding the solvent is 100% by weight. %, Preferably 40 to 80% by weight. When the content ratio of the alkali-soluble resin (B) having a protic polar group is 30 to 90% by weight, the film formed using the photosensitive insulating resin composition has sufficient developability by an aqueous alkaline solution. It is preferable because it has it.

Crosslinking agent (C)
The crosslinking agent (C) is not particularly limited as long as it acts as a crosslinking component (curing component) that reacts with the alkali-soluble resin (B). Examples of the crosslinking agent (C) include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolak resin epoxy compounds, resole resin epoxy compounds, poly (hydroxystyrene) epoxy compounds , Oxetane compounds, methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenol compounds, alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxy Alkyl group-containing phenolic compound, carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urine Resins, carboxymethyl group-containing phenol resin, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, mention may be made of carboxymethyl group-containing urea compounds and carboxymethyl group-containing phenol compounds and the like.

Among these crosslinking agents (C), methylol group-containing phenol compounds, methoxymethyl group-containing melamine compounds, methoxymethyl group-containing phenol compounds, methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds and acetoxymethyl group-containing phenol compounds Preferred are methoxymethyl group-containing melamine compounds (for example, hexamethoxymethylmelamine etc.), methoxymethyl group-containing glycoluril compounds, and methoxymethyl group-containing urea compounds. Methoxymethyl group-containing melamine compounds are trade names such as CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 305 (made by Mitsui Cyanamid Co., Ltd.), and methoxymethyl group-containing glycoluril compounds are trade names such as CYMEL 1174 (made by Mitsui Cyanamid Co., Ltd.) Also, methoxymethyl group-containing urea compounds are commercially available under trade names such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).

The content of the crosslinking agent (C) is usually 5 to 60 moles relative to all the acidic functional groups in the alkali-soluble resin (B) from the viewpoint of lowering the residual film rate, meandering of the pattern, swelling and developability. %, Preferably 10 to 50 mol%, more preferably 15 to 40 mol%.
Crosslinked fine particles (D)
The chemical amplification type negative photoresist composition of the present invention may further contain crosslinked fine particles (D) in order to improve the durability and thermal shock resistance of the resulting cured product.
The crosslinked fine particles (D) are not particularly limited as long as the glass transition temperature (Tg) of the polymer constituting the crosslinked fine particles is 0 ° C. or less, but a crosslinkable monomer having two or more unsaturated polymerizable groups , Simply referred to as “crosslinkable monomer”) and one or two or more “other monomers” selected so that the Tg of the crosslinked fine particles (D) is 0 ° C. or less preferable.
In particular, two or more of the other monomers described above are used in combination, and at least one of the other monomers has a functional group other than a polymerizable group such as a carboxyl group, an epoxy group, an amino group, an isocyanate group or a hydroxyl group. It is preferred that

Examples of the crosslinkable monomer include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol The compound which has multiple polymerizable unsaturated groups, such as di (meth) acrylate and polypropylene glycol di (meth) acrylate, can be mentioned. Among these, divinylbenzene is preferred.

The crosslinkable monomer used in the production of the crosslinkable fine particles (D) is preferably 1 to 20% by weight, more preferably 1 to 10% by weight, based on 100% by weight of all monomers used for copolymerization. % By weight, particularly preferably 1 to 5% by weight.

