Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0387—Polyamides or polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

• the present invention uses a positive type high heat resistant photosensitive resin composition used as a surface protective film for semiconductor devices, an interlayer insulating film, an interlayer insulating film for display devices, and the positive type high heat resistant photosensitive resin composition.
• the present invention relates to a method for producing a cured relief pattern having heat resistance and a semiconductor device containing the relief pattern.
• a negative polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like is used for a surface protective film and an interlayer insulating film of a semiconductor device.
• This negative polyimide resin is generally provided in the form of a photosensitive polyimide precursor composition, and is applied on a semiconductor device by coating, patterning with actinic rays, organic solvent development, thermal imidization treatment at high temperature, and the like.
• a surface protective film, an interlayer insulating film, and the like can be easily formed, and the process can be greatly shortened as compared with a conventional non-photosensitive polyimide precursor composition.
• the photosensitive negative polyimide precursor composition needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the development process. Measures to remove organic solvents have been demanded. In response, recently, various heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution have been proposed in the same manner as photoresists.
• an organic solvent such as N-methyl-2-pyrrolidone
• a composition in which an alkaline aqueous solution-soluble polyamic acid (polyimide precursor) or hydroxypolyamide (polybenzoxazole) precursor is mixed with a photoactive component such as a photosensitive diazoquinone compound is used as a positive photosensitive resin composition.
• the method has attracted attention in recent years.
• the development mechanism of this positive photosensitive resin is that the photosensitive diazoquinone compound in the unexposed area is insoluble in the alkaline aqueous solution, but when exposed, the photosensitive diazoquinone compound undergoes a chemical change to become an indenecarboxylic acid compound. It makes use of being soluble in an alkaline aqueous solution.
• wafer warpage the problem of warpage of silicon wafers formed with a polyimide film (hereinafter also simply referred to as “wafer warpage”) has become apparent. This is thought to be due to the residual stress generated from the difference in thermal expansion coefficient between the polyimide and silicon wafer. Therefore, a low thermal expansion and low stress (low stress) polyimide is strongly demanded compared to conventional polyimide ( For example, refer nonpatent literature 1).
• Patent Document 6 is a positive photosensitive composition containing a compound that generates an acid upon irradiation and a PBO precursor, and the residual stress of the polybenzoxazole film formed by the PBO precursor is 25 MPa or less.
• a positive photosensitive composition containing a certain PBO precursor is disclosed, there are various problems in lithography performance such as sensitivity and profile.
• Japanese Unexamined Patent Publication No. 56-27140 Japanese Laid-Open Patent Publication No. 2002-526793 Japanese Unexamined Patent Publication No. 2009-244479 Japanese Unexamined Patent Publication No. 2009-192760 Japanese Laid-Open Patent Publication No. 2006-010881 Japanese Laid-Open Patent Publication No. 2001-214055
• the present invention has lithography performance with excellent resolution and sensitivity, and cures at a low temperature of 300 ° C. or lower (preferably 250 ° C. or lower), that is, curing at a low temperature to prevent wafer warpage due to low stress.
• a photosensitive resin composition capable of forming a relief pattern, a relief pattern forming material, a photosensitive film, a polyimide film, a cured relief pattern, a production method thereof, and the cured relief pattern using the photosensitive resin composition
• An object is to provide a semiconductor device.
• a photosensitive resin composition comprising a resin having a repeating unit represented by the following general formula (1), and (b) a compound that generates an acid upon irradiation with actinic rays or radiation.
• R 1 represents a tetravalent organic group.
• R ⁇ 1 > may mutually be same or different.
• R 2 represents a divalent organic group.
• a plurality of R 2 may being the same or different.
• at least one of the plurality of R 2 is a divalent organic group having an alicyclic group.
• R 3 each independently represents a hydrogen atom or an organic group.
• at least one of the plurality of —CO 2 R 3 is a group that decomposes by the action of an acid to generate an alkali-soluble group.
• R 1 ' has the same meaning as R 1 in the general formula (1).
• R 3 ' has the same meaning as R 3 in Formula (1).
• at least one of the plurality of —CO 2 R 3 ′ is a group that decomposes by the action of an acid to generate an alkali-soluble group.
• R 4 is a divalent organic group having an alicyclic group.
• R 1 "has the same meaning as R 1 in the general formula (1).
• R 3 has the same meaning as R 3 in Formula (1).
• at least one of the plurality of —CO 2 R 3 ′′ is a group that decomposes by the action of an acid to generate an alkali-soluble group.
• R 5 is a divalent organic group different from R 4 .
• R 5 in the general formula (3) is a divalent group represented by any of the following formulas.
• At least one hydrogen atom of each aromatic ring is independently selected from the group consisting of fluorine atom, chlorine atom, bromine atom, methyl group, methoxy group, cyano group, phenyl group and trifluoromethyl group. It may be substituted by a species atom or group.
• the thermal decomposition temperature of —CO 2 R 3 in the general formula (1), —CO 2 R 3 ′ in the general formula (2) or —CO 2 R 3 ′′ in the general formula (3) is 100 to 220 ° C.
• the photosensitive resin composition according to any one of [1] to [4].
• Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
• Rb represents a single bond or a divalent linking group.
• Q represents an alkyl group, an alicyclic group which may contain a hetero atom, or an aromatic ring group which may contain a hetero atom. At least two of Ra, Rb and Q may be bonded to each other to form a ring.
• Rc, Rd, Re, Rf and Rg each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
• Rc and Rd may be bonded to each other to form a ring, or at least two of Re, Rf and Rg may be bonded to each other to form a ring.
• At least one of Rc and Rd is a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom. 7].
• the photosensitive resin composition as described in 7].
