WO2007119391A1 - Actinic energy radiation negative-working photoresist composition and cured product thereof - Google Patents

Abstract

Disclosed is an actinic energy radiation negative-working photoresist composition that is free from any toxic element, has good thermal stability, and has excellent resolution. The composition comprises a salt of an oniumfluorinated alkylfluorophosphoric acid, as a cation polymerization initiator represented by formula (4), wherein A represents a group VIA or VIIA (CAS notation) element having a valence of m; m = 1 to 2, n = 0 to 3, R represents an organic group, D represents a formula (5), E represents a group having a divalent group, G represents -O-, -S-, -SO-, -SO2-, -NH-, -NR'-, -CO-, -COO-, -CONH, an alkylene having 1 to 3 carbon atoms or phenylene, a = 0 to 5, X- represents a formula (6), Rf represents an alkyl in which not less than 80% of hydrogen atoms have been substituted by a fluorine atom, and b = 1 to 5. The composition further comprises a cation-polymerizable compound, and a solvent.

Description

 Specification

 Active energy ray negative photoresist composition and cured product thereof

 [0001] The present invention uses a specific fluorinated alkyl fluorophosphate as an active energy ray cationic polymerization initiator, so that the thermal stability is good, the type of the solvent is not selected, and the strength is high. High-productivity, high resolution after development, a thick film, high aspect ratio resist pattern can be obtained, and active energy beam negative photo that can be used as a permanent pattern with high mechanical strength The present invention relates to a resist composition, a dry film resist, and a cured product obtained by patterning using the resist composition. Background art

 [0002] In recent years, micro electro mechanical systems (MEMS) that integrate various electrical and mechanical elements such as sensors, circuits, actuators, and microstructures have been developed. It is used in a wide range of fields including communication equipment, automobiles, consumer equipment, medicine, and noise. Semiconductor microfabrication technology is applied to the production of this system. The production is performed by applying a photoresist to a substrate, patterning the coating film by photolithography technology, and using this as a mask for chemical etching. It is done by making full use of elect mouth forming technology such as electrolytic etching or electric plating. In addition, the patterned film itself may become a permanent film and become a part of the system structure or parts.

[0003] Photoresist compositions used for semiconductor microfabrication are suitable for thin film pattern formation, but have thicknesses ranging from several tens to several hundreds / zm required for the production of precision parts used in MEMS, etc. The film is not suitable for pattern formation with a high aspect ratio. This is because, in the case of a thick film where the transparency of the resist composition at the exposure wavelength is low, the light does not reach the lower layer of the resist film, resulting in poor resolution. This is due to factors such as poor drying and the inability to obtain a smooth coating film. Further, since the mechanical strength of the resulting resist pattern is low, the resistance to etching is low, and so-called “permanent pattern” (a pattern formed by resist is used permanently. There is a problem that it cannot be applied to the production of

 [0004] Therefore, a composition containing a novolac type epoxy resin and an active energy ray cationic polymerization initiator as a photoresist yarn composition which has improved these drawbacks (Patent Documents 1, 2, 3, 4 ) And epoxy polymerization (bridge) resists such as a composition containing an acrylic polymer having an epoxy group and a photoacid generator (active energy ray cationic polymerization initiator) (Patent Document 5) have been developed. It was.

 [0005] The process for obtaining a resist film is provided with a step of heating (pre-beta step) in order to volatilize the solvent component contained after the resist composition is applied to a substrate. In the conventional resist composition as described above, the thicker the resist film after coating, the more the solvent component in the composition evaporates, and as a result, when the tack (adhesiveness) remains in the coating film, The resist film adheres to the mask used during exposure, and the mechanical strength and resolution of the resist film after the exposure process and the development process are deteriorated. As a means to solve this, if the temperature during pre-beta is increased, the thermal stability of the resist composition will be low, resulting in partial polymerization and sufficient contrast between the exposed and unexposed areas during development. However, there is a problem that the resolution is lowered. This is because the active energy ray cation polymerization initiator (mainly OH-SbF salt) contained in the composition decomposes partly at high temperatures, so that the resin in the unexposed part

 6

 It is because it will superpose | polymerize. Further, if the pre-beta temperature is kept low and the solvent is volatilized by extending the time of the process, the above problems are almost eliminated, but the productivity is lowered, which is not industrially preferable.

[0006] For these reasons, a composition using a solvent having a low boiling point is disclosed in a publication.

 (Patent Document 1), where cyclopentanone is used as a solvent. However, the lower the boiling point of the solvent used, the more difficult it is to control the drying property of the coating film. Accordingly, there has been a demand for a resist composition that has excellent thermal stability of the resist composition, high productivity, and excellent resolution after development. In addition, if the thermal stability of the resist composition increases, the life of the composition itself as a product becomes longer, which is also meaningful in terms of quality control.

 Patent Document 1: US2005Z0147918

Patent Document 2: US2005Z〇260522 Patent Document 3: Japanese Patent Laid-Open No. 2005-250067

 Patent Document 4: Japanese Patent Laid-Open No. 10-62991

 Patent Document 5: Patent No. 3033549

 Patent Document 6: US-2002/0076651 ^-Disclosure of Invention

 Problems to be solved by the invention

[0007] Based on the above background, an object of the present invention is to provide an active energy ray negative photoresist composition having good thermal stability.

 A further object of the present invention is to provide an active energy ray negative photoresist composition having good thermal stability and excellent resolution after development.

 A still further object of the present invention is to provide an active energy ray negative photoresist composition suitable for obtaining a resist pattern having a thick film and a high aspect ratio.

 A still further object of the present invention is to provide an active energy ray negative photoresist composition that has good thermal stability and provides strong mechanical strength after development.

 A still further object of the present invention is to provide a dry film photoresist obtained from the above composition and a cured product obtained by patterning using the same.

 Means for solving the problem

[0008] As a result of investigations for the above-mentioned purpose, the present inventors have found that when a compound in the form of a salt of a fluorinated alkyl fluorophosphate cation is used as an active energy ray cationic polymerization initiator, the active sensitivity suitable for the above-mentioned purpose is obtained. The present inventors have found that an energy beam negative photoresist composition can be obtained, and further studied and completed the present invention. That is, the present invention provides the following.

 [0009] 1. An active energy ray negative photoresist composition comprising an active energy ray cationic polymerization initiator (1), a cationic polymerizable compound (2), and a solvent (3). Oh! The active energy ray cationic polymerization initiator (1) has the following formula (4),

[0010] [Chemical 1]

 [In the formula (4), A represents an element of valence m of Group VIA or VIIA (CAS notation), m is 1 or 2, n is an integer of 0 to 3, R Represents an organic group bonded to A, and a plurality of R may be the same or different from each other! /, And D may be represented by the following formula (5),

[0012] [Chemical 2]

 [In the formula (5), E represents a divalent group, G represents —O—, —S—, —SO—, —SO—, —NH—

 2

 , —NR, —, —CO—, —COO—, —CONH, an alkylene group having 1 to 3 carbon atoms or a fullerene group, and a is an integer of 0 to 5. Is a structure represented by

 ΧΊ next formula (6),

[0014] [Chemical 3]

[(Rf) bPF6 b]

[In the formula (6), Rf represents an alkyl group having 1 to 8 carbon atoms in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and b is an integer of 1 to 5. ] Represents a fluorinated alkylfluorophosphate cation represented by the formula: An active energy ray negative photoresist composition, which is an fluorinated alkyl fluorophosphate represented by the formula:

 2. The active energy ray negative photoresist composition as described in 1 above, wherein A in formula (4) is S.

 3. The active energy ray negative photoresist composition as described in 1 or 2 above, wherein R in formula (4) is a phenyl group which may have a substituent.

 4. The active energy ray negative photoresist composition as described in 3 above, wherein the substituent of R is a phenolthio group.

 5. In Equation (4), D is the following group:

[0016] [Chemical 4]

5. The active energy single-line negative photoresist composition as described in any one of 1 to 4 above, wherein at least one group of which force is also selected.

 6. In formula (6), Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, b is 2 or 3, the above 1! Type photoresist composition.

 7. The cation polymerizable compound (2) is a bisphenol A novolac resin or a bisphenol F novolac resin having at least two epoxy groups in one molecule, 1 or 6 or 6 of the active energy ray negative photoresist composition.

 8. Solvent (3) is at least one selected from the group consisting of methyl ethyl ketone, cyclopentanone, cyclohexanone, gamma-butyral rataton, and propylene glycol monomethyl ether acetate. 7. A positive-sensitive negative-line photoresist composition.

 9. A dry film resist obtained by applying the above-mentioned 1 !, 8 !, or any of the active energy ray negative photoresist compositions onto a film-like support and drying.

10. The above 1 !, 8 !, any of the active energy ray negative photoresist compositions or the dried active energy ray negative photoresist composition of the dry film resist described in 9 above are cured. Become a cured product. The invention's effect

 [0017] According to the present invention, an active energy ray negative photoresist composition having good thermal stability can be obtained. Therefore, the pre-beta temperature of the resist film after being applied to the substrate can be increased as compared with the prior art, and the solvent can be volatilized more quickly and reliably, thereby improving the productivity of the resist film. In addition, the resist composition of the present invention has high thermal stability, hardly undergoes thermal polymerization during the pre-beta process, and can reliably remove the solvent, thereby improving the resolution when developed. To help. In addition, the pre-beta temperature can be increased as compared with the conventional one, which makes it easier to produce a thicker resist film than the conventional one, which helps to obtain a resist pattern with a high aspect ratio. Furthermore, the resist composition of the present invention can be used to obtain a permanent pattern because the cured product has high mechanical strength. In fact, the resist composition of the present invention does not contain poisonous metals such as antimony arsenic and is therefore safe to handle and / or the environment.

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0018] In the above formula (4) representing the active energy linear cationic polymerization initiator (1) of the composition of the present invention, A represents an element of group VIA to VIIA (CAS notation), organic group R and structure Combined with D to form oum [Α "]. Among the elements of group VIA to VIIA, preferred are S, I and Se, which are excellent in force thione polymerization initiation ability, and particularly preferred is thermal. It is an excellent S. m in formula (4) is 1 or 2 which is equal to the valence of element A.

[0019] R in the above formula (4) is an organic group bonded to A, and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms. Represents an alkyl group having 2 to 30 carbon atoms or an alkyl group having 2 to 30 carbon atoms, preferably an aryl group having 6 to 30 carbon atoms, particularly preferably a phenyl group, In any group, it can be substituted. Examples of substituents are alkyl, hydroxy, alkoxy, alkylcarbonyl, aryloylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylothiocarbonyl, acyloxy, arylothio, alkylthio, aryl, heterocyclic ring, May be substituted with at least one selected from the group consisting of aryloxy, alkylsulfiel, arylsulfiel, alkylsulfol, arylsulfol, alkyleneoxy, amide-containing nitro-containing groups and halogen power Good. The number of R is m + n (m— 1) + 1, and the plurality of R may be the same or different from each other. Also, two or more R's can be directly or — 0—, — S—, — SO—, —SO—, — N

 2

A ring structure containing element A may be formed by bonding via H, 1 NR, 1, CO, 1 COO, 1 CONH, an ananylene having 1 to 3 carbon atoms, or a phenol group. Where R, is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

 [0020] In the above, the aryl group having 6 to 30 carbon atoms includes monocyclic aryl groups such as a phenol group and naphthyl, anthracel, phenanthryl, pyrel, chrysal, naphthacenyl, Examples thereof include condensed polycyclic aryl groups such as benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone and anthraquinone.

 [0021] As described above, examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, and a plurality of heteroatoms are the same. Specific examples that may or may not be monocyclic heterocyclic groups such as chael, furanyl, biranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, birazinyl, and indolyl, benzofuranyl, isobenzo Furanyl, benzocenyl, isobenzothenyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, atalidinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromyltoyl -Le What condensed polycyclic heterocyclic group.