Moreover, as said other monomer, For example, Diene compounds, such as butadiene, an isoprene, a dimethyl butadiene, a chloroprene, a 1,3- pentadiene, (meth) acrylonitrile, alpha-chloro acrylonitrile, alpha-chloromethyl acrylonitrile, alpha-methoxy acrylonitrile Unsaturated nitrile compounds such as α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile, (meth) acrylamide, dimethyl (meth) acrylamide, N, N'- Methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-) Unsaturated amides such as hydroxyethyl, (meth) acrylamide, N, N-bis (2- hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide, etc., methyl (meth) acrylate, (meth) acrylic acid Ethyl, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate etc (meth) acrylate Aromatic vinyl compounds such as esters, styrene, α-methylstyrene, o-methoxystyrene, p-hydroxystyrene, p-isopropenylphenol, diglycidyl ethers of bisphenol A, diglycidyl ethers of glycols, etc. and (meth) acrylics Acid, Hydroxide Epoxy (meth) acrylate obtained by the reaction with alkyl (meth) acrylate and the like, urethane (meth) acrylates obtained by the reaction of hydroxyalkyl (meth) acrylate and polyisocyanate, glycidyl (meth) acrylate ( ) Epoxy group-containing unsaturated compounds such as allyl glycidyl ether, (meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β -Unsaturated acid compounds such as (meth) acryloxyethyl and hexahydrophthalic acid-β- (meth) acryloxyethyl, amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate and diethylamino (meth) acrylate, hydroxy Ethyl (meth) acrylate, Examples thereof include hydroxyl group-containing unsaturated compounds such as hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.

Among these other monomers, butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, styrene, p-hydroxystyrene, p-isopropenyl phenol, glycidyl (meth) acrylate, (meth) acrylic Acids, hydroxyalkyl (meth) acrylates and the like are preferred.

In addition, in the production of the crosslinked fine particles (D), it is preferable that at least one kind of diene compound, specifically, butadiene be used as another monomer. Such a diene compound is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and particularly preferably 40 to 70% by weight with respect to 100% by weight of all monomers used for copolymerization.
When a diene compound such as butadiene is copolymerized at 20 to 80% by weight with respect to 100% by weight of all monomers as another monomer, the crosslinked fine particle (D) becomes a rubber-like soft fine particle and the obtained curing The occurrence of cracks in the film can be prevented, and a cured film excellent in durability can be obtained.

The crosslinked fine particles (D) may be used alone or in combination of two or more.

The average particle diameter of the crosslinked fine particles (D) is usually 30 to 500 nm, preferably 40 to 200 nm, more preferably 50 to 120 nm.
The method of controlling the particle size of the crosslinked fine particles (D) is not particularly limited. For example, in the case of synthesizing the crosslinked fine particles by emulsion polymerization, the number of micelles in the emulsion polymerization is controlled by the amount of the emulsifier used. It can be controlled.
The average particle diameter of the crosslinked fine particles (D) is a value measured by diluting a dispersion of the crosslinked fine particles according to a conventional method using a light scattering flow distribution measuring apparatus or the like.

The compounding amount of the crosslinked fine particles (D) is preferably 0.5 to 50 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (B). When the blending amount of the crosslinked fine particles (D) is 0.5 to 50 parts by weight, the compatibility or dispersibility with other components is excellent, and the thermal shock resistance and heat resistance of the obtained cured film are improved. be able to.

Adhesion aid (E)
The resin composition for negative photoresist of the present invention may contain an adhesion assistant in order to improve the adhesion to the substrate.
As said adhesion | attachment adjuvant, the functional silane coupling agent etc. which have reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, etc. are mentioned, for example.

The blending amount of the adhesion promoter is preferably 0.2 to 10 parts by weight, and more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (B). When the compounding amount of the adhesion assistant is 0.2 to 10 parts by weight, it is preferable because the storage stability is excellent and good adhesion can be obtained.

Solvent (F)
The resin composition for a negative photoresist of the present invention can contain a solvent in order to improve the handleability of the resin composition or to adjust the viscosity and storage stability.

  As the solvent, carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene glycol, ethylene glycol Polyalcohols such as monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate monoethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether And their derivatives; cyclic ethers such as dioxane Ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, 2- Methyl hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. Esters; and aromatic hydrocarbons such as toluene and xylene.

  When a solvent is used, the use ratio of the solvent is preferably 15 to 1000 parts by weight, more preferably 30 parts by weight with respect to 100 parts by weight of the onium gallate salt (acid generator) represented by Formula (1) of the present invention. -500 parts by weight. The solvents used may be used alone or in combination of two or more.

Sensitizer (G)
The resin composition for a negative photoresist of the present invention can contain a sensitizer, if necessary. As such a sensitizer, conventionally known ones can be used.