• [19] [1] A photosensitive film formed of the photosensitive resin composition according to any one of [16]. [20] [1] A polyimide film obtained by heat-treating the photosensitive resin composition according to any one of [16]. [21] (A) forming a photosensitive film according to [19] on a substrate; (A) a step of exposing the photosensitive film with actinic rays or radiation; (C) A process for developing the photosensitive film so as to remove the exposed portion with an aqueous alkaline developer, and (d) a method for producing a cured relief pattern comprising a step of heat-treating the obtained relief pattern. [22] A cured relief pattern obtained by the production method according to [21]. [23] [22] A semiconductor device comprising the cured relief pattern according to [22]. [24] Resin which has a repeating unit represented by following General formula (1).
• R 1 represents a tetravalent organic group.
• R ⁇ 1 > may mutually be same or different.
• R 2 represents a divalent organic group.
• a plurality of R 2 may being the same or different.
• at least one of the plurality of R 2 is a divalent organic group having an alicyclic group.
• R 3 each independently represents a hydrogen atom or an organic group.
• at least one of the plurality of —CO 2 R 3 is a group that decomposes by the action of an acid to generate an alkali-soluble group.
• the photosensitive resin composition of the present invention has lithography performance with excellent resolution and sensitivity, and can form a cured relief pattern that prevents wafer warpage due to low stress in so-called low-temperature curing.
• a relief pattern forming material having lithography performance with excellent resolution and sensitivity, excellent low stress characteristics in so-called low temperature cure, and capable of forming a cured relief pattern that prevents wafer warpage,
• a photosensitive film, a polyimide film, a cured relief pattern, a manufacturing method thereof, and a semiconductor device including the cured relief pattern can be provided.
• the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent.
• the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
• exposure in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, etc., unless otherwise specified.
• the exposure with the particle beam is also included in the exposure.
• the photosensitive resin composition of the present invention contains (a) a resin having a repeating unit represented by the following general formula (1), and (b) a compound that generates an acid upon irradiation with actinic rays or radiation.
• R 1 represents a tetravalent organic group.
• R ⁇ 1 > may mutually be same or different.
• R 2 represents a divalent organic group.
• a plurality of R 2 may being the same or different.
• at least one of the plurality of R 2 is a divalent organic group having an alicyclic group.
• R 3 each independently represents a hydrogen atom or an organic group.
• at least one of the plurality of —CO 2 R 3 is a group that decomposes by the action of an acid to generate an alkali-soluble group.
• the photosensitive resin composition of the present invention containing the resin (a) having a repeating unit represented by the general formula (1) has lithography performance with excellent resolution and sensitivity. In so-called low temperature curing, The reason why it is possible to form a cured relief pattern that prevents wafer warpage due to low stress is not clear, but is estimated as follows.
• the repeating unit represented by the general formula (1) can form a linear and rigid polyimide by thermosetting, and at least one of a plurality of R 2 present in the resin (a) is a fat. Linearity and rigidity can be improved by using a divalent organic group having a cyclic group. Thereby, it is presumed that the thermal expansibility can be particularly lowered, low stress can be achieved, and wafer warpage can be prevented.
• R 2 present in the resin (a) is a divalent organic group having an alicyclic group, the light transmission property such as i-line at the time of exposure is not impaired and the resolution is improved. It is estimated that the lithography performance with excellent sensitivity is achieved.
• the resin (a) having a repeating unit represented by the general formula (1) is a resin whose solubility in an alkaline developer is increased by the action of an acid.
• the resin having the repeating unit of the general formula (1) is preferably insoluble or hardly soluble in an alkali developer.
• the repeating unit represented by the general formula (1) includes a compound having four carboxyl groups with R 1 as a nucleus, a carboxylic acid anhydride thereof, or a hydrogen atom in at least one of the four carboxyl groups. It is composed of an acid component derived from a compound substituted with a group capable of leaving by the action of an acid and a diamine component derived from a compound having two amino groups with R 2 as a nucleus.
• the tetravalent organic group R 1 preferably has 4 to 30 carbon atoms, and more preferably a tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group. .
• a plurality of R 1 present in the resin (a) may be the same or different.
• Examples of the monocyclic aromatic group in the tetravalent organic group R 1 include a benzene ring group and a pyridine ring group.
• Examples of the condensed polycyclic aromatic group in the tetravalent organic group R 1 include a naphthalene ring group and a perylene ring group.
• Examples of the monocyclic aliphatic group in the tetravalent organic group R 1 include a cyclobutane ring group, a cyclopentane ring group, and a cyclohexane ring group.
• Examples of the condensed polycyclic aliphatic group in the tetravalent organic group R 1 include a bicyclo [2.2.1] heptane ring group, a bicyclo [2.2.2] octane ring group, and a bicyclo [2.2. 2] Oct-7-ene ring group and the like.
• the tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group for the tetravalent organic group R 1 the above-mentioned monocyclic or condensed polycyclic aliphatic group or The aromatic group itself may be used, but a plurality of monocyclic or condensed polycyclic aliphatic groups or aromatic groups are linked via a single bond or a divalent linking group, and 4 as R 1 A valent linking group may be formed.
• the divalent linking group is preferably an alkylene group (an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group), an oxygen atom, a sulfur atom, a divalent sulfone group, or an ester bond. , Ketone group, amide group and the like.
• the acid component having a group derived from at least four carboxyl groups with R 1 as a nucleus include pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2, 3,3 ′, 4′-biphenyltetracarboxylic anhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 2 , 2 ′, 3,3′-benzophenonetetracarboxylic anhydride, 4,4′- (Hexafluoroisopropylidene) diphthalic anhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5,6- Pyridinetetracarboxylic anhydride, 3,4,9,
• a component derived from pyromellitic acid anhydride a component derived from 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid anhydride
• the content of the acid component derived from the compound having four carboxyl groups with R 1 as a nucleus in the resin (a) is 20 to 70 mol% with respect to all repeating units constituting the resin (a). It is preferably 30 to 60% by mole.
• Examples of the divalent organic group R 2 include a divalent group having an alicyclic group, a divalent group having an aromatic group, and a divalent group containing a silicon atom.
• a plurality of R 2 present in the resin (a) may be the same or different.