[0022] In the above, the alkyl group having 1 to 30 carbon atoms includes a straight chain alkyl group such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and okudadecyl. Branched alkyl groups such as isopropyl, isobutyl, sec butyl, tert butyl, isopentyl, neopentyl, tert pentyl, isohexyl, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzyl, naphthylmethyl, anthra Examples include aralkyl groups such as senylmethyl, 1-phenylethyl and 2-phenylethyl. The alkenyl group having 2 to 30 carbon atoms includes val, allyl, 1-probe, iso-probe, 1-buturule, 2-butulyl, 3-butenyl, 1-methyl-1-propenyl, 1-Methyl-2-propenyl, 2-Methanol 1-Provenole, 2-Methylanol 2-Probenole, 1-Pentenole, 2-Pentenole, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-2 butyr, 1,2 dimethyl-1-probe, 1-decenyl, 2-decenyl, 8 decenyl, 1 Linear or branched, such as dodecenyl, 2 dodecenyl, 10 dodecenyl, cycloalkyl groups such as 2 cyclohexyl, 3 cyclohexenyl, or arylalkyl groups such as styryl and cinnamyl Is mentioned. In addition, the alkyl groups having 2 to 30 carbon atoms include: Etul, 1-Provure, 2-Propininole, 1 Butyninole, 2 Butininore, 3 Butyninole, 1-Methinore 2 Propininole ゝ 1, 1-Dimethyl-2 Propiel, 1-Pentyl -2, 2, 3, 4, 1, 2, 8, 1, 2, 10, 10 And a straight-chain or branched-chain group such as, or an arylalkyl group such as a ferrule.

The above-mentioned aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkyl group having 2 to 30 carbon atoms or alkyl group having 2 to 30 carbon atoms. The ru group may have at least one substituent. Examples of such substituents are straight chain alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, okudadecyl; isopropyl, isobutyl, sec Branched alkyl groups having 1 to 18 carbon atoms such as butynole, tert butinole, isopentinole, neopentinole, tert pentinole and isohexyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; hydroxy Groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, etc., linear or branched alkoxy groups having 1 to 18 carbon atoms; acetyl, propionyl, butanol, 2 —Mech 2- to 18-carbon straight-chain or branched alkyl carbonyl groups such as lupropionyl, heptanol, 2-methylbutanol, 3-methylbutanol, otatanyl, decanol, dodecanol, octadecanol; 7-11 carbon atoms such as benzoyl and naphthoyl Aryl carbonate group; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octa C2-C19 linear or branched alkoxy carbo group such as decyloxy carbo; phenoxy carbo, naphthoxy carbo ol etc. 7-: L 1 aryloxy carbo yl; phenol thiocarbol And aryloxythio groups having 7 to 11 carbon atoms such as naphthoxythiocarbol; acetoxy, ethylcarboloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec butyl Linear or branched acyloxy groups having 2 to 19 carbon atoms such as carbonyloxy, tert butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy; phenylthio, 2-methylphenol Diruthio, 3 methylphenylthio, 4 methylphenylthio, 2 Mouth Fenino Retio, 3 Black Mouth Fenino Recio, 4 Black Mouth Fenino Retio, 2 Bromo Fen Noreio, 3 Bromo Fenino Retio, 4 Bromo Fenino Retio, 2 Fonoleolofenino Retio, 3 Fonole Orofenorio Leo, 4 Pheninoretio, 2-hydroxypheninoretio, 4-hydroxyphenylthiol, 2-methoxyphenylthio, 4-methoxyphenylthio, 1 naphthylthio, 2 naphthylthio, 4 [4 (phenylthio) benzoyl] phenolthio, 4 [ 4-(Ferulthio) phenoxy] Ferulthio, 4 [4 (Ferulthio) Ferer] Ferthio, 4 (Ferlthio) Ferlthio, 4 Benzylfelthio, 4 Benzo 1 2 Black mouth phenyl thiol, 4 Benzyl 3 Black mouth phenyl thiol, 4 Benzyl 3—Methylthiol diruthio, 4 Benzyl 2— Methylthiol diruthio, 4 (4-methylthiobenzoyl) phenylthiol, 4-one (2-methylthiobenzoyl) phenolthiol, 4- (p-methylbenzoyl) phenolthiol, 4- (p-ethylbenzoyl) phenolthiol 4- (p-isopropylbenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) furthio, etc., aryl thio groups having 6 to 20 carbon atoms; methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec butylthio , Tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert pentylthio, octylthio, decylthio, dodecylthio, etc., linear or branched alkylthio groups having 1 to 18 carbon atoms; phenyl, tolyl, dimethylphenol, Aryl group having 6 to 10 carbon atoms such as naphthyl; chael, fuller, biranyl, pyrrole , Okisazoriru, thiazolyl, pin lysyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, Benzocheniru, quinolyl , Isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, attaridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzocenyl, xanthonyl, thixanthonyl, dibenzofuran-20 Groups: phenoxy, naphthyloxy, etc., aryloxy groups having 6 to 10 carbon atoms; methylsulfiel, ethylsulfuryl, pineololenorefininore, isopropinoresnorefininore, butinoresnorefininore, isobutinoresnore Fininole, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfininiole, isopentinolesnorefinole, neopentinolesnorephinore, tert-pentinore Linear or branched alkylsulfuric groups having 1 to 18 carbon atoms such as norefinyl and octylsulfier; carbonsulfuric groups such as phenolsulfuryl, tolylsulfuryl and naphthylsulfiel 6 to: arenoles of LO Norefi-Nole group; methinolesnorejo-nore, ethinolesnorejo-nore, propinolesnore honinole, isopropinolesnorehoninore, butinolesnorehoninore, isobutinolesnorehoninore, sec-bu chinolesnorehoninore, tert- Butinolesnorehoninore, pentinoresnorehoninore, isopentinoresnorejo-nore, neopentinoresnorejo-nore, tert-pentinoresnorejo-nore, otachinoresnorejo-nore 1 to 18 carbon straight-chain or branched alkyl sulphone groups; phenyl sulphone, tolyl sulphone (tosyl group), naphthyl sulphone Throat carbon number 6: Arirusuruho sulfonyl group LO;

[0024] [Chemical 5]

— 0 __ CH ₂ CHO— _ H,

I ... ⁽⁷⁾

Q ^k

[0025] An alkyleneoxy group represented by the above formula (7) (Q represents a hydrogen atom or a methyl group, k is an integer of 1 to 5); an unsubstituted amino group, an alkyl having 1 to 5 carbon atoms, and Z Or an amino group monosubstituted or disubstituted by aryl having 6 to 10 carbon atoms (specific examples of alkyl groups having 1 to 5 carbon atoms are straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl; isopropyl; Branched alkyl groups such as isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, etc. Examples of cycloalkyl groups such as cyclopropyl, cyclopropyl, cyclopentyl, etc. Specific examples of aryl groups having 6 to 10 carbon atoms Examples include phenyl, naphthyl, etc.); cyano group; nitro group; fluorine , Halogens such as chlorine, bromine and iodine.

 [0026] Also, two or more R's may be directly or — 0—, — S—, — SO—, —SO—, — NH

 2

-, -NR '-(R, is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms are methyl, ethyl, propyl, butyl And straight chain alkyl groups such as pentyl, etc., branched alkyl groups such as isopropyl, isobutyl, sec butyl, tert-butyl, isopentyl, neopentyl, tert pentyl, etc., and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, etc. Specific examples of aryl groups of ˜10 include phenol, naphthyl, etc.), —CO—, —COO—, —CONH, bonded via an alkylene or phenylene group having 1 to 3 carbon atoms. Examples of ring structures containing element A are as follows:

[0027] [Chemical 6]

 Such

[0028] [In the formula, A is an element of VIA group to VIIA group (CAS notation), L is —O—, —S—, —SO—, —SO 1, NH—, —NR ′ one, CO 1, COO, or one CONH. R,

2

 Is the same as above. Can be mentioned.

[0029] In formula (4), it is bound to element A of group VIA to group VIIA (CAS notation) of valence m! /, M + n (m—l) + 1 R may be the same or different from each other, but at least 1 of R More preferably, all of R's represent an aryl having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms which may have the above substituent.

[0030] D in the formula (4) showing the active energy ray cationic polymerization initiator (1) (5)

[0031] [Chemical 7]

 [0032] In E, E is a divalent group, and is a linear, branched or cyclic alkylene group having 1 to 8 carbon atoms such as methylene, ethylene, propylene; phenylene, xylylene, naphthylene, biphenylene, 6-20 carbon arylene groups such as anthracene; dibenzofurandyl, dibenzothiopheneyl, xanthenezyl, phenoxathiyl, thianthrene dil, bitiofensyl, biflangyl, thixanthone diyl, xanthone diyl, carbazole diyl Represents a divalent group of a heterocyclic compound having 8 to 20 carbon atoms, such as atalidine diyl, phenothiazine diyl, and phenazine diyl. Here, a divalent group of a heterocyclic compound is a divalent group formed by removing one hydrogen atom in each of two ring carbon atomic energy different from the heterocyclic compound!

 [0033] The divalent group of the alkylene group, arylene group or heterocyclic compound may have at least one substituent. Specific examples of the substituent may include methyl, ethyl, propyl, butyl, pentyl, octyl. A linear alkyl group having 1 to 8 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, etc .; a branched alkyl group having 1 to 8 carbon atoms; cyclopropyl, cyclohexyl and the like having 3 to 8 carbon atoms Alkyl groups; alkoxy groups having 1 to 8 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, etc .; 6-carbon atoms such as phenol and naphthyl: LO aryl group; hydroxy group; cyano group; nitro group or Examples include halogens such as fluorine, chlorine, fluorine, and iodine.

 [0034] G in the above formula (5) is —O—, —S—, —SO—, —SO—, —NH—, —NR, — (R,

 2

Represents the same as defined above), —CO—, —COO—, —CONH—, C 1-3 alkylene or phenylene group. Examples of the alkylene group having 1 to 3 carbon atoms include linear or branched alkylene groups such as methylene, ethylene and propylene. [0035] In the above formula (5), a is an integer of 0 to 5. a + 1 E may be the same or different, and a G may be the same or different.

 A typical example of D represented by the above formula (5) is shown below.

 When a = 0

 [0037] [Chemical 8]

 [0038] When a = l

[0039] [9]

 [0040] When a = 2

[0041] [Chemical 10]

C ₀ ^^ ⁰

 [0042] When a = 3

[0043] [Chemical 11]

S-

 [0046] n in the formula (4) represents the number of repetitions of [D—A + R 1] units, and is an integer of 0 to 3, preferably 0 or 1.

 [0047] Preferable examples of the atom ion [A +] in the formula (4) are sulfone, odonium, and selenium. Typical examples include the following.

[0048] Examples of sulfone ions include triphenyl sulfone, tri-p-tolyl sulfone, tri-o-tolyl sulfone, tris (4-methoxyphenol) sulfone, 1-naphthyl diphenol. Rusulfol, 2 naphthyl diphenyl sulfone, Tris (4 fluorophenol) sulfone, Tri-1-naphthyl sulfone, Tri-2-naphthyl sulfone, Tris (4- Hydroxyphenyl) sulfol, 4-(phenylthio) phenyl diphenylsulfur, 4- (p-tolylthio) phenyl p-tolylsulfol, 4 (4-methoxyphenylthio) phenol (4-Methoxyphenol) sulfo 4- (phenylthio) phenenolebis (4-funoleolophenol) sulfo 4- (phenylthio) phenol Bis (4-methoxyphenol) ) Sulfome, 4-(Fuerthio) Ferrite p Tolyl Sulfol, Bis [4 (Diphenylsulfo-) phenol] sulfide, Bis [4 {Bis [4 (2-hydroxyethoxy) phenol] sulfo} phenol Sulfide, bis {4 [Bis (4-fluorophenyl) sulfo] phenol} sulfide, bis {4-—bis (4-methylphenol) ) Sulfo] phenyl} sulfide, bis {4— [bis (4-methoxyphenyl) sulfo-] phenol} sulfide, 4 (4 benzoyl 2-cyclothiolthio) phenol (4 -Fonorelophe-Nole), Snorehonium, 4 (4 Benzoinole-2-Black Feninoret), Feninore Disulfol, 4 (4 Benzoylthiol) Ferrubis (4 -Fluoro Fenore) Sunolehonum, 4 (4 Benzoinole-Noretio) Fue-Norezifere-Norestnorejoum, 7—Isopropyl 9-oxo 10 Thia 9,10 Dihydroanthracene 2 —Ildi-p-tolylsulfurum, 7-isopropyl—9—oxo— 10 thia-9, 10 — dihydroanthracene 2-yldisulfol 2-methyl (2-di (tolyl) sulfo) thioxanthone, 2 [(diphenyl) sulfo-thio] thioxanthone, 4- Four (4—tert-butylbenzoyl) phenolthiol p-tolylsulfol, 4 [4- (tert-butylbenzoyl) phenolthio] phenol disulfol, 4 [4- (benzoylphenol) -Luthio)] Fergie p-tolylsulfurum, 4 [4 (Benzyl-Felthio)] Fuel-disulfolsulfome, 5— (4-Methoxyphenyl) thianthrenium, 5-Futhulanthane Triaryl sulfones such as rhenium, 5-tritylanthanthrenium, 5- (4—ethoxyphenyl) thiaanthrhenium, 5- (2, 4, 6 trimethylphenol) thiaanthrhenium; diphenol Diaryl sulfone, such as sylsulfome, diphenol-norm 4—-trofenacinolesnoreum, diphe-norebenzinoresnoreum, diphen-nolemethylsulfo-um; Dil sulfone, 4-hydroxyphenyl methyl benzyl sulfone, 4-methoxyphenyl methyl benzyl sulfone, 4-acetocarboxyl methyl benzyl sulfone, 2-naphthylmethyl benzyl sulfone , 2-naphthylmethyl (1 ethoxycarbonyl) ethenoles norejoum, ueno methenole enocinoles nore hum, 4-hydroxyphenol methylphenacyl sulfome, 4-methoxyphenol Methylphenacyl sulfone, 4-acetocarboxoxymethyl methylphenacyl sulfone, 2-naphthylmethylphenacyl sulfone, 2-naphthyloctadecylphenacyl sulfone, 9-anthrace Monoaryl sulfones such as rumethylphenacyl sulfone; dimethylphenacyl sulfone, Le tetrahydronaphthyl Chio Hue - © beam, dimethyl base Njirusuruho - © beam, benzyl tetrahydropyran Chio Hue - © arm, O Kuta decyl methyl Hue Na Examples include trialkylsulfoms such as sylsulfo-um, which are described in the following references.