  As a sensitizer, as a sensitizer, benzoquinone {1,4-benzoquinone, 1,2-benzoquinone etc.}; naphthoquinone {1,4-naphthoquinone, 1,2-naphthoquinone etc.}; anthraquinone {2-methyl anthraquinone , 2-ethyl anthraquinone, etc.}, anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10 -Dipropoxy anthracene etc .; Pyrene; 1,2-Benzanthracene; Perylene; Tetracene; Coronene; Thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4- Ethylthioxanthone etc .; Phenothiazine {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenylphenothiazine etc} xanthone; Naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1, 4-Dihydroxynaphthalene, 4-methoxy-1-naphthol, etc.}; Ketone {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy -2-Methylpropiophenone and 4-benzoyl-4'-methyldiphenyl sulfide etc .; Carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole and N-glycidyl Carbazole and the like}; chrysene {1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene and the like}; phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene and 9 -Hydroxy-10-ethoxyphenanthrene etc.} and the like.

  When the sensitizer is contained, the content of the sensitizer is preferably 1 to 300 parts by weight, and more preferably 5 to 200 parts by weight with respect to 100 parts of the acid generator.

  The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of the acid generator.

Other Additives The resin composition for negative photoresists of the present invention may, if necessary, contain other additives to the extent that the properties of the present invention are not impaired. As such other additives, inorganic fillers, quenchers, leveling agents, surfactants and the like can be mentioned.

The preparation method of the resin composition for negative photoresists of this invention is not specifically limited, It can prepare by a well-known method. It can also be prepared by stirring each component into a fully stoppered sample bottle by placing it on a wave rotor.

In order to form the cured product of the present invention, first, the above-described resin composition for negative photoresist according to the present invention is used as a support (a copper foil with a resin, a silicon wafer coated with a copper-clad laminate or a metal sputtered film, alumina The composition is coated on a substrate or the like and dried to evaporate a solvent or the like to form a coating film. Thereafter, exposure is performed through a desired mask pattern, and heat treatment (hereinafter, this heat treatment is referred to as "PEB") is performed to promote the reaction between the alkali-soluble resin (B) and the crosslinking agent (C). Next, development is carried out with an alkaline developer to dissolve and remove the unexposed area, whereby a desired pattern can be obtained. Furthermore, a cured film can be obtained by performing heat treatment to develop insulating film characteristics.

As a method of coating a resin composition on a support body, application methods, such as a dipping method, a spray method, a bar coat method, a roll coat method, or a spin coat method, can be used, for example. In addition, the thickness of the coating film can be appropriately controlled by adjusting the solid content concentration and viscosity of the coating means and the composition solution.
Examples of radiation used for exposure include ultraviolet light such as a low pressure mercury lamp, high pressure mercury lamp, metal halide lamp, g-line stepper, h-line stepper, i-line stepper, gh-line stepper, ghi line stepper, electron beam, and laser beam. . Further, the exposure amount is appropriately selected depending on the light source to be used, the resin film thickness and the like, but for example, in the case of ultraviolet irradiation from a high pressure mercury lamp, the resin film thickness is 1 to 50 μm, it is about 100 to 50000 J / m 2.

After the exposure, the above-mentioned PEB treatment is carried out in order to accelerate the curing reaction of the alkali-soluble resin (B) and the crosslinking agent (C) by the generated acid. Although PEB conditions differ with the compounding quantity of a resin composition, the film thickness to be used, etc., it is 70 to 150 degreeC normally, Preferably it is 80 to 120 degreeC, and it is about 1 to 60 minutes. Thereafter, it is developed with an alkaline developer to dissolve and remove the unexposed area to form a desired pattern. As a developing method in this case, a shower developing method, a spray developing method, an immersion developing method, a paddle developing method and the like can be mentioned. As development conditions, it is about 1 to 10 minutes normally at 20-40 degreeC.