• R 2 is a divalent group having an alicyclic group
• the diamine component having R 2 as a nucleus is sometimes referred to as an alicyclic diamine component
• R 2 is a divalent group having an aromatic group.
• the diamine component of R 2 to the core of, sometimes called the aromatic diamine component the diamine component of the R 2 at the core when the divalent group R 2 contains a silicon atom, that silicon diamine There is also.
• At least one of R 2 in the diamine component present in the resin (a) is a divalent group having an alicyclic group.
• the alicyclic group that R 2 may have is preferably a divalent alicyclic group having 3 to 20 carbon atoms, such as a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or bicyclo [2.2.
• Polycyclic cycloalkylene groups such as a heptylene group, norbornylene group, tetracyclodecanylene group, tetracyclododecanylene group, adamantylene group, and the like can be given.
• the divalent group having an alicyclic group for R 2 may be the alicyclic group itself, but a plurality of alicyclic groups are preferably an alkylene group (an alkylene group having 1 to 6 carbon atoms, for example, Methylene group, ethylene group, propylene group, etc.) may be linked to form a divalent group having an alicyclic group as R 2 , and the amino group and alicyclic group in the diamine component are alkylene groups.
• the alicyclic group and alkylene group that can form a divalent group having an alicyclic group may have a substituent, and an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) as such a substituent. ), Halogen atoms and the like.
• Particularly preferred diamine components having an alicyclic structure having R 2 as a nucleus include a 5-amino-1,3,3-trimethylcyclohexanemethylamine component, a cis-1,4-cyclohexanediamine component, and trans-1,4- Cyclohexanediamine component, 1,4-cyclohexanediamine component (cis, trans mixture), 4,4′-methylenebis (cyclohexylamine) component and its 3,3′-dimethyl-substituted product, bis (aminomethyl) bicyclo [2.2 .1] heptane component, 1,3-diaminoadamantane component, 3,3′-diamino-1,1′-biadamantyl component, 4,4′-hexafluoroisopropylidenebis (cyclohexylamine) component, Of which 3,3′-diamino-1,1′-biadamantyl component, trans-1,4-cyclo From the viewpoint of he
• the content of the alicyclic diamine component having two amino groups with R 2 as a nucleus in the resin (a) is 20 to 70 mol% with respect to all repeating units constituting the resin (a). Preferably, it is 30 to 60 mol%.
• the aromatic group in the divalent group having an aromatic group for R 2 is preferably an aromatic group having 5 to 16 carbon atoms, and examples thereof include a phenylene group and a naphthylene group. Further, the aromatic group may contain a hetero atom such as a nitrogen atom or an oxygen atom, and examples thereof include a divalent benzoxazole group.
• the divalent group having an aromatic group for R 2 may be the aromatic group itself, but a plurality of aromatic groups are linked via a single bond or a divalent linking group, and R 2
• the divalent group which has an aromatic group as may be formed, and the amino group in the diamine component and the aromatic group may be linked via a divalent linking group.
• the divalent linking group is preferably an alkylene group (an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group), an oxygen atom, a sulfur atom, a divalent sulfone group, or an ester bond. , Ketone group, amide group and the like.
• the aromatic group and alkylene group that can form a divalent group having an aromatic group may have a substituent, and as such a substituent, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) may be used.
• an alkoxy group such as a halogen atom and a methoxy group
• an aryl group such as a cyano group and a phenyl group.
• Specific examples of the aromatic diamine component having R 2 as a core include, for example, an m-phenylenediamine component, a p-phenylenediamine component, a 2,4-tolylenediamine component, a 3,3′-diaminodiphenyl ether component, 3, 4'-diaminodiphenyl ether component, 4,4'-diaminodiphenyl ether component, 3,3'-diaminodiphenyl sulfone component, 4,4'-diaminodiphenyl sulfone component, 3,4'-diaminodiphenyl sulfone component, 3,3 ' -Diaminodiphenylmethane component, 4,4'-diaminodiphenylmethane component,
• aromatic diamine components include p-phenylenediamine component, 4,4′-diaminodiphenyl ether component, 3,3′-diaminodiphenylsulfone component, 4,4′-diaminodiphenylsulfone component, and 2,2′-bis.
• (4-aminophenyl) hexafluoropropane component 1,4-bis (4-aminophenoxy) benzene component, imino-di-p-phenylenediamine component, 4,4'-diaminobiphenyl component, 4,4'-diamino Benzophenone component, 3,3′-dimethoxy-4,4′-diaminobiphenyl component, 3,3′-dimethyl-4,4′-diaminobiphenyl component, 2,2′-dimethyl 4,4′-diaminobiphenyl component, 2,2′-bis (trifluoromethyl) benzidine component, o-toluidine sulfone component, 2,2-bis (4-amino Nophenoxyphenyl) propane component, 9,9-bis (4-aminophenyl) fluorene component, 4,4′-di- (3-aminophenoxy) diphenylsulfone component, 4,4′-diaminobenz
• the diamine component may be substituted with a hydroxyl group.
• bisaminophenol components include 3,3′-dihydroxybenzidine component, 3,3′-diamino-4,4′-dihydroxybiphenyl component, and 4,4′-diamino-3,3′-dihydroxy.
• Biphenyl component 3,3′-diamino-4,4′-dihydroxydiphenylsulfone component, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone component, bis- (3-amino-4-hydroxyphenyl) methane Component, 2,2-bis- (3-amino-4-hydroxyphenyl) propane component, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane component, 2,2-bis- (4 -Amino-3-hydroxyphenyl) hexafluoropropane component, bis- (4-amino-3-hydroxyphenyl) methane component, 2 2-bis- (4-amino-3-hydroxyphenyl) propane component, 4,4′-diamino-3,3′-dihydroxybenzophenone component, 3,3′-diamino-4,4′-dihydroxybenzophenone component, 4 , 4'-diamino-3,3'
• R 2 in the general formula (1) is a divalent group having an aromatic group selected from the following.