 Regarding triarylsulfo-um, US Pat. No. 4,231,951, US Pat. No. 4,256,828, JP-A-7-61964, JP-A-8-165290, JP-A-7-10914, JP-A-7 — 25922, JP-A-8-27208, JP-A-8-27209, JP-A-8-165290, JP-A-8-301991, JP-A-9-143212, JP-A-9-278813, JP-A-10-7680 JP-A-10-287643, JP-A-10-245378, JP-A-8-157510, JP-A-10-203, JP-A-8-245556, JP-A-8-157451, JP-A-7- 324069, JP-A-9-268205, JP-A-9-278935, JP-A-2001-288205, JP-A-11-80118, JP-A-10-182825, JP-A-10-330353, JP-A-10-152495 JP-A-5-239213, JP-A-333834, JP-A-9

— 12537, JP-A-8-325259, JP-A-8-160606, JP-A 2000-186071 (US Pat. No. 6,368,769), etc .; For dialyl sulfone, JP-A-7-300504, JP-A-64-45357, JP-A-64-29419, etc .; Monoaryl sulfones are disclosed in JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (US Pat. 6093753), JP-A-2-196812, JP-A-2-1470, JP-A-2-196812, JP-A-3-237107, JP-A-3-17101, JP-A-6-228086, JP-A-6-28086 10-152469, JP-A-300505, JP-A-2003-277353, JP-A-2003-277352, etc .; with regard to trialkylsulfone, JP-A-4-308563, JP-A-5-140210, JP-A-5 — 140209, JP-A-5-230189, JP-A-6

— 2731532, JP 58-37003, JP 2-178303, JP 10-33868 8, JP 9-9, JP 11-228534, JP 8-27102, JP 7-333834, JP-A-5-222167, JP-A-11-21307, JP-A-11-35613, US Pat. No. 6,310,014 and the like.

[0050] The iodine ions include diphenyl rhododonium, di-tritriordonium, bis (4-dodecylphenol) jordonium, bis (4-methoxyphenol) jordanium, (4- (Cutyloxy) Fuel rhodonum, Bis (4 decyloxyfel) rhodonum, 4— (2 Hydroxytetradecyloxy) fuerol rhodonium, 4— Examples thereof include isopropylphenol (p-tolyl) ododonium, isobutylphenol (p-tolyl) ododome, and the like. Macromolecules, 10, 1307 (1977), JP-A-6-184170, US Pat. U.S. Pat.No. 4,256,828, U.S. Pat.No. 4,351,708, JP 56-135519, JP 58-38350, JP 10-195117, JP 2001-139539, JP 2000 00-510516, JP 2000 — 119306 etc. [This is listed!

 [0051] Examples of selenium ions include triphenyl selenium, tri-p-tolyl selenium, tri-o-tolyl selenium, tris (4-methoxyphenol) selenium, 1-naphthyldiphenyl selenium, tris (4 fluorophenol) selenium. , Tri 1-naphthyl selenium, tri 1 naphthyl selenium, tris (4 hydroxyphenol) selenium, 4 (phenyl thio) ferrodiphenyl selenium, 4- (p-tolylthio) ferro p-tolyl selenium Triaryl selenium such as diphenyl phenacyl selenium, diphenyl benzene selenium, diphenyl selenium such as diphenyl methyl selenium; phenol methylbenzyl selenium, 4-hydroxyphenol methylbenzyl selenium , Phenylmethylphenacyl selenium, 4-hydride Monoaryl selenium such as roxyphenyl methylphenacyl selenium, 4-methoxymethoxymethyl phenacyl selenium; dimethyl phenyl selenium, phenacyl tetrahydroselenophyl, dimethylbenzyl selenium, benzyltetrahydroselenophyl And trialkyl selenium such as octadecylmethylphenacyl selenium, etc., which are described in JP-A-50-151997, JP-A-50-151976, JP-A-53-22597, etc. Has been.

[0052] Of these oniums, preferred are sulfonium and ododonium, and particularly preferred are triphenyl sulfone, tri-p-tolyl sulfone, 4- (phenolic) Rudiphenyl sulfone, bis [4- (diphenylsulfo) phenol] sulfide, bis [4- {bis [4 (2-hydroxyethoxy) phenol] sulfo} phenol ] Sulfide, Bis {4 [Bis (4 fluorophenol) sulfo] phenol} sulfide, 4 (4-Benzolinole-2—Black-mouthed Fe-Noretio) Fe-Norebis (4-Hunoleo-Headed-Nore ) Snorephonium, 4— (4-Benzylphenol-thiol) phenoldisulfol, 7—Isopropyl-1, 9-oxo-1, Thia-1,9,10 Dihydroanthracene, 2-yldi-p-tolylsulfo, 7-Isopropyl 9-oxo 10 Thia 9, 10 Dihydroa Intrase 2-yldiphenyl sulfone, 2-[(di-p-tolyl) sulfo-o] thioxanthone, 2 [(diphenyl) sulfo-] thioxanthone, 4— [4— (4—tert— (Butylbenzoyl) phenolthio] phenyl p-tolylsulfone, 4 [4 (benzoylphenol)] diphenylsulfol, 5- (4-methoxyphenyl) thiaanthrhenium, 5— Phenylthiaanthrhenium, diphenylphenacyl sulfone, 4-hydroxyphenol methylbenzyl sulfone, 2-naphthylmethyl (1-ethoxycarbole) ethyl sulfone, 4-hydroxyphenol Sulfon ions such as methylphenacylsulfo-um and ota-decylmethylphenacylsulfo-um, as well as diphenol-dinitrone, di-tri-trimethyl, bis (4-dodecylphenyl) -iodo. , Bis (4-Methoxyphenol) Feldonium, (4-Octyloxyfehl) Feldhoordium, Bis (4-decyloxy) Feldhodenum, 4- (2-Hydroxytetradecyloxy) ) Feoderm ion, 4-isopropylbutyl (p-tolyl) and 4-isobutylphenol (p-tolyl) odo-um, and so on.

 [0053] In the formula (4) showing the active energy ray cationic polymerization initiator (1), X- is a pair. X— is a fluorinated alkyl fluorophosphate-one represented by the formula (6), and n + 1 X— may be the same or different from each other. It should be noted that it is not excluded that the resist composition of the present invention further contains some amount of other ions unless the object of the present invention is impaired. Any other conventionally known ion can be used, for example, halogen ions such as F-, Cl-, Br-, I-; OH-; CIO-; FSO-, C1SO ―, C

 4 3 3

Sulfonic acid ions such as H 2 SO—, CH 2 SO—, CF 2 SO—; sulfuric acid such as HSO—, SO ²

3 3 6 5 3 3 3 4 4 Ions; Carbonate ions such as HCO—, CO ² , etc .; Phosphorus such as H PO—, HPO ² —, PO ³

 3 3 2 4 4 4

 Acid ions; Fluorophosphate ions such as PF— and PF OH—; BF—, B (C F) —, B (C H

 6 5 4 6 5 4 6

Borate ions such as CF) —; AlCl—; BiF— and the like. Others include SbF―, S

4 3 4 4 6 6 Fluoroantimonate ions such as bF OH—, or fluorine such as AsF— or AsF OH—

5 6 5

 Forces that include arsenate ions These are not preferred because they contain the toxic element Sb or As.

[0054] In the fluorinated alkyl fluorophosphate ion represented by the formula (6), Rf is a fluorine atom. It represents an alkyl group substituted with a elementary atom, preferably having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl and cyclobutyl. And the ratio of the hydrogen atom of the alkyl group substituted by a fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. . When the fluorine atom substitution rate is less than 80%, the cationic polymerization initiating ability of the salt of the present invention and the salt of the transition metal complex is lowered.

[0055] Particularly preferred Rf is a linear or branched alkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include CF, CF CF, (CF) CF, CF CF CF

 3 3 2 3 2 3 2 2

, CF CF CF CF, (CF) CFCF, CF CF (CF) CF, and (CF) C.

 3 2 2 2 3 2 2 3 2 3 3 3

 In the above formula (6), the number b of Rf is an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3. b Rf may be the same or different.

 [0057] Preferable! / As a specific example of fluorinated alkyl fluorophosphates, [(CF CF) PF

 3 2 2 4

] ―, [(CF CF) PF] ―, [((CF) CF) PF] ―, [((CF) CF) PF] ―, [(CF CF CF

 3 2 3 3 3 2 2 4 3 2 3 3 3 2 2

) PF] ―, [(CF CF CF) PF] ―, [((CF) CFCF) PF] ―, [((CF) CFCF) PF

2 4 3 2 2 3 3 3 2 2 2 4 3 2 2 3 3

]-, [(CF CF CF CF) PF] — and [(CF CF CF CF) PF] —

 3 2 2 2 2 4 3 2 2 2 3 3

 Of these, [(CF CF) PF]-, [(CF CF CF) PF]-, [((CF) CF) PF]-, [((CF)

 3 2 3 3 3 2 2 3 3 3 2 3 3 3

CF) PF]-, [((CF) CFCF) PF] — and [((CF) CFCF) PF] — are preferred,

2 2 4 3 2 2 3 3 3 2 2 2 4

 (CF CF) PF] — and [(CF CF CF) PF] — are particularly preferred.

 3 2 3 3 3 2 2 3 3

 [0058] The fluorinated alkyl fluorophosphates of the present invention and the transition metal complex may be used alone as a force thione polymerization initiator, or two or more of them may be used alone. May be used together. Moreover, you may use together with another conventionally well-known cationic polymerization initiator. Other powers Thion initiators include, for example, ionic ions such as sulfoyuum, odonium, selenium, ammonium and phospho- um, or transition metal complex ions and various ionic salts. Examples include halogen ions such as F-, Cl-, Br-, I-; OH-; CIO-

 Four

Sulfonic acid ions such as FSO-, C1SO-, CH SO-, C H SO-, CF SO-; HSO

3 3 3 3 6 5 3 3 3 -Sulfate ions such as SO; Carbonate ions such as HCO-, CO, HPO-, HPO

4 4 3 3 2 4 4 1, Phosphate ions such as PO ³ ; Fluorophosphate ions such as PF-, PF OH-;

 4 6 5 4

Borate ions such as B (C F) —, B (C H CF) —; AlCl—; BiF—; SbF—, SbF OH—

Fluoroantimonate ions such as 6 5 4 6 4 3 4 4 6 6 5; Fluoroarsenate ions such as AsF- and AsF OH-

 6 5

 And the like. Further, it may be used in combination with ammonium or fluorinated fluorinated alkyl fluorophosphate. However, fluoroantimonate ions and fluoroarsenate ions are not preferable because they contain toxic elements.

 [0059] The above sulfo-um ion, iodine-um ion, or selenium ion includes all known ones, and typical examples and references are as described in the present specification.