Furthermore, in order to fully develop the characteristics as an insulating film after development, it can be sufficiently cured by heat treatment. Such curing conditions are not particularly limited, but depending on the application of the cured product, the composition can be cured by heating at a temperature of 50 to 250 ° C. for about 30 minutes to 10 hours. In addition, heating can be performed in two steps to sufficiently promote curing or prevent deformation of the obtained pattern shape, for example, in the first step, at a temperature of 50 to 120 ° C., for 5 minutes to 2 It is also possible to heat for about 10 minutes to 10 hours at a temperature of 80 to 250 ° C. for curing. Under such curing conditions, a common oven, an infrared furnace, or the like can be used as heating equipment.

<Use>
Next, applications of the resin composition for negative photoresist of the present invention will be described.
The resin composition for negative photoresist of the present invention is not only used for film formation of a film which is present only for a predetermined period like a photoresist and is removed when it becomes unnecessary, and is removed after film formation. It can also be used for film formation of a permanent film (cured film) which continues to remain in the product.

For example, it can be used as a planarizing film covering a transistor, or an interlayer insulating film covering a rewiring layer of a semiconductor device.
Furthermore, it can be applied to a color filter resist blended with a pigment or a dye, an interlayer insulating film for display, etc. by taking advantage of the good transparency, heat-resistant color-changing property, and insulation property.

Furthermore, the resin composition for negative photoresist of the present invention may be a microlens array. For example, the resin composition for a negative photoresist of the present invention can be filled into a mold for a microlens array, and then photocured and optionally thermally cured to form a microlens array.
The microlens array manufactured in this manner can be used for liquid crystal display devices, plasma displays, field emission displays, electroluminescent displays and the like.

  Hereinafter, the present invention will be further described by way of examples, but the present invention is not intended to be limited thereto. Incidentally, unless otherwise specified, parts mean parts by weight and% mean% by weight.

<Synthesis of Photoacid Generator>
Synthesis Example 1 Synthesis of Lithium Tetrakis (pentafluorophenyl) Gallate In a 125 mL four-necked flask sufficiently dried under a nitrogen atmosphere, 360 parts of super dehydrated diethyl ether and 30 parts of pentafluorobromobenzene were charged, and this was used as dry ice / acetone. The bath was cooled to -78 ° C. 70 parts of a 2.5 mol / L n-butyllithium hexane solution was added dropwise over 10 minutes, and then stirred at -78 ° C for 30 minutes. To this, 68 parts of a diethyl ether solution in which 5 parts of gallium (III) chloride were dissolved was added dropwise over 10 minutes, and the mixture was stirred at -78 ° C for 3 hours. The reaction solution was stirred while gradually returning to room temperature, and allowed to return to room temperature and then stirred for additional 5 hours. The precipitated solid was filtered, the reaction solution was transferred to an evaporator, and the solvent was distilled off to obtain an off-white product. The product was washed four times with 50 parts of super dehydrated hexane and then vacuum dried overnight to obtain lithium tetrakis (pentafluorophenyl) gallate. The product was identified by ¹⁹ F-NMR.

Synthesis Example 2 Synthesis of Photoacid Generator (A-1) Diphenyl sulfoxide (1.6 parts, 8 mmol), diphenyl sulfide (1.5 parts, 8 mmol), acetic anhydride (2.5 parts, 24 mmol), trifluoro The lomethanesulfonic acid (1.5 parts, 10 mmol) and 13 parts of acetonitrile were mixed uniformly and reacted at 40 ° C. for 6 hours. The reaction solution was cooled to room temperature, poured into 60 parts of ion exchanged water, extracted with 60 parts of dichloromethane, and washed with ion exchanged water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was evaporated to give a brown liquid product. To this, add 20 parts of ethyl acetate, dissolve in a water bath at 60 ° C., add 60 parts of hexane, stir, cool to 5 ° C., leave for 30 minutes, and remove the supernatant twice. The product was washed. This was transferred to a rotary evaporator and the solvent was distilled off to obtain [4- (phenylthio) phenyl] sulfonium triflate.
(Double decomposition method)
The triflate is dissolved in 50 parts of dichloromethane, and 66 parts of an equimolar aqueous solution of lithium tetrakis (pentafluorophenyl) gallate is mixed at room temperature, stirred for 3 hours as it is, and the dichloromethane layer is separated twice with water by liquid separation operation. After washing, it was transferred to a rotary evaporator and the solvent was distilled off to obtain A-1.