• X 1 represents —O—, —S—, —C (CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO—.
• * Represents a bonding position with —NH— or —OH bonded to R 2 in the general formula (1).
• —NH— and —OH bonded to R 2 are bonded to each other in the ortho position (adjacent position).
• the content of the aromatic diamine component having two amino groups with R 2 as a nucleus in the resin (a) is 5 to 40 mol% with respect to all repeating units constituting the resin (a). Preferably, it is 10 to 30 mol%.
• the R 2 in order to enhance the adhesion to the substrate can be a silicon diamine component as the diamine component to the nucleus.
• examples include bis (4-aminophenyl) dimethylsilane component, bis (4-aminophenyl) tetramethylsiloxane component, bis (4-aminophenyl) tetramethyldisiloxane component, bis ( ⁇ -aminopropyl) tetramethyl.
• Examples thereof include a disiloxane component, a 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis ( ⁇ -aminopropyl) tetraphenyldisiloxane component.
• a disiloxane component a 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis ( ⁇ -aminopropyl) tetraphenyldisiloxane component.
• a disiloxane component examples thereof include a disiloxane component, a 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyld
• R 5 and R 6 represent a divalent organic group
• R 7 and R 8 represent a monovalent organic group.
• a plurality of R 7 may be the same as or different from each other.
• the plurality of R 8 may be the same as or different from each other.
• Examples of the divalent organic group represented by R 5 and R 6 include a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, a phenylene group having 6 to 20 carbon atoms, carbon This represents a divalent alicyclic group of 3 to 20 or a group constituted by combining these.
• the monovalent organic group represented by R 7 and R 8 represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. . More specifically, the following can be mentioned.
• the content of the silicon diamine component having at least two amino groups with R 2 as a nucleus in the resin (a) is 5 to 40 mol% with respect to all repeating units constituting the resin (a). Preferably, it is 10 to 30 mol%.
• the resin (a) having the repeating unit represented by the general formula (1) is thermoset to be polyimide, the viewpoint of improving linearity and rigidity and achieving low stress to prevent wafer warpage, From the viewpoint of enhancing the adhesiveness with the substrate, the viewpoint of enhancing the alkali solubility after exposure, and the like, it has a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3).
• a resin is preferred.
• R 1 ' has the same meaning as R 1 in the general formula (1).
• R 3 ' has the same meaning as R 3 in Formula (1).
• at least one of the plurality of —CO 2 R ′ 3 is a group that decomposes by the action of an acid to generate an alkali-soluble group.
• R 4 is a divalent organic group having an alicyclic group.
• R 1 "has the same meaning as R 1 in the general formula (1).
• R 3 has the same meaning as R 3 in Formula (1).
• at least one of the plurality of —CO 2 R 3 ′′ is a group that decomposes by the action of an acid to generate an alkali-soluble group.
• R 5 is a divalent organic group different from R 4 .
• divalent organic group having an alicyclic group for R 4 include those similar to the specific examples and preferred examples of the divalent group having an alicyclic group for R 2 .
• examples of the divalent organic group R 5 different from R 4 include the divalent group having an aromatic group and the divalent group containing a silicon atom described above for R 2 .
• R 5 in the general formula (3) is a fragrance from the viewpoint of improving linearity and rigidity, achieving low stress and preventing wafer warpage, and improving heat resistance when cured to polyimide.
• a divalent group having an aromatic group is preferred, and specific examples and preferred examples of the divalent group having an aromatic group for R 5 include a divalent group having an aromatic group for R 2 . Specific examples and preferred examples are the same.
• a divalent group represented by any of the following formulas is more preferable.
• At least one hydrogen atom of each aromatic ring is independently selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, a phenyl group, and a trifluoromethyl group. It may be substituted by a species atom or group.
• Examples of the organic group for R 3 , R 3 ′ or R 3 ′′ preferably have 1 to 20 carbon atoms.
• a group that decomposes by the action of an acid to generate an alkali-soluble group an alkyl group, A cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a silicon atom-containing group, —CORc (Rc is an alkyl group, an aryl group, a cycloalkyl group), —SO 2 Rd (Rd is an alkyl group, Aryl group, cycloalkyl group, o-quinonediazide group), or a combination thereof.
• the alkyl group represented by R 3 , R 3 ′ or R 3 ′′ may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms in the alkyl chain. It may have an oxygen atom, a sulfur atom, or a nitrogen atom, specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group And straight chain alkyl groups such as n-dodecyl group, n-tetradecyl group and n-octadecyl group, and branched alkyl groups such as isopropyl group, isobutyl group, t-butyl group, neopentyl group and 2-ethylhexyl group.
• the substituent include a cyano group, a halogen atom, a
• the cycloalkyl group represented by R 3 , R 3 ′ or R 3 ′′ may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, which may be polycyclic, Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
• the aryl group represented by R 3 , R 3 ′ or R 3 ′′ may have a substituent, preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a naphthyl group, And anthryl group.
• the aralkyl group represented by R 3 , R 3 ′ or R 3 ′′ may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group, A naphthylmethyl group and a naphthylethyl group are mentioned.
• the alkoxy group represented by R 3 , R 3 ′ or R 3 ′′ may have a substituent, preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, Examples include propoxy group, n-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group and the like.
• the silicon atom-containing group represented by R 3 , R 3 ′ or R 3 ′′ is not particularly limited as long as silicon is contained, but a silyloxy group (trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy) is preferable.
• the alkenyl group represented by R 3 , R 3 ′ or R 3 ′′ is a group having a double bond at an arbitrary position of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group or silicon atom-containing group.
• the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6.
• a vinyl group and an allyl group are preferable.
• the alkynyl group represented by R 3 , R 3 ′ or R 3 ′′ has a triple bond at any position of the above alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group and silicon atom-containing group.
• Preferred are those having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, such as ethynyl group and propargyl group.