[0060] Examples of the above-mentioned ammonia ions include tetramethyl ammonium, ethyltrimethyl ammonium, jetyldimethyl ammonium, triethylmethyl ammonium, tetraethyl ammonium, trimethylpropyl ammonium. -Um, trimethylisopropyl ammonium, trimethyl-n-butylammonium, trimethylisobutylammonium, trimethyl-t-butylammonium, trimethyl-n-hexylammonium, dimethyl n- Tetraalkyl ammonium such as propyl ammonium, dimethyldiisopropyl ammonium, dimethyl n-propylisopropyl ammonium, methyltri-n-propyl ammonium, methyltriisopropyl ammonium; N , N Dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N, N Pyrrolidinum such as Jetylpyrrolidinum; N, N '— Dimethinoyl imidazolinum, N, N' — Getinoreyl imidazolinum, N ethyl N '— Methylimidazolium, 1, 2, 3 Trimethyl imidazolium, 1, 3, 4 Trimethyl imidazolium, 1, 3 Jetyl—2-Methyl imidazolium, 1, 3 Jetyl—4-Methyl imidazolium, 1, 2 , 3, 4—Imidazoles such as tetramethylimidazolium; N, N ′ —dimethyltetrahydropyrimidium, N, N ′ —jetyltetrahydropyrimidium, N ethyl N ′ —Tetrahydropyrimidium such as methyltetrahydropyrimidium, 1, 2, 3 trimethyltetrahydropyrimidium; N, N '—dimethylmorpholium, N ethyl-N methylmorpholium, N , N Morphium such as Jetylmolholium; N, N Dimethylpiberidium, N —Methylbiberidium, N, N '—Peberidium, such as Jetylpiveridium; N—Methylpyridium, N-Ethylpyridium, N—n—Propylpyridium, N—Isopropylpyridium , N—n—butylpyridium, N—benzylpyridium, Nphenacylpyridium, etc .; N, N ′ —dimethylimidazolium, N ethyl—N—methylol Imidazolium, N, N '— Getino Rei Midazolium, 1, 2 Getinore 3—Methyl imidazolium, 1, 3 Jetruo 2—Methyl imidazolium, 1—Methyl 3— n—Propyl 2, 4 N-methylquinolium, N-ethylquinolium, N-n-propylquinolium, N-isopropylquinolium, N-n-butylquinolium, N-benzylquinolium, N-phenacylcyl Quinolium such as L; N-methinoreisoquinolium, N ethinoreisoquinolium, N-n-propinoreisoquinolium, N isopropylisoquinolium, Nn-butylisoquinolium, N benzene Isoquinolium such as noreisoquinolium and N-phenacylisoquinolium; thiazoum such as benzylbenzothiazoum and phenacinobenzothiazum; and arridium such as benzylataridium and phenacyltharidium It is done.

 [0061] These include US Patent No. 4069055, Patent Publication No. 2519480, JP-A-5-222111, JP-A-5-222111, JP-A-5-262813, JP-A-5-255256, JP-A-5-255256. 7-109303, JP-A-10-101718, JP-A-2-268173, JP-A-9-32 8507, JP-A-5-132461, JP-A-9-221652, JP-A-7-43854, JP 7-43901, JP-A-5-262813, JP-A-4-327574, JP-A-2-433202, JP-A-60-203628, JP-A-57-209931, JP-A-9-221652, etc. Are listed.

[0062] Examples of the above phosphonium ions include tetraphenyl phosphonium, tetra p-tolyl phosphonium, tetrakis (2-methoxyphenol) phosphonium, and tetrakis (3-methoxyphenyl) phosphones. Tetralinole phosphomes such as -um, tetrakis (4-methoxyphenol) phosphomume; triphenyl pendyl phosphome, triphenylphenacyl phosphine, triphenylmethylphosphome, triphenyl butylphospho Triarinorephosphomumes such as rum; triethylbenzylphosphome, tributylbenzylphosphome, tetraethylphosphome, tetrabutylphosphome, tetrahexylphosphome, Examples thereof include tetraalkylphosphonium such as triethylphenacylphosphome and tributylphenacylphosphome. These are described in JP-A-6-157624, JP-A-5-105692, JP-A-7-82283, JP-A-9 202873, and the like.

 [0063] In the present invention, when two or more of the fluorinated alkyl fluorophosphates of the formula (4) are used in combination as the active energy ray cationic polymerization initiator (1), the amounts of each other The ratio is arbitrary and not limited. When other cationic polymerization initiators are used in combination, the quantity ratio to the fluorinated alkyl fluorophosphate of formula (4) may be arbitrary, but usually the fluorinated alkyl fluoride of formula (4). The other cationic polymerization initiator is 10 to 900 parts by mass, preferably 25 to 400 parts by mass with respect to 100 parts by mass of the olophosphate (in the following description, parts represent parts by mass).

In the present invention, as the active energy ray cationic polymerization initiator (1), in order to facilitate dissolution in the cationically polymerizable compound (2), arabic tanning solvents are used. You may use what was dissolved in. Examples of solvents include alcohols such as methanol, ethanol, _n -propyl alcohol, isopropyl alcohol, n-butanol, and isobutanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, and methyl. Ketones such as n-propyl ketone, cyclopentanone and cyclohexanone; ethers such as jetyl ether, tert-butyl ether, tetrahydrofuran, 1,3 dioxane, 1,4 dioxane; propylene carbonate, ethylene carbonate, 1, 2 —Carbonates such as butylene carbonate, dimethylolate carbonate, and jetinole carbonate; ethyl acetate, lactyl acetate, butyl acetate sorb acetate, carbinol acetate, β-propiolatathone, j8-butyrolol T, y butyrolatataton, δ valerolatataton, ε-force prolatataton and other esters; ethylene glycol monomethyl etherate, ethylene glycol monoethanolateolate, propylene glycolenolemonomethinoretel, propylene glycol norenomethino Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl etherate, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether Monoalkyls such as ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Glycol ethers: ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl enoate, diethylene glycinole methino ree tenole, diethylene glycol diol ether, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether Dialkyl glycol ethers such as ethyl ether, triethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tripropylene glycol dimethyl ether; ethylene glycol monomethylenoethyl acetate, ethylene glycol monomethenoate etherate Acetate, propylene Aliphatic carboxylic acid esters of monoalkyl glycol ethers such as ethyl monomethyl ether acetate and propylene glycol monoethyl ether acetate; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; hexane, ethane and decane Aliphatic hydrocarbons such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha and other petroleum solvents;

[0065] When these solvents are used, the use ratio is usually 15 to L000 parts, preferably 100 parts by weight with respect to 100 parts of the active energy-linear cationic polymerization initiator of (1) of the present invention. Is between 30 and 500cm.

 [0066] Examples of the cationically polymerizable compound (2) in the composition of the present invention include cyclic ether compounds such as epoxide oxetanes, ethylenically unsaturated compounds such as butyl ethers and styrene, and Bicycloorthoesters, spiroorthocarbonates, spiroorthoesters and the like can be mentioned.

[0067] Examples of the epoxide include conventionally known epoxides, and examples of the aromatic epoxide include monovalent and polyvalent phenols having at least one aromatic ring, such as phenol, tare zonole, xylenol, biphenol, bisphenol. A, bisphenol f, triphenol methane, trisole methane, biphenol, tetramethylbiphenol, dihydroxynaphthalene, binaphthol, bis (4-hydroxyphenol) diphenol methane, phenol novolak, xylylene novolak, cresolol novolak, xylenol novolak , Bifuenol novolak, bisphenol A novolak, bisphenol F novolak, triphenol Glycidyl ether of rumethane novolak, dicyclopentadiene phenol novolak, terpene phenol nopolac and brominated compounds thereof or compounds further added with alkylene oxide, and glycidyl monovalent and polyvalent carboxylic acid having at least one aromatic ring Esters such as diglycidyl phthalate, diglycidyl

3 Methyl phthalate, etc .; As the alicyclic epoxide, a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent, for example, 3, 4-epoxycyclohexylmethyl-3, 4 —Epoxycyclohexanecarboxylate, 3, 4 Epoxy 1-methylcyclohexylene 3,4 Epoxy 1-methylhexanecarboxylate, 6-Methyl-3,4 Epoxycyclohexyl Methyl-6-methyl-3,4-Epoxycyclohexane Carboxylate, 3, 4 Epoxy 3-Methylcyclohexylmethyl- 3, 4-Epoxy 3-methylcyclohexane force Ruboxylate, 3, 4 Epoxy-5-Methylcyclohexylmethyl- 3, 4-Epoxy 5-methylcyclohexanecarboxylate, 2- (3,4 epoxy cyclohexyl -5, 5-spiro 3, 4-epoxy) cyclohexane metadioxane, bis (3,4-epoxy cyclohexylmethyl) adipate, 3, 4 epoxy-6-methylcyclohexyl carboxylate, methylene bis (3,4-epoxy Cyclohexane), dicyclopentadiene epoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), etc .; examples of polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof include: Diglycidyl ether of diethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of polypropylene glycol, diglycidyl ether of butanediol, diglycidyl ether of hexanediol, hydrogenated bisphenol A diglycidyl Ether, hydrogenated bisphenol F diglycidyl ether, triglycidyl ether of glycerin, diglycidyl ether, monoglycidyl ether, triglycidyl ether of trimethylolpropane, diglycidino ether, monoglycidyl ether, tetraglycidyl ether of sorbitol , Triglycidyl ether, diglycidinole ethere, monoglycidyl ether, triglycidyl ether of trimethylolpropane, diglycidyl ether, monoglycidyl ether, tetraglycidyl ether of pentaerythritol, triglycidyl ether, diglycidyl ether Monoglycidyl ether, hexaglycidyl ether of dipentaerythritol, etc .; polyglycidyl esters of aliphatic polybasic acids, such as diglycidyl tetrahydrophthalate

, Diglycidyl hexahydrophthalate, diglycidyl hexahydro-3-methyl phthalate, etc .; epoxyated products of long chain unsaturated compounds such as epoxy soybean oil and epoxy polybutadiene; epoxy groups such as glycidyl group, 3, 4 epoxy in the molecule 1-Cyclohexylmethyl group, 5, 6 Epoxy—2 Bicyclo [2.2.1] heptyl group, 5 (6) —Epochichetil-2 bicyclo [2.2.1] heptyl group, 5, 6 Epoxy-2 Bicyclo [2 2. 1] heptylmethyl group, 3, 4 epoxytricyclo [5. 2. 1. 0 ² ' ⁶ ] decyl group, 3, 4 —epoxytricyclo [5. 2. 1. 0 ² ' ⁶ ] decyl group Oxetyl group, 3, 4 epoxy tetracyclo [4. 4. 0. I ² ' ^5. 1 ⁷ . ] Dodecyl group, 3, 4 epoxytetracyclo [4. 4.0. I ² ' ^5. I ⁷ , ¹ . ] (Meth) acrylate homopolymers having epoxy groups such as dodecylmethyl groups or copolymers of these with other unsaturated monomers, such as JP-A-11 174677, JP-A-11-15159, JP-A-2005- No. 250067, Japanese Patent Application Laid-Open No. 2004-133424, and references described in the specification, and further described in Journal of Polym. Sci., Part A, Polym. Chem., Vol. 28,497 (1990). Examples thereof include polyfunctional epoxides having a dimethylsiloxane skeleton.