Synthesis Example 3 Synthesis of Photoacid Generator (A-2) Diphenyl sulfoxide (1.6 parts, 8 mmol), diphenyl sulfide (1.5 parts, 8 mmol) was added to 4-[(phenyl) sulfinyl] biphenyl (2. A-2 was obtained in the same manner as in Synthesis Example 2 except that the amount was changed to 2 parts, 8 mmol) and 4- (phenylthio) biphenyl (2.1 parts, 8 mmol).

Synthesis Example 4 Synthesis of Photoacid Generator (A-3) Diphenylsulfoxide (1.6 parts, 8 mmol), diphenyl sulfide (1.5 parts, 8 mmol), 2- (phenylthio) thioxanthone (2.6 parts, A-3 was obtained in the same manner as in Synthesis Example 2 except that 8 mmol) and 2-[(phenyl) sulfinyl] thioxanthone (2.5 parts, 8 mmol) were changed.

<Synthesis of polymer>
Synthesis Example 5 Synthesis of Polymer (B-2a) In an appropriately sized reaction vessel equipped with a stirrer and a condenser, maleic anhydride (MA, 122.4 parts, 1.25 mol), 2-norbornene (NB) , 117.6 parts, 1.25 mol) and dimethyl 2,2′-azobis (2-methylpropionate) (11.5 parts, 50.0 mmol), and methyl ethyl ketone (MEK, 150.8 parts) and It was dissolved in toluene (77.7 parts). The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated with stirring at 60 ° C. for 16 hours. Thereafter, MEK (320 parts) was added to the solution, and sodium hydroxide (12.5 parts, 0.31 mol), butanol (463.1 parts, 6.25 mol), toluene ( The mixture was added to the suspension of 480 parts) and mixed at 45 ° C. for 3 hours. Then, the mixture is cooled to 40 ° C., treated with formic acid (88 mass% aqueous solution, 49.0 parts, 0.94 mol), protonated, and then MEK and water are added to separate an aqueous layer. Removed the inorganic residue. Subsequently, methanol and hexane were added and the organic layer was separated to remove the unreacted monomer. Further, PGMEA was added, and methanol and butanol in the system were distilled off under reduced pressure to a residual amount of less than 1%. Thereafter, the reaction solution was heated to 125 ° C. and allowed to react until the alkali dissolution time was in the optimum range.
This obtained 1107.7 parts of 20 mass% polymer solutions (GPC Mw = 13,700, Mn = 7,400).

Synthesis Example 6 Synthesis of Polymer (B-2b) Maleic anhydride (4.9 parts, 50 mmol), 5- (2-hydroxy-2), in a reactor of an appropriate size equipped with a stirrer and a condenser. Measure 2-bis trifluoromethyl) ethyl-2-norbornene (13.7 parts, 50 mmol) and dimethyl 2,2'-azobis (2-methyl propionate) (1.15 parts, 5 mmol), methyl ethyl ketone It was dissolved in MEK, 2.7 parts) and toluene (8.0 parts). The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated with stirring at 60 ° C. for 16 hours. Thereafter, MEK (35 parts) was added to the solution and poured into a large amount of methanol to precipitate a polymer. The polymer was collected by filtration and further washed with methanol, and then vacuum dried at 30 ° C. for 16 hours to obtain 5.3 parts of a white solid (GPC Mw = 10,560, Mn = 6,910).