• At least one of the plurality of —CO 2 R 3 present in the resin (a) is a group that decomposes by the action of an acid to generate an alkali-soluble group.
• Formula (2) -CO 2 R 3 in ' is the same for -CO 2 R 3 "in formula (3).
• the group that decomposes by the action of an acid to generate an alkali-soluble group is a group that decomposes by the action of an acid to generate an alkali-soluble group such as a hydroxyl group or a carboxyl group on the resin side (hereinafter also referred to as an acid-decomposable group).
• the acid-decomposable group is preferably a group that decomposes by the action of an acid and generates a carboxyl group as an alkali-soluble group on the resin side.
• a preferred group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid. Examples of the group capable of leaving with an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), —C (R 01 ) (R 02 ). ) (OR 39 ) and the like.
• R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• R 36 and R 37 may be bonded to each other to form a ring.
• R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• the acid-decomposable group is preferably a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, an enol ester group or the like.
• a tertiary alkyl ester group and an acetal ester group are more preferable, and a photosensitive film having high sensitivity and high resolution can be obtained by using them.
• the tertiary alkyl ester group as the acid-decomposable group is preferably an ester group in which the hydrogen atom of the carboxyl group is substituted with a group represented by the following general formula (AI).
• T represents a single bond or a —Rt—COO— group.
• Rt represents an alkylene group or a cycloalkylene group.
• Rx 1 to Rx 3 each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx 1 to Rx 3 may combine to form a cycloalkyl group (monocyclic or polycyclic).
• Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group, — (CH 2 ) 2 — group, or — (CH 2 ) 3 — group.
• the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
• Examples of the cycloalkyl group represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
• Examples of the cycloalkyl group formed by combining two of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group
• a polycyclic cycloalkyl group such as a group is preferred.
• a monocyclic cycloalkyl group having 5 or 6 carbon atoms is particularly preferable.
• An embodiment in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-described cycloalkyl group is preferable.
• Each of the above groups may have a substituent.
• substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, Examples thereof include alkoxycarbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.
• Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms.
• Z represents the substituent which each said group may have, and when there exist multiple, each is independent.
• p represents 0 or a positive integer.
• the tertiary alkyl ester group as the acid-decomposable group includes a group represented by the following general formula (I) and a group represented by the following general formula (II) as the group represented by the general formula (AI).
• a tertiary alkyl ester group having at least one of the above is more preferable.
• R 2 , R 4 , R 5 and R 6 each independently represents an alkyl group or a cycloalkyl group.
• R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
• the alkyl group in R 2 may be linear or branched, and may have a substituent.
• the cycloalkyl group in R 2 may be monocyclic or polycyclic and may have a substituent.
• R 2 is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.
• R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
• the alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.
• the alkyl group in R 4 , R 5 , and R 6 may be linear or branched and may have a substituent.
• the alkyl group those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.
• the cycloalkyl group in R 4 , R 5 and R 6 may be monocyclic or polycyclic and may have a substituent.
• the cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.
• Examples of the group represented by the general formula (I) include groups represented by the following general formulas (Ia) and (Ib).
• R 2 has the same meaning as R 2 in formula (I).
• the group represented by the general formula (II) is preferably a group represented by the following general formula (II-a).
• R 4 and R 5 have the same meaning as in general formula (II).
• the acetal ester group as the acid-decomposable group is preferably an ester group in which a hydrogen atom of a carboxyl group is substituted with a group represented by the following general formula (III).
• Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
• Rb represents a single bond or a divalent linking group.
• Q represents an alkyl group, an alicyclic group which may contain a hetero atom, or an aromatic ring group which may contain a hetero atom.
• At least two of Ra, Rb and Q may be bonded to each other to form a ring. This ring is preferably a 5-membered ring or a 6-membered ring.
• Ra is particularly preferably a hydrogen atom, a methyl group, a phenyl group or a benzyl group, and a photosensitive film having good sensitivity can be obtained.
• Ra is a group represented by the following general formula (IV) or (V) from the standpoint of preventing degradation of the acetal ester group as an acid-decomposable group during storage due to steric hindrance and preventing a decrease in patternability. Is also preferable.
• Rc, Rd, Re, Rf and Rg are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, cyano.
• Ra is a group represented by the general formula (IV) or (V)
• the progress of the imidization reaction during storage can be suppressed in the resin having the repeating unit represented by the general formula (1), and the patterning property Can be prevented.
• the alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group as Rc, Rd, Re, Rf, Rg is an alkyl group, cycloalkyl group, aryl group, aralkyl group for R 3 in the general formula (1), The thing similar to what was mentioned above as an alkoxy group is mentioned.
• the aryloxy group as Rc, Rd, Re, Rf, Rg is preferably an aryloxy group having 6 to 10 carbon atoms, and specific examples include phenoxy, toluyloxy, 1-naphthoxy and the like.
• the alkoxycarbonyl group as Rc, Rd, Re, Rf, Rg is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms, specifically, methoxycarbonyl, ethoxycarbonyl, linear or branched propoxycarbonyl, cyclopentyloxycarbonyl, Examples include cyclohexyloxycarbonyl.
• Examples of the aryloxy moiety of the aryloxycarbonyl group as Rc, Rd, Re, Rf, and Rg include the same aryloxy groups as those described above.
• At least one of Rc and Rd in the general formula (IV) is a cycloalkyl group, an aryl group, or an aralkyl. It is preferably a group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and more preferably at least one is an aryl group.
• the divalent linking group as Rb is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene group.
• an alkylene group preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group
• a cycloalkylene group preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group
• a cycloalkylene group having 3 to 15 carbon atoms such as a cyclopentylene group or a cyclohexylene group
• R 0 is a hydrogen atom or an alkyl group (eg, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, Hexyl group and octyl group).
• Rb is preferably a single bond, an alkylene group, or a divalent linking group comprising a combination of an alkylene group and at least one of —O—, —CO—, —CS— and —N (R 0 ) —.
• An alkylene group, or a divalent linking group composed of a combination of an alkylene group and —O— is more preferable.