As oxetanes, conventionally known ones such as, for example, 3-ethyl-3-hydroxymethyl oxetane, (3-ethyl-3-oxeta-methoxy) methylbenzene, [1- (3-ethyl-3-oxeta-methoxy) ethyl] phenol ether , Isobutoxymethyl (3-ethyl 3-oxeta-methyl) ether, isobornyl oxychetyl (3-ethyl 3-oxeta-methyl) ether, isobornyl (3-ethyl 3-oxetamethyl) ether, 2-ethyl Xylyl (3ethyl 3-oxeta-methyl) ether, Ethyl diethylene glycol (3-ethyl-3-alkyl ether), Dicyclopentyl (3-ethyl-3-oxeta-methyl) ether, Dicyclopentenyl (3-ethyl) 3-Oxetanylmethyl) ether, tetrahydroph Furyl (3-ethyl-3-ethylacetal) ether, tetrabromophenol (3-ethyl-3-ethyl-ether) ether, 2-tetrabromophenoloxy (3-ethyl 3-oxeta-methyl) ether, Tribromophenol (3-ethyl 3-oxeta -Rumethyl) ether, 2 tribromophenoxetyl (3 ethyl-3-oxeta-methyl) ether, 2 hydroxyethyl (3 ethyl 3 oxeta-lmethyl) ether, 2 hydroxypropyl (3 ethyl-3-oxetanyl) Methyl) ether, butoxetyl (3-ethyl 3-oxeta-methyl) ether, pentachlorophenol (3-ethyl 3-oxeta-methyl) ether, pentabromophenol (3-ethyl 3-oxeta-methyl) ether, Borol (3 ethyl 3-oxeta-methyl) ether, 3, 7 Bis (3-oxetal) -5-oxanonenonane, 3, 3, 1 (1, 3— (2-methylol) propane Diylbis (oxymethylene)) bis (3-ethyloxetane), 1,4 bis [(3 ethyl 3-oxeta-lmethoxy) methyl] benzene, 1,2 bis [(3 ethyl 3-Oxeta-lmethoxy) methyl] ethane, 1,3 bis [(3 ethyl 3-oxeta-noremethoxy) methyl] propane, ethylene glycol bis (3-ethynole 3-3-oxeta-methyl) ether, dicyclopenta-bis (3-ethyl) 3 —Oxetermethyl) ether, triethyleneglycol bis (3-ethyl-3-ethyl) ether, tetraethylenedaricol bis (3-ethyl-3-oxeta-methyl) ether, tricyclodecanedildimethylene ( 3-Ethyl-3-oxeta-l-methyl) ether, trimethylolpropane tris (3-Ethyl 3-oxetanylmethyl) ether, 1,4 bis (3-ethyl 3-oxeta-lmethoxy) butane, 1, 6 bis (3 Ethyl —3-oxetanylmethoxy) hexane, pentaerythritol tris (3 Ethyl 3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-ethyl-ether) ether, polyethylene glycol bis (3-ethyl-3-oxomethyl) ether, dipentaerythritol hexakis (3-ethyl-3) —Oxetanyl methyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl 3-oxeta-methyl) ether, 3-ethyl-3-phenoxymethylo Xetane, 3-ethyl-3- (4-methylphenoxy) methyloxetane, 3-ethyl 3- (4 fluorophenoxy) methyloxetane, 3-ethyl-3- (1 naphthoxy) methyloxetane, 3-ethyl-3- (2 naphthoxy) Methyloxetane, 3- Chilu 3— {[3- (Ethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxetane, phenol novolak oxeta For example.

 [0069] Examples of the ethylenically unsaturated compound include conventionally known cationically polymerizable compounds such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutino levino reetenole, cyclohexino levino reetenole, 2-chloroethinorevinino ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl butyl ether, 2-acetoxetyl butyl ether, diethylene glycol noremonobi-norethenore, 2-ethinorehexino levi Aliphatic monovinyl ethers such as 2-noreatenore, dodecinorebi-noreether, octadecyl vinyl ether, allyl vinyl ether, 2-methacryloyl oxychetyl butyl ether, 2-ataryl leuoxy schitil bilyl ether; 2 Aromatic monobutyl ethers such as enochetyl vinyl ether, vinyl vinyl ether, p-methoxyphenol vinyl ether; butanedio mononole 1,4-divininoreethenore, triethyleneglyconoresininoreethenore, 1, 4 Benzene divinyl ether, Hydone quinone divinyl ether, Cyclohexane dimethanol dibule ether (1, 4 bis [(Buroxy) methyl] cyclohexane), Jetylene glycolo-resinino enoate, Dipropylene glyconoresinini Polyfunctional butyl ethers such as Noleyatenole and hexanediol dibule ether; Styrenes such as styrene, OC methyl styrene, ρ-methoxy styrene, p-tert-butoxy styrene; N vinylcarbazole, N butyl pyrrolidone Cations such as Etc. compatibility nitrogen-containing monomer can be mentioned.

[0070] Examples of the bicycloorthoesters include 1-phenyl 4-ethyl 2, 6, 7 trioxa bicyclo [2. 2. 2] octane, 1-ethyl 4-hydroxymethyl-2, 6, 7 trioxabi cyclo [2. 2. 2] Octane and so on.

[0071] Spiro orthocarbonates include 1, 5, 7, 11-tetraoxaspiro [5.5] undecane, 3, 9-dibenzyl-1, 5, 7, 11-tetraoxaspiro [5.5] undecane And so on.

 [0072] Spiro orthoesters include 1, 4, 6 trioxaspiro [4. 4] nonane, 2-methyl

1, 4, 6 trioxaspiro [4. 4] nonane, 1, 4, 6 trioxaspiro [4. 5] decane. These cationically polymerizable compounds are disclosed in JP-A-11 060996, JP-A-09-302269, JP-A-2003-026993, JP-A-2002-206017, JP-A-11-349895, and JP-A-10-. No. 212343, JP 2000-119306, JP 10-67812, JP 2000 00-186071, JP H08-85775, JP 08-134405, US2005 / 01 47918, US2005Z0260522, JP 2005-250067, JP-A-10-62991, Patent No. 3033549, Photopolymer social gathering “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV'EB Curing Technology” ( 1982, Comprehensive Technology Center), Radtech Study Group “UV'EB Curing Materials” (1992, CM1), Technical Information Association “UV Curing Failure Inhibition Causes and Countermeasures” (2003, (Technical Information Association), Epoxy Oil Resin Technology Association, “Introduction Epoxy Resin, Part 1 Fundamentals I” (2003, Carboxymethyl 榭脂 Technology Association), the colorant, 68, (5), 286- 293 (1995), Fine Chemical, 29, are described, for example, (19), 5- 14 (2000).

 [0074] Of these cationically polymerizable compounds, aromatic epoxides having excellent etching resistance, resistance to plating, and mechanical strength of the resist after pattern formation are preferred. Functionality of epoxy groups in one molecule Bisphenol A novolak or bisphenol F novolac resin having a radix of 2 or more is particularly preferred. These cationically polymerizable compounds may be used alone or in combination of two or more.

 [0075] The active energy-sensitive linear cationic polymerization initiator (1) is used in an amount of usually 0.05 to 30 parts per 100 parts of the cationic polymerizable compound (2) relative to the cationic polymerizable compound (2). However, it is preferably 0.1 to 15 parts. Appropriate use ratios are the properties of the cationic polymerizable compound, the type and irradiation amount of active energy rays, temperature, curing time, humidity, coating thickness, etc. Determined by considering various factors. If the proportion of the active energy-sensitive cationic polymerization initiator is less than 0.05 parts, the polymerization of the cationic polymerizable compound is insufficient, and if it is more than 30 parts, it is cured by an unreacted cationic polymerization initiator or its decomposition product. The properties of the product may deteriorate, or the amount of active energy rays absorbed by the cationic polymerization initiator itself may increase, so the curability at the deep part of the coating film may decrease.

[0076] In the composition of the present invention, the solvent (3) is suitable for dissolving the active energy-sensitive cationic polymerization initiator (1) and the cationic polymerizable compound (2) and applying them to the substrate. Liquidity As long as it is possible to obtain a uniform and smooth coating film in the pre-beta (solvent component removal step) and it does not remain in the resist coating film, it may be any material. Examples of such a solvent include the same solvents described above as solvents that can be used when dissolving the active energy ray cationic polymerization initiator (1). Also, these solvents can be used alone, or one of them can be used alone, or two or more can be used together.

 [0077] Among these solvents (3), methyl ethyl ketone, cyclopentanone, cyclohexanone, gamma butyrolatatane, or propylene glycol monomethyl ether acetate, which can provide fluidity of the composition and a uniform coating film, is preferable. Better ,.

 [0078] The use ratio of the solvent (3) is usually 5 to 300 parts, preferably 10 to L00 parts with respect to 100 parts of the cationically polymerizable compound (2).

 [0079] The resist composition of the present invention includes a sensitizer, a pigment, a filler, an antistatic agent, a flame retardant, an antifoaming agent, a flow regulator, a light stabilizer, a solvent, a non-reactive soot as necessary. Additives such as fats and radical polymerizable compounds can be used.

[0080] A conventionally known sensitizer can be used in combination with the resist composition of the present invention, particularly those cured by irradiation with active energy rays, if necessary. Examples of such sensitizers are described in JP-A-11 279212 and JP-A-09-183960. Specifically, anthracene, 9,10 dibutoxyanthracene, 9,10 dimethoxyanthracene, 2 Thiruth 9, 10 Dimethoxyanthracene, 2-tert-butyl-9,10 Dimethoxyanthracene, 2,3 Dimethyl-9,10 Dimethoxyanthracene, 9-methoxy 10-Methylanthracene, 9,10 Jetoxyanthracene, 2 Ethyl 9,10 Jetoxy Anthracene, 2-tert-butyl-9,10 methoxyanthracene, 2,3 dimethyl-9,10- ethoxyanthracene, 9 ethoxy-10-methylanthracene, 9,10 dipropoxy cyanthracene, 2 ethyl-9,10 dipropoxyanthracene, 2-tert-Butyl 9, 10 Dipropoxyanthracene, 2, 3 Dimethylolene 9, 10 Dipropo Cyantracene, 9 Isopropoxy, 10-Methylanthracene, 9,10 Dibenzyloxyanthracene, 2 Ethyl-9,10 Dibenzyloxyanthracene, 2--tert 9,10 Dibenzyldioxyanthracene, 2,3 Dimethyl-9 10 Dibenzyloxyanthracene, 9 Monobenzyloxy 10-methylanthracene, 9, 10 G α-Methylbenzyloxy Cyantracene, 2 ethyl 9, 10 di α-methylbenzyloxyanthracene, 2 —tert 9, 10 Di-α-methylbenzyloxyanthracene, 2, 3 dimethyl-9, 1 0 Di-α-methylbenzyloxyanthracene, 9 (α-methylbenzyloxy) 10-methylanthracene, 9, 10 diphenylanthracene, 9-methoxyanthracene, 9-ethanthanthracene, 9-methylanthracene, 9 bromoanthracene, 9-methylthioanthracene, 9-eth Anthracene such as ruthioanthracene; pyrene; 1, 2, benzanthracene; perylene; tetracene; coronene; thixanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-cyclothioxanthone, 2-isopropylthixanthone, 2, 4 Thioxa such as Jetylthioxanthone Phenothiazine; xanthone; 1 naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 1,5 dihydroxynaphthalene, 1,6 dihydroxynaphthalene, 2,7 dihydroxynaphthalene , 2, 7 Dimethoxynaphthalene, 1, 1, -thiobis (2 naphthol), 1, 1 'be (2 naphthol), 4-methoxy-1 naphthol and other naphthalenes; dimethoxyacetophenone, diethoxyacetophenone, 2- Hydroxy-2-methyl-1 phenylpropane 1-one, 4 isopropyl 2 hydroxy-2 methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2, 2-dimethoxy-1,2-diphenyl-1-one , P dimethylaminoacetophenone, p —tert butyl dichloro Acetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin mono n-butyl ether , Benzoin isobutyl ether, 1 [4 — (2-hydroxyethoxy) phenol] — 2-hydroxy-2-methinole 1-propane 1 1-one, benzophenone, o methyl benzoylbenzoate, Michler's ketone, 4, 4, 1 Ketones such as bis-detylaminobenzophenone, 4, 4'-dichroic benzophenone, 4-benzoyl 4, —methyldiphenylsulfide; N-phenylcarbazole, N-ethylcarbazole, poly N vinylcarbazole, N— Glycidylcarba Power carbazole such as Lumpur; 1, 4-dimethoxy chrysene, 1, 4-jet carboxymethyl chrysene, 1, 4 Jipu port Pokishitarisen, 1, 4-dibenzyl O carboxymethyl Tari Sen, 1, 4-di-α-methylbenzyl Talycenes such as oxytalicene; 9 hydroxyphenanthrene, 9-methoxyphenanthrene, 9 ethoxyphenanthrene, 9-pentenoreoxyphenanthrene, 9, 10 dimethoxyphenanthrene, 9, 10 diethoxyphenanthrene, 9, 10 Dipropoxyphenanthrene, 9, 10 Dibenzyloxyphenanthrene, 9, 10 G α-Methylbenzyloxyphenanthrene, 9-hydroxy 10-methoxyphenanthrene, 9-hydroxy 10-ethoxyphenanthrene, etc. Phenanthrenes.

 [0081] When these sensitizers are used, the use ratio is usually 0.005 to 20 parts, preferably 0.01 to 10 parts, per 100 parts of the resist composition of the present invention. These sensitizers can be used alone, or one of them can be used alone, or two or more can be used together.