Synthesis Example 7 Synthesis of Polymer (B-2c) Maleic anhydride (4.9 parts, 50 mmol), 5-phenylethyl-2-norbornene (In an appropriately sized reaction vessel equipped with a stirrer and a condenser) 7.5 parts, 50 mmol) and dimethyl 2,2'-azobis (2-methylpropionate) (1.15 parts, 5 mmol) are weighed, methyl ethyl ketone (5.5 parts) and toluene (1.8 parts) It was dissolved in The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated with stirring at 60 ° C. for 16 hours. Thereafter, MEK (24 parts) was added to this solution, and then poured into a large amount of methanol to precipitate a polymer. The polymer was collected by filtration and further washed with methanol, and then vacuum dried at 30 ° C. for 16 hours to obtain 5.7 parts of a white solid (GPC Mw = 9,920, Mn = 6,100). 5.0 parts of this polymer was dissolved in 20 parts of THF, and a solution of 1.2 parts of sodium methoxide in 2.5 parts of methanol was added thereto. The mixture was reacted at 60 ° C. for 3 hours, neutralized with 3.5 parts of formic acid, and washed three times with water to remove neutralized salts. The reaction solution was then poured into a large amount of hexane to precipitate a polymer. The polymer was collected by filtration, further washed with hexane, and vacuum dried at 30 ° C. for 16 hours to obtain 5.5 parts (GPC Mw = 10,460, Mn = 6,600).

Synthesis Example 8 Synthesis of Polymer (B-2d) In an appropriately sized reaction vessel equipped with a stirrer and a condenser, maleic anhydride (4.9 parts, 50 mmol), 5-butyl-2-norbornene (9) .9 parts, 50 mmol) and dimethyl 2,2'-azobis (2-methyl propionate) (1.15 parts, 5 mmol) are weighed, methyl ethyl ketone (MEK, 6.4 parts) and toluene (2.1 parts) Dissolved in The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated with stirring at 60 ° C. for 16 hours. Thereafter, MEK (29 parts) was added to the solution and poured into a large amount of methanol to precipitate a polymer. The polymer was collected by filtration, further washed with methanol, and vacuum dried at 30 ° C. for 16 hours to obtain 8.0 parts of a white solid (GPC Mw = 10,300, Mn = 6,000). A solution of 5.0 parts of this polymer in 20 parts of THF, to which 1.0 part of sodium methoxide was dissolved in 2.5 parts of methanol, was added. The mixture was reacted at 60 ° C. for 3 hours, neutralized with 2.8 parts of formic acid, and washed three times with water to remove neutralized salts. The reaction solution was then poured into a large amount of hexane to precipitate a polymer. The polymer was collected by filtration and further washed with hexane, and then vacuum dried at 30 ° C. for 16 hours to obtain 5.0 parts (GPC Mw = 10,470, Mn = 6,100).

<Adjustment of Negative Photoresist-1>
(Examples 1 to 6 and Comparative Examples 1 to 3)
Photoacid generator (A-1 to A-4), novolak resin (B-1a to B-1b), compound having two or more oxirane rings, compound having methylol group or compound having alkoxyalkyl group (C -1 to C-3), adhesion assistant (E-1), solvent (F-1) and sensitizer (G-1) in uniform amounts as shown in Table 1 to obtain a negative photoresist Resin composition was obtained.

<UV curing (residual film rate) evaluation-1>
After spin-coating the resin composition for negative photoresists obtained above on a silicon wafer substrate, it is dried by heating at 110 ° C. for 3 minutes using a hot plate to form a resin coating film having a thickness of about 20 μm. Obtained. Thereafter, pattern exposure (i ray; 500 mJ / cm ² ) was performed using TME-150 RSC (manufactured by Topcon Corporation), and post exposure bake (110 ° C.) for 3 minutes was performed on a hot plate at 110 ° C. (PEB). Thereafter, development was carried out for 2 minutes by a dipping method using a 2.38% by weight tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 50 μm line and space pattern.

<Heat resistance (yellowing) test-1>
The silicon substrate with a pattern obtained by the above UV curing evaluation was heated for 15 minutes on a hot plate adjusted to 200 ° C., and the hue of the pattern portion was visually evaluated. Evaluation criteria are as follows.

(Evaluation criteria)
◎: colorless (no yellowing of the coating)
○: light yellow to yellow ×: brown

<Metal Corrosion Test-1>
The silicon substrate with a pattern obtained by the above-mentioned UV curing evaluation was left for 720 hours under 80 ° C./85% wet heat conditions, and a metal corrosion test was conducted. The substrate after the test was visually evaluated for metal corrosion. Evaluation criteria are as follows.