• R 0 has the same meaning as R 0 described above.
• the alkyl group as Q is the same as the alkyl group as Ra described above, for example.
• Examples of the alicyclic group and aromatic ring group as Q include the cycloalkyl group and aryl group as Ra described above.
• the number of carbon atoms is preferably 3-18.
• a group in which a plurality of aromatic rings are connected via a single bond is also included in the aromatic group as Q.
• Examples of the alicyclic group containing a hetero atom and the aromatic ring group containing a hetero atom include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole. And pyrrolidone.
• the alicyclic group and aromatic ring group as Q may have a substituent, and examples thereof include an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. It is done.
• (—Rb-Q) is particularly preferably a methyl group, an aryloxyethyl group, a cyclohexylethyl group, or an arylethyl group, which improves solubility and thermal stability.
• any of Rb and Q and Ra are bonded to form a propylene group or a butylene group and contain an oxygen atom
• a 5-membered ring or a 6-membered ring is formed is mentioned.
• N C When the total carbon number of Ra, Rb and Q is expressed as N C , when N C is large, the alkali dissolution rate change of the resin (a) before and after the removal of the group represented by the general formula (III) is eliminated Increases, the dissolution contrast becomes harder, and the resolution is improved.
• the range of N C is preferably 2 to 20, and 2 to 15 is particularly preferable.
• N C is 20 or less, the glass transition temperature of the polymer compound is suppressed from being lowered, and further, the generation of defects in which a desorbed substance from the acid-decomposable group adheres to the pattern is suppressed.
• At least one of Ra, Rb and Q is preferably an electron-withdrawing group or a group having an electron-withdrawing group.
• the electron withdrawing group include an alkoxy group, aryl group, alkenyl group, alkynyl group, halogen atom, acyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, aryloxy group, nitrile group (cyano group).
• An alkylsulfonyl group, an arylsulfonyl group, a nitro group, and the like, and an alkoxy group, an aryl group, and an acyl group are preferable.
• the thermal decomposition temperature of —CO 2 R 3 in the general formula (1), —CO 2 R 3 ′ in the general formula (2) or —CO 2 R 3 ′′ in the general formula (3) is 100 to 220 ° C. Preferably, it is 120 to 210 ° C., more preferably 140 to 200 ° C.
• the thermal decomposition temperature can be determined, for example, by differential thermobalance analysis. When the thermal decomposition temperature is too low, the storage stability of the photosensitive resin composition of the present invention may be lowered. If the thermal decomposition temperature is too high, the stress increases and the wafer warpage may increase. In addition, decomposition products remain in the film, which may cause outgassing and decrease in reliability.
• the thermal decomposition temperature By setting the thermal decomposition temperature to 100 to 220 ° C., the stress of the cured relief pattern according to the present invention is further reduced, and the wafer warpage is further reduced.
• the reason why the stress is further lowered is not clear, but by setting the thermal decomposition temperature to 100 to 220 ° C., —CO 2 R 3 in the repeating unit represented by the general formula (1) is converted to —CO 2 during low temperature curing. It is presumed that the in-plane orientation of the polyimide film is enhanced and the stress is reduced by ring closure of the imide after 2 H.
• R 3 , R 3 ′ or R 3 ′′ capable of achieving the thermal decomposition temperature as described above
• Examples include a structure in which Ra in the general formula (III) is a group represented by the general formula (IV) or the following general formula (VII).
• R 7 to R 8 each independently represents a hydrogen atom, an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic), and at least one of R 7 to R 8 is a hydrogen atom. .
• Rh represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
• Specific examples and preferred examples of the alkyl group and cycloalkyl group for R 7 to R 8 include the same as the specific examples and preferred examples described above for the alkyl group and cycloalkyl group for Rx 1 to Rx 3. .
• the alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group as Rh is the same as that described above as the alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group for R 3 in the general formula (1).
• the aryloxy group as Rh is preferably an aryloxy group having 6 to 10 carbon atoms, and specific examples include phenoxy, toluyloxy, 1-naphthoxy and the like.
• the alkoxycarbonyl group as Rh is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms, and specific examples include methoxycarbonyl, ethoxycarbonyl, linear or branched propoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl and the like.
• Examples of the aryloxy moiety of the aryloxycarbonyl group as Rh include the same aryloxy groups as those described above.
• a hydrogen atom and an organic group can be mixed in R 3 . It is preferably 100 mol% to 20 mol%, more preferably 100 mol% to 40 mol%, respectively, based on the total R 3 in the resin (a).
• the dissolution rate with respect to the aqueous alkali solution is changed, and by this adjustment, a photosensitive resin composition having an appropriate dissolution rate can be obtained.
• the proportion of the group that decomposes by the action of an acid to generate an alkali-soluble group, the so-called protection rate is preferably 40 to 100%, and preferably 45 to 100 % Is more preferable.
• terminal blocker can be made to react with the terminal of the polymer which has as a main component the structural unit represented by General formula (1).
• the terminal capping agent monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used.
• terminal blocker react it is preferable at the point which can control the repeating number of a structural unit, ie, molecular weight, in a preferable range.
• acid deactivation due to neutralization of the terminal amine and the generated acid can be suppressed by the terminal blocking agent.
• various organic groups such as a crosslinking reactive group having a carbon-carbon unsaturated bond can be introduced as a terminal group.
• Monoamines used for end-capping agents are 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy- 6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2 -Hydroxynaphthalene, 1-carboxy-8-amino Naphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-
• 5-amino-8-hydroxyquinoline 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Amino salicylic acid, 5-amino salicylic acid, 6-amino salicy Acid, 2-aminobenzenesulfonic acid, 3-aminobenzo
• Acid anhydrides, monocarboxylic acids, monoacid chloride compounds and active ester compounds used as end-capping agents are phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride Acid anhydrides such as 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1- Hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carbo Sinaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy
• phthalic anhydride maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynyl Benzo Monocarboxylic acids such as these, and monoacid chlor
• the introduction ratio of the monoamine used for the terminal blocking agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component.