 [0082] Examples of the pigment include conventionally known pigments, for example, inorganic pigments such as titanium oxide, iron oxide, and carbon black, and organic pigments such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments. .

 [0083] The ratio of these pigments to be used is generally 0.1 to 300 parts, preferably 1 to 200 parts, per 100 parts of the resist composition of the present invention. In addition, these pigments may be used alone or in combination of two or more.

 [0084] As the filler, conventionally known ones such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, slag, talc, calcium silicate, lithium aluminum silicate, etc. Is mentioned. When these fillers are used, the amount used is usually 10 to 300 parts, preferably 30 to 200 parts, per 100 parts of the resist composition of the present invention. In addition, these fillers may be used alone or in combination of two or more.

[0085] Antistatic agents are conventionally known, for example, glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, Ν, ビ ス bis (2-hydroxyethyl) alkylamine, polyoxyethylene alkyl. Nonionic type such as amine, polyoxyethylene alkylamine fatty acid ester, alkyldiethanolamide; Alon type such as alkyl sulfonate, alkylbenzene sulfonate, alkyl phosphate; Tetraalkyl ammonia Cation-type salts such as salt, trialkylbenzil ammonium salt; alkylbetaine, alkylimidazole Amphoteric type such as umbetaine; quaternary ammonium group-containing styrene mono (meth) tarylate copolymer, quaternary ammonium group-containing styrene-acrylonitrile-maleimide copolymer and polyethylene oxide, Examples include ionic and nonionic polymer types such as polyether ester amide, polyether amide imide, ethylene oxide-epoxychlorohydrin copolymer, and methoxypolyethylene glycol (meth) acrylate copolymer. It is done.

 [0086] When these antistatic agents are used, the use ratio is usually 0.01 to 10 parts, preferably 0.05 to 5 parts, per 100 parts of the resist composition of the present invention. Also, these antistatic agents may be used alone or in combination of two or more.

 [0087] Conventionally known flame retardants such as antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide aluminum Inorganic compounds such as magnesium hydroxide and calcium aluminate; bromines such as tetrabromophthalic anhydride, hexabromobenzene and decabromobiphenyl ether; phosphate esters such as tris (tribromophenol) phosphate Things.

 [0088] When these flame retardants are used, the use ratio is usually 0.1 to 20 parts, preferably 0.5 to LO parts, with respect to 100 parts of the resist composition of the present invention. These flame retardants may be used alone or in combination of two or more.

 [0089] Conventionally known antifoaming agents, for example, alcohols such as isopropanol, n-butanol, octethyl alcohol, hexadecyl alcohol; metal stalagmites such as calcium stearate and aluminum stearate; Phosphate esters such as tributyl phosphate; Fatty acid esters such as glycerin monolaurate; Polyethers such as polyalkylene glycol; Silicones such as dimethyl silicone oil and silica 'silicone compound; Mineral in which silica powder is dispersed Oils.

 [0090] When these antifoaming agents are used, the amount used is usually 0.01 to 10 parts, preferably 0.05 to 5 parts, per 100 parts of the resist composition of the present invention. These antifoaming agents may be used alone or in combination of two or more.

[0091] As the flow regulator, conventionally known ones such as hydrogenated castor oil, acid-polyester are used. Examples thereof include lens, organic bentonites, colloidal silica, amide waxes, metal stannic acids, and acrylate polymers.

 [0092] When these flow regulators are used, the amount used is usually 0.01 to 10 parts, preferably 0.05 to 5 parts, per 100 parts of the resist composition of the present invention. In addition, these flow regulators may be used alone or in combination of two or more.

 [0093] Conventionally known light stabilizers, for example, ultraviolet absorption types such as benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof; radical scavenging types represented by hindered amines; nickel Examples include quenching types such as complexes.

 [0094] When these light stabilizers are used, the use ratio is usually 0.005 to 40 parts, preferably 0.01 to 20 parts, relative to 100 parts of the resist composition of the present invention. In addition, these photostabilizers may be used alone or in combination of two or more.

[0095] In addition, the active energy-sensitive negative resist composition of the present invention has a polyfunctional OH group-containing compound, a crosslinking agent, non- A reactive resin or radical polymerizable compound can be added. Examples of polyfunctional OH-containing compounds include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,3 butanediol, 1, 4 -Butanediol, 1,6 hexanediol, 1,2,4 butanetriol, 1,2 cyclohexanediol, 1,3 cyclohexanediol, 1,4-cyclohexanediol, 1,2 cyclohexanedi Methanol, 1,4-cyclohexanedimethanol, 1,3,5-cyclohexane trimethanol, 1,2 cyclopentanediol, 1,3 cyclopentanediol, 1,2 cyclooctanediol, 1,5 cyclooctanediol , Tricyclodecane dimethanol, 2, 3 nobornane All, 2 (3) —Hydroxy-1,5 bis (hydroxymethyl) norbornane, 2,3 Dihydroxy 5 (6) —Hydroxymethylnorbornane, 1,4 Anhydroerytriol, L arabinose, L arabitol, D Cellobiose, cellulose, 1,5 decalindiol, glucose, galactose, ratatose, macro Polyose Prolatatone Polyol, Trimethylolpropane, Glycerin, Pentaerythritol, Polyesterdiol, Polycarbonatediol, Bisphenol-8, etc., as described in lutose, mannose, mannan-toll, US—6716568, US-2005 / 0266335 Bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, phenol novolac resin, cresol novolac resin, and their alkylene oxide adducts. Examples of these OH group-containing compounds are described in JP-A Nos. 2005-263379 and 2000-186071.

 [0096] Examples of the crosslinking agent include conventionally known amino compounds such as melamine resin, urea resin, guanamine resin, glycoluril formaldehyde resin, succinamide-formaldehyde resin, ethylene urea-formaldehyde resin. In particular, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethyliurea resin, ethoxymethylated urea resin, propoxymethyliurea Resins, alkoxymethylated melamines such as butoxymethyl iurea resins, and the like can be suitably used.

 [0097] Examples of the non-reactive resin include polyester, polyacetate butyl, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polybutyl ether, polybutyl propylal, polybutene, hydrogenated styrene butadiene block copolymer, ( Examples thereof include a copolymer of (meth) acrylic acid ester and polyurethane. The number average molecular weight of these coconut resins is 1000 to 500000, preferably 5000 to 100000 (the number average molecular weight is measured by a general method such as GPC).

 [0098] In order to facilitate the dissolution of these resins in the resist composition of the present invention, it is desirable that they should be dissolved in the above-mentioned solvent in advance before compounding.

[0099] Examples of radical polymerizable compounds are “Photopolymer Handbook” (1989, Industrial Research Committee) edited by Photopolymer Social Meeting, “UV'EB Curing Technology” (1982, General Technology). Surgery Center), Radtech Study Group “UV'EB Curing Materials” (1992, CM1), Technical Information Association “UV Curing Failure Inhibition Causes and Countermeasures” (2003, Technical Information Association) It is described in. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxy Monofunctional monomers such as ethyl (meth) acrylate, 1, 6 hexanediol mono (meth) acrylate, styrene, bicyclohexene, isobutylene, butadiene; ethylene glycol, propylene glycol, bisphenol A or its Bifunctional alcohols such as hydrides or di (meth) acrylates of these alkylene oxide adducts, difunctional monomers such as dibenzene, polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol or the like Polyfunctional monomers such as (meth) acrylates of the alkylene oxide adducts; epoxides obtained by reacting epoxides such as aromatic epoxides, alicyclic epoxides, and aliphatic epoxides with (meth) acrylic acid (Meth) atalylates; phthalic acid, a Aromatic polybasic acids such as phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, aliphatic polybasic acids such as succinic acid, adipic acid, and sebacic acid, and ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, Dipropylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,3 butanediol, 1,4 butanediol, 1,6 hexanediol, trimethylolpropane, glycerin, pentaerythritol, bisphenol and their alkylene oxides Polyhydric alcohols such as adducts Polyester (meth) acrylates obtained by esterifying the obtained hydroxy-terminated polyester with (meth) acrylic acid; isophorone diisocyanate , Cycloaliphatic isocyanates such as dicyclohexylmethane diisocyanate, aliphatic isocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, toluene diisocyanate, phenyl diisocyanate, diphene -Polyfunctional isocyanates such as aromatic isocyanates such as rumethane diisocyanate and ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentino glycol, polytetramethylene glycol, 1,3 butanediol 1, 4 butanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, bisphenol, hydrogenated bisphenol and poly-prolatatonedio Isocyanate-terminated prepolymers from polyhydric alcohols such as polyols, polyester diols, polycarbonate diols, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) atarylate, pentaerythritol tri (meth) Examples include uretan (meth) acrylates obtained by reaction with hydroxy group-containing (meth) acrylates such as acrylate.

 [0100] When these polyfunctional OH group-containing compound, crosslinking agent, non-reactive resin, and radical polymerizable compound are used, the use ratio is usually 1 to: 100 parts per 100 parts of the composition of the present invention. Parts, preferably 5 to 50 parts. Further, any one of these polyfunctional OH group-containing compounds, crosslinking agents, non-reactive resins, and radical polymerizable compounds may be used alone or in combination of two or more. Well, ...

[0101] When using the above radical polymerizable compounds, it is preferable to use a radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight thereof by radical polymerization. . These radical polymerization initiators include conventionally known ones. Examples of the thermal radical polymerization initiator include organic peroxides such as ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, 2 , 2-bis (te rt butylperoxy) butane, peroxyketals such as 1, 1 bis (tert butylperoxy) cyclohexane, tert butyl hydride peroxide, cumene hydride peroxide, etc. Dialkyl peroxides such as oxides, disilver oxides such as isobutyryl peroxide, lauroyl peroxide, and benzoyl peroxide, peroxydicarbonates such as diisopropylperoxydicarbonate, tert butylperoxyiso Peroxyesters such as thiolate, 2,5 dimethyl-2,5 di (benzoylperoxy) hexane, and azo compounds such as 1,1, -azobis (cyclohexane—one strength rubonitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4 dimethyl-4-methoxyvalero-tolyl), 2,2,1azobis (2-methylpropionamidine) dihydride chloride, 2, 2, -azobis [2-methyl-N- (2-probe) propionamidine] dihydrochloride, 2,2, -azobis (2-methylpropionamide), 2, 2, -azobis [2-methyl-N- ( 2-hydroxyethyl) propionamide], 2,2, -azobis (2-methylpropane), 2,2'-azobis (2,4,4 trimethylpentane), dimethyl 2,2'-azobis (2-methyl) Propionate) And the like. Photo radical polymerization initiators include acetophenone, p-tert butyltrichloroacetophenone, 2, 2-diethoxyacetophenone. Acetophenone compounds such as benzophenone, o Benzophenone compounds such as methyl benzoylbenzoate, 4 benzoyl 4, 4-methyldiphenylsulfide, 4, 4, bis (dimethylamino) benzophenone, 4, 4, 1bis (jetylamino) benzophenone, etc. Michler's ketone compounds; benzoin compounds such as benzoin and benzoin methyl ether; thixanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2 cyclothioxanthone, 2 isopropinoretioxanthone, 2,4 jetinorexanthone Thioxanthone compounds; for example, isacylphosphine compounds such as monoacylphosphine oxide and bisacylphosphine oxide.

 [0102] The use ratio of these radical polymerization initiators is usually 0.01 to 20 parts, preferably 0.1 to L0 parts with respect to 100 parts of the radical polymerizable compound. These radical polymerization initiators may be used alone or in combination of two or more.

 [0103] The preparation of the active energy-sensitive negative resist composition of the present invention can be performed by mixing and stirring by a usual method, and using a disperser such as a dissolver, a homogenizer, or a three-roll mill. You may mix. You may heat as needed. Further, after mixing, it may be further filtered using a mesh, a membrane filter or the like.

 [0104] As described below, a resist film is formed by applying the active energy ray negative resist composition of the present invention to a substrate, and heating and drying (pre-beta) the substrate coated with the resist composition. A step of selectively exposing the obtained resist film in accordance with a desired pattern using active energy rays, a step of improving the contrast by heat-treating the exposed resist film (PEB), and a heat treatment A good pattern can be formed by developing the subsequent resist film and dissolving and removing the unexposed resist material to obtain a pattern layer. Especially, a pattern with a thick film and a high aspect ratio can be obtained. It is possible.