(Evaluation criteria)
◎: The color change of the silicon substrate was not visually recognized at all.
○: The color change of the silicon substrate was slightly felt visually.
Δ: The silicon substrate appeared slightly blackish visually.
X: The silicon substrate was discolored to black.

A-4: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-200K)
B-1a: cresol novolak resin (Asahi Organic Material Industry Co., Ltd., trade name: EP 4020 G)
B-1b: Novolak resin (Asahi Organic Material Industry Co., Ltd. product name: MXP 5560 BF, weight average molecular weight = 7800)
C-1: 3: trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: ZX-1542)
C-2: B-5: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: MX-270)
C-3 :: Ethyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., trade name)
E-1: 3-glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBM-403)
F-1: methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 2-butanone)
G-1: 1: 9, 10-butoxyanthracene (manufactured by Kawasaki Kasei Kogyo Co., Ltd., trade name: DBA)

<Adjustment of Negative Photoresist-2>
(Examples 7 to 16 and Comparative Examples 4 to 6)
Photoacid generator (A-1 to A-4), polymer (B-2a to B-2d), crosslinking agent (C-4 to C-8), adhesion assistant (E-1), solvent (F-) 2) The sensitizer (G-1) was uniformly mixed in the amount shown in Table 2 to obtain a resin composition for negative photoresist.

<UV curing (residual film rate) evaluation-1>
After spin-coating the resin composition for negative photoresists obtained above on a silicon wafer substrate, it is dried by heating at 110 ° C. for 3 minutes using a hot plate to form a resin coating film having a thickness of about 20 μm. Obtained. Thereafter, pattern exposure (i ray; 500 mJ / cm ² ) was performed using TME-150 RSC (manufactured by Topcon Corporation), and post exposure bake (110 ° C.) for 3 minutes was performed on a hot plate at 110 ° C. (PEB). Thereafter, development was carried out for 2 minutes by a dipping method using a 2.38% by weight tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 50 μm line and space pattern.

<Heat resistance (yellowing) test-1>
The silicon substrate with a pattern obtained by the above UV curing evaluation was heated for 15 minutes on a hot plate adjusted to 200 ° C., and the hue of the pattern portion was visually evaluated. Evaluation criteria are as follows.

(Evaluation criteria)
◎: colorless (no yellowing of the coating)
○: light yellow to yellow ×: brown

<Metal Corrosion Test-1>
The silicon substrate with a pattern obtained by the above-mentioned UV curing evaluation was left for 720 hours under 80 ° C./85% wet heat conditions, and a metal corrosion test was conducted. The substrate after the test was visually evaluated for metal corrosion. Evaluation criteria are as follows.

(Evaluation criteria)
◎: The color change of the silicon substrate was not visually recognized at all.
○: The color change of the silicon substrate was slightly felt visually.
Δ: The silicon substrate appeared slightly blackish visually.
X: The silicon substrate was discolored to black.

A-4: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-200K)
C-4: trimethylolpropane triglycidyl ether (Epolite 100 MF, manufactured by Kyoeisha Chemical Co., Ltd.)
C-5: 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021 P, manufactured by Daicel Corporation)
C-6: Hydrogenated bisphenol A diglycidyl ether (Epolite 4000 MF, manufactured by Kyoeisha Chemical Co., Ltd.)
C-7: 1,2-Epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (EHPE 3150, manufactured by Daicel Corporation)
C-8: xylylene bis oxetane (OXT-121, manufactured by Toagosei)
E-1: 3-glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBM-403)
F-2: Propylene glycol monomethyl ether acetate (PGMEA, manufactured by Wako Pure Chemical Industries, Ltd., trade name: acetic acid 2-methoxy-1-methylethyl)
G-1: 1: 9, 10-butoxyanthracene (manufactured by Kawasaki Kasei Kogyo Co., Ltd., trade name: DBA)

From the results of Tables 1 and 2, the resin composition for negative photoresists using an acid generator containing an onium gallate salt obtained according to the present invention is excellent in UV curing performance and is a cured product after a heat resistance test. It is suitable as a resin composition used for an interlayer insulating film, a resist for overcoat, and a resist for color filter because it has high transparency (hard to yellow) and excellent resistance to metal corrosion.