• the introduction ratio of the compound selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the end-capping agent is in the range of 0.1 to 100 mol% with respect to the diamine component.
• the amount is particularly preferably 5 to 90 mol%.
• a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
• the end-capping agent introduced into the polymer can be easily detected by the following method.
• a polymer having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component that are constituent units of the polymer.
• the end-capping agent can be easily detected by gas chromatography (GC) or NMR measurement.
• GC gas chromatography
• NMR nuclear magnetic resonance
• PLC pyrolysis gas chromatography
• infrared spectrum 13 CNMR spectrum.
• the resin (a) used in the photosensitive resin composition of the present invention preferably has a structural unit represented by the general formula (1) as a main component.
• the main component as used herein means that 70 mol% or more of the structural unit represented by the general formula (1) is contained. More preferably, it is 80 mol% or more, and most preferably 90 mol% or more.
• the resin used in the present invention is a copolymer of the structural unit represented by the general formula (1) and other structural units, or contains the structural unit represented by the general formula (1). It may be a mixture of a plurality of resins.
• a resin containing the structural unit represented by the general formula (1) and a resin not containing the structural unit represented by the general formula (1) (for example, in the general formula (1), R 2 is an aromatic ring only.
• a resin the resin containing the structural unit represented by the general formula (1) is preferably contained in an amount of 50% by mass or more, and more preferably 75% by mass or more.
• the type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.
• the resin (a) containing the repeating unit represented by the general formula (1) preferably has a mass average molecular weight of 200,000 or less from the viewpoint of alkali dissolution rate, film physical properties, etc. 200,000 is more preferable, 2,000 to 100,000 is more preferable, and 3,000 to 100,000 is particularly preferable. By adjusting to this molecular weight range, it is possible to obtain a photosensitive film having low stress, excellent mechanical properties, and excellent resolution with few development defects.
• the molecular weight can be measured by a gel permeation chromatography method and determined using a standard polystyrene calibration curve.
• the dispersity (molecular weight distribution) is preferably 1.0 to 4.0, and more preferably 1.0 to 3.5.
• any conventionally known method may be used (see, for example, the latest polyimide: basics and applications (edited by Japan Polyimide Research Group)).
• a method of reacting tetracarboxylic dianhydride and diamine compound at low temperature a diester is obtained by tetracarboxylic dianhydride and alcohol, and then in the presence of an amine and a condensing agent.
• polyamic acid is obtained by reacting a diamine compound and tetracarboxylic dianhydride in an organic solvent at ⁇ 20 to 50 ° C. for several minutes to several days, and then reacting with basic halides or under acidic conditions.
• R 1 , R 2 and R 3 have the same meaning as in general formula (1).
• organic solvents that can be used in the synthesis reaction of the polyamic acid include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, and 1,3-dimethyl-2-imidazolidinone.
• Solvents aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, pyridine, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, Examples thereof include ether solvents such as tetrahydrofuran, dioxane and diglyme. Of these, amide solvents are preferred, and high molecular weight polyamic acid can be obtained.
• the boiling point of the organic solvent used for the polymerization reaction is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher.
• the concentration of the solute in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.
• the polyamic acid ester obtained as described above is formed on a substrate such as a semiconductor substrate together with the component (b), and a relief pattern can be formed by a subsequent lithography process. By heat treatment of this pattern, polyamic acid ester or polyamic acid is dehydrated and closed, and a cured polyimide film is obtained.
• the polyamic acid ester having the structural unit represented by the general formula (1) has a film formed from the precursor having an i-line transmittance of 1% or more per film thickness of 20 ⁇ m, and 5% or more. It is preferably 10% or more, more preferably 10 to 80%. When this value is less than 1%, it is difficult to obtain a photosensitive resin composition capable of forming a pattern with high resolution and good shape.
• the transmittance of i-line (light having a wavelength of 365 nm) can be measured with a spectrophotometer (for example, Hitachi U3410 type, manufactured by Hitachi, Ltd.).
• the residual stress of the cured polyimide film formed by imide ring closure from the polyamic acid ester having the structural unit represented by the general formula (1) is preferably 25 MPa or less, more preferably 20 MPa or less. preferable.
• the warpage amount of the silicon wafer and the residual strain inside the silicon chip increase.
• the residual stress of the polyimide film can be measured at a normal temperature (25 ° C.) with a thin film stress measuring device (for example, FLX-2320 manufactured by Tencor).
• the polyamic acid ester having the structural unit represented by the above general formula (1) that satisfies these characteristics can suppress the aromatic ring ⁇ conjugation length by selecting an appropriate monomer, and has a rigid and straight main chain. It will have a structure that can be formed.
• the resin (a) may be used alone or in combination. Further, a resin other than the resin (a) may be used in combination.
• composition of the present invention is a compound that generates acid upon irradiation with actinic ray or radiation (also referred to as “photoacid generator” or “(b) component”). Containing. These may be used in combination of two or more. Moreover, a sensitizer etc. can also be used together for sensitivity adjustment.
• the photoacid generator is used as a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, or a microresist.
• Known compounds that generate an acid upon irradiation with active light or radiation and mixtures thereof can be appropriately selected and used.
• Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.
• a group that generates an acid upon irradiation with actinic rays or radiation or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. 3914407, JP 63-26653, JP 55-164824, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP The compounds described in 63-146029 and the like can be used.
• R 201 , R 202 and R 203 each independently represents an organic group.
• R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
• X ⁇ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF 4 ⁇ , PF 6 ⁇ , SbF 6 —
• An organic anion having a carbon atom is preferable.
• Preferred organic anions include organic anions represented by the following general formula.
• Rc 1 represents an organic group.
• the organic group in Rc 1 include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these which may be substituted is a single bond, —O—, — And groups linked by a linking group such as CO 2 —, —S—, —SO 3 —, —SO 2 N (Rd 1 ) —.