[0105] (A) Formation of coating film: The resist composition of the present invention is applied to a substrate. There are no particular restrictions on the coating method. Screen coating methods such as curtain coating, blade coating, spin coating, spray coating, dip coating, and slit coating can be applied. Since the resist composition of the present invention can be made into a high concentration resist solution, it can be applied to a thick film by a simple method such as spin coating. In addition, the support substrate to which the resist composition of the present invention is applied and the surface state thereof are not particularly limited. Examples of the supporting substrate include silicon, glass, metal, ceramic, and organic polymer. These supporting base materials can also be subjected to pretreatment of the base material for the purpose of improving adhesiveness. For example, improvement of adhesiveness can be expected by performing silane treatment.

 [0106] (B) Drying of coating film: The substrate coated with the resist composition of the present invention in the above step is dried by heating (pre-beta) to obtain a resist film. There are no particular restrictions on the drying conditions, but the temperature varies depending on the type and proportion of each component in the composition of the present invention, the coating film thickness, etc. Preferred to do ,. Usually, it is 60 to 160 ° C, preferably 70 to 140 ° C for about 1 minute to 5 hours. If the drying temperature is too high, the composition may cause a thermal reaction, which may cause defects in pattern formation. Note that the thickness of the resist film is not particularly limited, and is usually about several to zm to several mm. Even a thick film of 50 / zm or more can be processed with high accuracy in the subsequent steps. A particularly preferred film thickness is 50 m to 2 mm.

 (C) Active energy ray irradiation: The resist film obtained in the above step is selectively exposed to an active energy ray in accordance with a desired pattern. The active energy line used for the exposure is not particularly limited. Examples of these active energy rays include ultraviolet rays, visible rays, far ultraviolet rays, near ultraviolet rays, X-rays, electron beams, and the like. As a source of these active energy lines, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressures, etc. Mercury lamp, metalno, ride lamp, xenon lamp, carbon arc lamp, fluorescent lamp, solid state laser, argon laser, He—Cd laser, KrF excimer laser, ArF excimer laser, F laser, etc.

 2

 Active energy rays in the ultraviolet to visible light region (about 100 to about 800 nm) obtained from the above are used. The amount of active energy ray irradiation varies depending on the type of each component in the composition, the blending amount, and the film thickness of the coating film. For example, when using an ultrahigh pressure mercury lamp, it is 100 to 5000 miZcm2.

(D) Heat (PEB: Post Exposure Bake): The post-development contrast is improved by heating the resist film exposed in the above process. If this step is omitted, a pattern with good contrast that does not have a sufficient curing reaction of epoxy resin cannot be obtained. This heat treatment step is performed at a temperature within a range where the unexposed portion of the resist does not cause a thermal reaction and becomes insoluble in the developer. And need to be done in time. A preferred temperature is 70 to 170 ° C, more preferably 80 to 150 ° C, and a preferred time is 0.5 minutes to 5 hours. If the temperature is too low or the time is too short, the contrast will be insufficient, and if the temperature is too high or if the time is too long, problems such as insolubilization of unexposed areas in the developer will occur.

 (E) Development: A pattern layer is obtained by developing the resist film that has been heat-treated in the above-described step and dissolving and removing the resist material in the unexposed areas. The developer is not particularly limited as long as it is a solvent that dissolves and removes the negative resist in the unexposed areas. For example, propylene glycol monoalkyl ether such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Lactic acid alkyl esters such as acetates, methyl lactate and ethyl lactate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, ethylene glycol monomethino ethenole, ethylene glycol monoethanol Ethylene glycol monoalkyl ethers such as ethynole etherenole, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl etherenoate acetate, etc. Glyconomonomonoalkyl ether acetates, 2-heptanone, γ-butyrolatatane, alkyl alkoxypropionates such as methyl methoxypropionate, ethyl ethoxypropionate, pyruvate alkyl esters such as methyl pyruvate, ethyl pyruvate, Examples thereof include ketones such as methyl ethyl ketone, cyclopentanone and cyclohexanone, Ν-methylpyrrolidone, Ν, ジ メ チ ル -dimethylacetamide, dimethyl sulfoxide, propylene carbonate and diacetone alcohol.

[0110] Examples of alkaline aqueous solution developers include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, η-propylamine, jetylamine, —Η—propylamine, triethylamine, methyljetylamine, dimethylethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5. 4.0 ] -7-Undecene, 1,5-Diazabicyclo [4. 3. 0] —5-Nonane and other alkaline aqueous solutions can be used. In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the alkaline aqueous solution. It is also possible to use a caloric aqueous solution as a developer. Of these developers, γ-petit-mouth rataton, propylene glycol monomethyl ether acetate, and the like are particularly preferable.

 [0111] As the development method, any of a spray method, a paddle method, an immersion method, and the like may be used, but the immersion method is preferable because there is little pattern destruction such as peeling of the pattern. Moreover, an ultrasonic wave etc. can also be irradiated as needed.

 [0112] Although a rinsing step is preferably performed after development as necessary, the rinsing step, the rinsing liquid, and the rinsing method can be performed with known liquids and methods without particular limitations.

 [0113] Furthermore, after the development or rinsing step, the resist pattern can be heated under known conditions to further advance the curing and thereby stabilize the pattern.

 [0114] When a pattern is formed by the above-described pattern forming method, the resist composition can be applied by a simple method such as spin coating with high film thickness accuracy and high film thickness controllability, and exposure is performed according to the desired pattern accuracy. A light source can be selected, batch exposure using a photomask or the like is possible, and a resist pattern having a high exposure accuracy with a short exposure time, high productivity, high turnability, and a high aspect ratio can be obtained.

 [0115] Since the resist pattern obtained from the resist composition of the present invention can be a thick permanent film, it can also be used as a component such as an electronic component, an optical component, or a biochip. Of course, there are various uses because the pattern can be a non-thick film.

 That is, the resist pattern obtained by the pattern forming method can be used as a component such as MEMS. The resist pattern can be used for an original application of a resist that forms another pattern via the resist pattern. For example, when the application of the active energy ray negative resist composition of the present invention is applied to a copper-clad laminate for a printed wiring board, a wiring pattern can be formed. In this case, after forming the resist pattern on the substrate, the ability to etch the copper foil by contacting with a chemical solution such as acid. The resist pattern formed according to the present invention is very stable against the chemical solution, so it has good resistance as an etching mask. Therefore, a wiring pattern can be formed.

[0117] Furthermore, the resist pattern obtained by the pattern forming method can be used as a solder mask. In this case, the application of the active energy ray negative resist composition to the printed wiring board having a circuit pattern formed by etching the copper foil of the copper-clad laminate. After applying a cloth and forming a resist pattern, an electronic component is connected to the obtained wiring board by soldering using a jet soldering method or a reflow soldering method. Is formed. Since the resist pattern formed according to the present invention is thermally stable and exhibits good resistance as a solder mask, an electronic circuit unit can be formed.

 [0118] It is also possible to provide another material at least in the concave portion of the pattern layer formed by the above method to form the second pattern layer. When a metal is used as the other material, for example, if it is provided by a plating process, a composite structure of a resist pattern layer and a metal pattern layer can be obtained. The method of the plating process is not particularly limited, but the electrolytic plating method is preferable. As a method of performing metal plating such as copper, nickel, silver, gold, solder, copper Z-nickel multilayer, or a composite system of these, known methods can be used. For example, “Surface Treatment Technology Overview” (Technical Data Center Co., Ltd., 1987Z12Z21 first edition, pages 281 to 422). In the case of using the electrolytic plating method, it is preferable that the surface of the supporting substrate on which the active energy ray negative resist composition is applied is conductive because the electrolytic plating process can be easily performed.

 [0119] In addition, a resin can be used as a material for forming the second pattern layer. In this case, for example, a light or thermosetting resin is provided by a casting method or a coating method, and then light or heat is used. When the second pattern layer is formed by curing the resin, the composite structure of the resist pattern layer and the resin pattern layer can be obtained. The light or thermosetting resin is not particularly limited, but for example, the use of light or thermosetting PDMS (polydimethylsiloxane) is particularly preferable because it is easily cured by light or heat.

[0120] The composition of the present invention can also be used for forming a resist film (photosensitive layer) of a dry film resist. A dry film resist is obtained by forming a resist film (photosensitive layer) on a support such as a polymer film as a base material. The film thickness of the resist film formed using the composition of the present invention is not particularly limited and is usually several; zm to several mm. Even a thick film of 50 μm or more can be processed accurately in the subsequent steps. can do. A particularly preferred film thickness is 50 / ζ πι to 2πιπι. Examples of the polymer film used for the support include, for example, polyethylene terephthalate, polyester resin such as aliphatic polyester, Examples thereof include films made of polyolefin resin such as pyrene and low density polyethylene, and among these, films made of polyester and low density polyethylene are preferred. Further, since these polymer films need to be removed from the resist film (photosensitive layer) later, it is preferable that these polymer films can be easily removed from the resist film (photosensitive layer). The thickness of these polymer films is usually 5 to: LOO μm, preferably 10 to 30 μm.

 [0121] The dry film resist can be produced by a resist film (photosensitive layer) forming step in which the composition is applied onto a support and dried. Also, by providing a cover film on the formed resist film (photosensitive layer), a support, a photosensitive layer, and a cover film are sequentially laminated, and a dry film resist having films on both sides of the resist film (photosensitive layer). Can also be manufactured. Force Bar film is peeled off when using dry film resist. By using a cover film on the resist film (photosensitive layer) before use, the resist film (photosensitive layer) can be protected and has excellent pot life. It becomes a dry film resist. The cover film may be the same as the polymer film used for the support described above, and the cover film and the support may be the same material or different materials, and the thickness may also be different. Even if they are the same, they can be different! / ヽ.

 [0122] In order to form a resist film on a substrate using a dry film resist, first, a bonding step of bonding the resist film (photosensitive layer) of the dry film resist and the substrate is performed. Here, when using a dry film resist provided with a cover film, the cover film is peeled off to expose the resist film (photosensitive layer), and then brought into contact with the substrate. Then, the resist film (photosensitive layer) and the substrate are thermocompression bonded at about 40 to 120 ° C. using a pressure roller or the like, and the resist film (photosensitive layer) is laminated on the substrate. Then, an exposure process in which the resist film (photosensitive layer) is exposed through a negative mask on which a desired exposure pattern is formed, a process in which the support is peeled off from the resist film (photosensitive layer), and an unexposed portion is removed with a developer. Then, a cured resist film can be produced on the surface of the substrate by performing a developing process for developing and a thermosetting process for thermally curing the resist film (photosensitive layer). The actinic light used for exposure, the developer, and the thermosetting process conditions of the resist film can be used in the same manner as described above.

 Example

[0123] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is limited to the examples. It is not intended to be done.

 [0124] (Production Example 1) Production of potassium tris (pentafluoroethyl) trifluorophosphate

 According to US Pat. No. 6,264,818, tris (pentafluoroethyl) difluorophosphorane (gas chromatographic purity 97%, yield 72%) was synthesized by electrofluorination of triethylphosphine.

Next, potassium fluoride 18. Og and 600 ml of dimethoxyethane were vigorously stirred and suspended in a 1 L reaction vessel, and the resulting tris (pentafluoroethyl) was maintained while maintaining the liquid temperature at 20-30 ° C. ) Difluorophosphorane 119. Og was added dropwise. After stirring at room temperature for 24 hours, the reaction solution was filtered, and dimethoxyethane was distilled off under reduced pressure to obtain 136. Og of white powder. It was confirmed by ¹⁹ F and ³¹ P-NMR that this was tris (pentafluoroethyl) trifluorophosphate.

[Production Example 2] Production of potassium tris (heptafluoropropyl) trifluorophosphate

 Tris-heptafluoropropyl difluorophosphorane (gas chromatographic purity 89%, yield 52%) was synthesized by electrolytic fluorination of tris-n-propylphosphine according to US Pat. No. 6,264,818.

Next, 18 ml of potassium fluoride and 600 ml of dimethoxyethane were placed in a 1 L reaction vessel and suspended by stirring. The resulting tris (heptafluoropropyl) was maintained while maintaining the liquid temperature at 20-30 ° C. Difluorophosphorane 161. Og was added dropwise. After stirring for 24 hours, the reaction solution was filtered, and dimethoxyethane was distilled off under reduced pressure to obtain white powder 177. Og. It was confirmed by ¹⁹ F and ³¹ P—NMR that this was potassium tris (heptafluoropropyl) trifluorophosphate.