The resin composition for negative photoresist of the present invention comprises a paint, a coating agent, various coating materials (hard coat, stain resistant coating material, antifogging coating material, anti-fogging coating material, optical fiber, etc.), back treatment agent for adhesive tape , Release coatings for pressure-sensitive adhesive labels (release papers, release plastic films, release metal foils, etc.), printing plates, dental materials (dental formulations, dental composites) inks, inkjet inks, resist films, liquid resists Negative resists (surface protective films such as semiconductor elements, interlayer insulating films, permanent film materials such as planarizing films), resists for MEMS, negative photosensitive materials, various adhesives (temporary fixing agents for various electronic parts, Adhesive for HDD, adhesive for pickup lens, adhesive for functional film for FPD (deflection plate, anti-reflection film etc.), resin for holography, FP Materials (color filter, black matrix, partition material, photo spacer, rib, alignment film for liquid crystal, sealing agent for FPD etc.), optical member, molding material (for construction material, optical component, lens), casting material, putty, It is suitably used for glass fiber impregnating agents, sealing materials, sealing materials, sealing materials, optical semiconductor (LED) sealing materials, optical waveguide materials, nanoimprint materials, materials for light fabrication, materials for micro-optical shaping, and the like.

Claims (6)

A component (A) comprising an acid generator containing an onium gallate salt represented by the following general formula (1), a component (B) which is an alkali-soluble resin having a protic polar group, and a crosslinking agent component (C) A resin composition for negative photoresist, comprising:

[In formula (1), R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 18 carbon atoms or Ar, provided that at least one is Ar,
Ar is an aryl group having 6 to 14 carbon atoms (not including the carbon number of the following substituents), and a part of hydrogen atoms in the aryl group is an alkyl group having 1 to 18 carbon atoms, a halogen atom is A substituted alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an alkynyl group of 2 to 18 carbon atoms, an aryl group of 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, -OR ⁶ Alkoxy group or aryloxy group represented, acyl group represented by R ⁷ CO-, acyloxy group represented by R ⁸ COO-, alkylthio group or arylthio group represented by -SR ⁹ , -NR ¹⁰ R ¹¹ And may be substituted with an amino group represented by or a halogen atom,
R ^{6 to} R ^{9 each} represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
R ¹⁰ and R ^{11 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms;
E represents an element of valence n of 15 to 17 groups (IUPAC notation),
n is an integer of 1 to 3,
R ⁵ is an organic group bonded to E, the number of R ⁵ is n + 1, and (n + 1) R ⁵ may be identical to or different from each other, and two or more of R ⁵ may be directly to each other or -O -, - S -, - SO -, - SO 2 -, - NH -, - CO -, - COO -, - CONH-, ring structure containing an element E through an alkylene group or a phenylene group You may form ] The resin composition for a negative photoresist according to claim 1, wherein E in the above general formula (1) is S, I, N or P. The resin composition for a negative photoresist according to claim 1 or 2, wherein R ¹ , R ² , R ³ and R ^{4 in the} above general formula (1) are phenyl substituted with a perfluoroalkyl group or a fluorine atom. . Negative photoresist according to claim 1 or ^{2 R 1, R 2, R} 3, R 4 are pentafluorophenyl group or bis (trifluoromethyl) phenyl group in the above general formula (1) Resin composition. The gallate anion represented by [(R ¹ ) (R ² ) (R ³ ) (R ⁴ ) Ga] ⁻ in the above general formula (1) is [Ga (C ₆ F ₅ ) ₄ ] ^— or [Ga _{((CF 3) 2 C 6} H 3) 4] - a is claim 1 or 2 negative photoresist resin composition according to. The cured film obtained by hardening the negative photosensitive resin composition in any one of Claims 1-5.