 [0126] (Production Example 3) 4-—Production of (phenylthio) phenylsulfo-sulfumutris (pentafluoroethyl) trifluorophosphate

A reaction vessel was charged with 24.24 g of diphenylsulfoxide, 18.6 g of diphenylsulfide, and 86. Og of methanesulfonic acid, mixed uniformly, and then 15.8 g of acetic anhydride was added dropwise. After reacting at 40-50 ° C for 5 hours, it was cooled to room temperature. The reaction solution was added dropwise to entering a port was containers 20 mass _^0/0 aqueous solution 249g of tri scan potassium (penta Full O Roe chill) Torifuruororin acid created in the Production Example 1, and stirred well for 1 hour at room temperature. The yellowish slightly viscous oil Extraction was performed with 240 g of ethyl acetate, the aqueous layer was separated, and the organic layer was washed 3 times with 200 g of water. The solvent was distilled off from the organic layer, and 80 g of toluene was added to the resulting yellow residue to dissolve it. In order to remove impurities such as unreacted raw materials and by-products, 600 g of hexane was added to this toluene solution, and the mixture was allowed to stand after stirring well at 10 ° C for 1 hour. Since the solution was separated into two layers, the upper layer was removed by liquid separation. When 300 g of hexane was mixed well at room temperature with the remaining lower layer, pale yellow crystals were precipitated. This was filtered off and dried under reduced pressure to give 49-Og of 4- (phenylthio) phenyl disulfosulfo-mutris (pentafluoroethyl) trifluorophosphate. The compound was identified by ¹ H, ¹³ C, ¹⁹ F and ³¹ P-NMR.

 The obtained 4- (phenylthio) phenyl disulfol sulfomutris (pentafluoroethyl) trifluorophosphate 49. Og was dissolved in propylene carbonate 49. Og to prepare a 50 mass% propylene carbonate solution.

 (Production Example 4) Production of 4 (phenylthio) phenol disulfol-sulfumtris (heptafluoropropyl) trifluorophosphate

Tris (penta Full O Roe chill) 20 Weight _^0/0 aqueous solution of tris (hepta full O b propyl) potassium Torifuruororin acid except that 20 mass _^0/0 aqueous solution 326g of potassium Torifuruororin acid in the same manner as in Preparation Example 3 Thus, 53.8 g of 4- (phenylthio) phenol disulfol sulfomutris (heptafluoropropyl) trifluorophosphate was obtained. The compound was identified by ¹ H, ¹³ C, ¹⁹ F and ³¹ P-NMR.

The resulting 4 (Hue - thio) Hue - Rujifue - Rusuruho - Umutorisu was dissolved (Heputafuruoropu opening pill) triflate Ruo b phosphate 53. 8 g of propylene carbonate 53. 8 g, was created 5 0 mass _^0/0 propylene carbonate solution .

[0128] (Resist composition adjustment)

 Each component was mixed in the ratio shown in Table 1 to prepare a uniform active energy-sensitive linear resist composition.

[0129] [Table 1] Examples Examples Comparative Examples Comparative Examples Comparative Examples

 1 2 1 2 3 Powerful polymerizable compound CR- 1 1 00 1 00 1 00 1 00 1 00

 S- 1 1 0----

S-2-1 0---Active energy linearity

 P- 1--1 0--Cationic polymerization initiator P-2---1 0-

P-3----1 0 Solvent G BL 40 40 40 40 40

 [0130] * Ji! ^ -1: Bisphenol A Novolak type polyfunctional epoxy resin [Product name: EPON

 SU-8, manufactured by Shell Chemical Co., Ltd.]

 S—1: 4 (phenolthio) phenol disulfosulfumtris (pentafluoroethyl) trifluorophosphate in 50% propylene carbonate solution [cationic polymerization initiator obtained in Production Example 3]

 S—2: 50% propylene carbonate solution of 4 (phenylthio) phenol disulfol-sulfumtris (heptafluoropropyl) trifluorophosphate [force thione polymerization initiator obtained in Production Example 4]

 P— 1: 4 (Ferlethio) Fuel disulfosulfo-hexafluoroantimonate 50% propylene carbonate solution [Product name: CPI—101A, manufactured by SanPro]

 P—2: 50% of a mixture of 4 (phenylthio) phenylsulfo-hexafluoroantimonate and Thioji P-phenylenebis (diphenylsulfo-um) bis (hexafluoroantimonate) Propylene carbonate solution [trade name: UVR-6974, manufactured by Dow Chemical Company]

 P—3: 4— (Ferulthio) Fuel disulfosulfo-hexafluorophosphite 50% propylene carbonate solution [Product name: CPI—100P, manufactured by Sanpa Pro ]

 GBL: y Butyro Rataton

[0131] Each of the above resist compositions was subjected to the performance test of the following items.

[0132] <Dryability test>

The resist compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were applied on a silicon substrate under conditions such that the film thickness was 100 m using a spin coater. Dried on a 90 ° C and 150 ° C hot plate. Weigh the silicon substrate during drying at regular intervals, measure the time until the weight loss is eliminated, and judge according to the following evaluation criteria.

 ◎: Less than 30 minutes before the weight loss disappears.

 〇: Within 60 minutes until weight loss disappears.

 Δ: Less than 120 minutes before weight loss disappears.

 X: More than 120 minutes before the weight loss disappears.

 The shorter the time until weight loss disappears, the higher the productivity and the better the drying property.

[0133] <Resist pattern formation evaluation test>

 1. Application test

 The active energy ray negative resist compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were applied on a silicon substrate by a spin coater, then dried on a hot plate at 90 ° C. for 110 minutes, and 100 m thick. A resist film was obtained. A resist film was obtained in the same manner by changing the drying temperature to 150 ° C and the drying time to 30 minutes. The coatability of the obtained resist film was visually observed and judged according to the following evaluation criteria.

 ◯: The obtained coating film is uniform and uniform.

 X: The obtained coating film has unevenness such as pinholes and repellency.

[0134] 2. Sensitivity test

 The resist films of Examples 1 and 2 and Comparative Examples 1 to 3 obtained in the above coating property test were irradiated through a mask using a high-pressure mercury lamp as a light source (exposure amount: 1000 miZcm2). Thereafter, heat treatment was performed on a hot plate at 100 ° C. for 10 minutes, followed by development by immersing in propylene glycol monomethyl ether acetate for 30 minutes to obtain a resist pattern. The obtained resist pattern was observed with an optical microscope and judged according to the following evaluation criteria.

○: No pattern meandering or surface wrinkles due to swelling.

 Δ: Wrinkles are observed at the top of the pattern due to swelling, but no pattern meandering is observed.

 X: Pattern meandering is observed.

[0135] 3. Resolution test Further, the resolution of the resist pattern was observed with an optical microscope and judged according to the following evaluation criteria.

 A: A pattern with a mask line width of 10 μm is resolved (aspect ratio 10).

 ◯: Resolve a pattern with a mask line width of 20 μm (aspect ratio 5).

 X: Do not resolve.

[0136] 4. Film strength test

 After forming a resist film by the same method as the above pattern formation evaluation test, the coating film was exposed with a high-pressure mercury lamp without using a mask, and then heat-treated on a 100 ° C hot plate for 10 minutes to form a cured coating film. Obtained. The surface of the coating film after rubbed the cured coating film 20 times with absorbent cotton soaked with methyl ethyl ketone was observed and judged according to the following evaluation criteria.

 ◯: The surface is glossy with scratches.

 Δ: The surface is cloudy and gloss is lost.

 X: The coating film is scratched and peeled off.

 As there is no surface change after rubbing, the mechanical strength of the cured coating becomes stronger and the performance as a permanent film is superior.

[0137] <Storage stability test method>

 Immediately after adjusting the resist compositions obtained in Examples 1-2 and Comparative Examples 1-3 and at 80 ° C for 1 month, the viscosity after storage was measured at 25 ° C, and the storage stability was evaluated according to the degree of thickening. Judged by criteria.

 ○: Viscosity change from initial viscosity is less than 2 times

 X: Viscosity change from initial viscosity is 2 times or more

 The smaller the rate of increase in viscosity! /, The better the storage stability of the composition.

 [0138] Table 2 shows the results of the above tests.

[0139] [Table 2] Resist pattern formability

 Prebake Dry search Toxic element Resolution Coating film strength Storage stability

 Temperature (° c) Properties Applicability Sensitivity Degree

 Example 90 △ 〇 〇 ◎ ◎

 1 O None

 1 50 ◎ 〇 〇 ◎ ◎

 Example 90 Δ ○ o ◎ ◎

 150 ◎ ◎ ○ None

2 o o ◎

 Comparative example 90 △ o o ◎ ◎ X hole (S b) 1 1 50 ◎ ○ ○ ○ ◎

 Comparative example 90 △ 〇 o ◎ ◎ X

 Yes (S b) 2 1 50 ◎ o o X ◎ (gelation) Comparative example 90 Δ o X X X

 〇 None 3 1 50 ◎ 〇 X X X

[0140] As can be seen from Table 2, the resist composition of the present invention has a good resist pattern forming property even when the pre-beta temperature is high (150 ° C), and does not contain antimony. The mechanical strength of the membrane is high. Furthermore, as a result of the high thermal stability of the resist composition, it is excellent in storage stability.

 Industrial applicability

[0141] The present invention has good thermal stability, can increase the pre-beta temperature, improve the productivity of the resist film, and can improve the resolution of the pattern when developed, and a sensitive energy. Useful as a line negative photoresist composition. The present invention is also suitable for creating a permanent pattern because the strength of the cured product is high, and a pattern with a higher aspect ratio can be created by increasing the film thickness than in the past. It is also useful for producing optical parts, biochip parts and the like. In addition, since it does not contain toxic metals such as arsenic antimony, it has the advantage of being safe to handle and the environment.

Claims

The present invention relates to an active energy ray negative photoresist composition comprising an active energy ray cationic polymerization initiator (1), a cationic polymerizable compound (2) and a solvent (3), The active energy ray cationic polymerization initiator (1) has the following formula (4), [Chemical 1]

 [In the formula (4), A represents an element of valence m of group VIA or VIIA (CAS notation), m is 1 or 2, n is an integer of 0 to 3, and R is Represents a bonded organic group, and a plurality of R may be the same or different from each other! /, And D may have the following formula (5), [Chemical 2]

 [In the formula (5), E represents a divalent group, G represents —O—, —S—, —SO—, —SO—, —NH—  2  , —NR, —, —CO—, —COO—, —CONH, an alkylene group having 1 to 3 carbon atoms or a fullerene group, and a is an integer of 0 to 5. Is a structure represented by  X— is the following formula (6), [Chemical 3] [(Rf) bPF6 b] (6) [In the formula (6), Rf represents an alkyl group having 1 to 8 carbon atoms in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and b is an integer of 1 to 5. ] Represents a fluorinated alkylfluorophosphate cation represented by the formula: An active energy ray negative photoresist composition, which is an fluorinated alkyl fluorophosphate represented by the formula: 2. The active energy ray negative photoresist composition according to claim 1, wherein A in formula (4) is S. [3] The active energy ray negative photoresist composition according to claim 1 or 2, wherein R in the formula (4) has a substituent! /, May! /, And a phenol group. [4] The active energy ray negative photoresist composition according to claim 3, wherein the substituent of R is a phenolthio group. [5] D in Eq. (4) is the following group:  [Chemical 4]

 The active energy-sensitive negative photoresist composition according to any one of claims 1 to 4, wherein the composition is at least one selected group. [6] Rf in the formula (6) represents a perfluoroalkyl group having 1 to 4 carbon atoms, and b is 2 or 3. Negative photoresist composition.  [7] The cationically polymerizable compound (2) is characterized in that it is a bisphenol A novolak resin or a bisphenol F novolac resin having at least two epoxy groups in one molecule. The negative-type photoresist composition of any one of Claims 1 to 6 which is a sensitive energy ray. [8] Solvent (3) The solvent (3) is at least one selected from the group consisting of methyl ethyl ketone, cyclopentanone, cyclohexanone, gamma butyrolatathone and propylene glycol monomethyl ether acetate. To any of 7 Lugi single-line negative photoresist composition. [9] A dry film resist obtained by applying any one of the active energy ray negative photoresist compositions of claims 1 and 8 onto a film-like support and drying.  [10] The active energy ray negative photoresist composition of any one of claims 1 and 8, wherein the dry active material is a negative sensitive photoresist composition or a dry film resist dried dry resist composition according to claim 9. A cured product obtained by curing.