• Rd 1 represents a hydrogen atom or an alkyl group.
• Rc 3 , Rc 4 and Rc 5 each independently represents an organic group.
• Examples of the organic group for Rc 3 , Rc 4 and Rc 5 include the same organic groups as those for Rc 1 , preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Rc 3 and Rc 4 may be bonded to form a ring. Examples of the group formed by combining Rc 3 and Rc 4 include an alkylene group, a cycloalkylene group, and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred.
• the organic group of Rc 1 and Rc 3 to Rc 5 is preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group.
• a fluorine atom or a fluoroalkyl group By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved.
• Rc 3 and Rc 4 are combined to form a ring, so that the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved, which is preferable.
• the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
• Examples of the organic group for R 201 to R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
• Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
• Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
• the aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
• the aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like.
• the alkyl group and cycloalkyl group in R 204 to R 207 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
• the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent.
• Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group represented by R 204 to R 207 may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 15 carbon atoms). ), Aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.
• Triarylsulfonium salts are particularly preferable in terms of thermal stability and sensitivity, and it is preferable to use a sensitizer in combination. Two or more kinds of such compounds can be used in combination as required.
• the triarylsulfonium salt it is preferable that at least one aryl group has an electron withdrawing group as a substituent, and the total Hammett value of the substituents bonded to the aryl skeleton is preferably larger than 0.18. .
• the electron withdrawing group means a substituent having a Hammett value (Hammet substituent constant ⁇ ) larger than 0.
• the sum of Hammett values of substituents bonded to the aryl skeleton in the specific photoacid generator is preferably 0.18 or more, more preferably greater than 0.46. Preferably, it is more preferably larger than 0.60.
• the Hammett value represents the degree of electron withdrawing property of a cation having a triarylsulfonium salt structure, and there is no particular upper limit from the viewpoint of increasing sensitivity, but from the viewpoint of reactivity and stability. Is preferably more than 0.46 and less than 4.0, more preferably more than 0.50 and less than 3.5, and particularly preferably more than 0.60 and less than 3.0.
• the Hammett value in the present invention uses the numerical values described in Naoki Inamoto, Chemistry Seminar 10 Hammett's Law-Structure and Reactivity (published by Maruzen Co., Ltd. in 1983).
• Examples of the electron withdrawing group introduced into the aryl skeleton include a trifluoromethyl group, a halogen atom, an ester group, a sulfoxide group, a cyano group, an amide group, a carboxyl group, and a carbonyl group.
• the Hammett values of these substituents are shown below.
• a trifluoromethyl group (—CF 3 , m: 0.43, p: 0.54), a halogen atom [for example, —F (m: 0.34, p: 0.06), —Cl (m: 0. 37, p: 0.23), -Br (m: 0.39, p: 0.23), -I (m: 0.35, p: 0.18)], an ester group (for example, -COCH 3 , O: 0.37, p: 0.45), sulfoxide group (for example, —SOCH 3 , m: 0.52, p: 0.45), cyano group (—CN, m: 0.56, p: 0.66), an amide group (for example, —NHCOCH 3 , m: 0.21, p: 0.00), a carboxy group (—COOH, m: 0.37, p: 0.45), a carbonyl group (— CHO, m: 0.36, p: (043)) and the
• nonionic substituents such as a halogen atom and a halogenated alkyl group are preferable from the viewpoint of hydrophobicity.
• —Cl is preferable from the viewpoint of reactivity, and imparts hydrophobicity.
• —F, —CF 3 , —Cl, and —Br are preferable.
• substituents may be introduced into any one of the three aryl skeletons of the triarylsulfonium salt structure, or may be introduced into two or more aryl skeletons. Moreover, the substituent introduced into each of the three aryl skeletons may be one or plural. In the present invention, the sum of Hammett values of substituents introduced into these aryl skeletons is preferably more than 0.18, more preferably more than 0.46.
• the number of substituents to be introduced is arbitrary. For example, only one substituent having a particularly large Hammett value (for example, a Hammett value exceeding 0.46 alone) may be introduced into one position of an aryl skeleton having a triarylsulfonium salt structure. Moreover, for example, a plurality of substituents introduced and the sum of the Hammett values exceeding 0.46 may be introduced.
• the Hammett value of the substituent varies depending on the position where it is introduced, the sum of Hammett values in the specific photoacid generator according to the present invention is determined by the type of substituent, the position of introduction, and the number of introductions. become.
• the Hammett's rule is usually expressed in the m-position and p-position, but in the present invention, the substituent effect at the o-position is calculated as the same value as the p-position as an index of electron withdrawing property.
• Preferred substitution positions are preferably m-position and p-position, and most preferably p-position from the viewpoint of synthesis.
• Preferred in the present invention is a sulfonium salt that is tri- or more substituted with a halogen atom, and most preferred is a sulfonium salt that is tri-substituted with a chloro group, specifically, each of the three aryl skeletons. And preferably have a triarylsulfonium salt structure in which —Cl is introduced, and more preferably —Cl is substituted at the p-position.
• Examples of the sulfonate anion possessed by the triarylsulfonium salt contained in the composition of the present invention include an aryl sulfonate anion, an alkane sulfonate anion, and the like, which are substituted with a fluorine atom or an organic group having a fluorine atom.
• An anion is preferred.
• Examples of the compound having a triarylsulfonium salt structure are J.P. Am. Chem. Soc. 112 (16), 1990; 6004-6015, J.A. Org. Chem. 1988; It can be easily synthesized by the methods described in 5571-5573, WO02 / 081439A1 pamphlet, or European Patent (EP) No. 1113005.
• triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate or 4-phenylthiophenyl diphenylsulfonium trifluoroacetate and the like.
• diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2′-hydroxy- 1'-tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecoxy) phenyliodonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetra Decaoxy) phenyliodonium-p-toluenesulfonate, etc .; diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butyl) Sulfon
• oxime compounds more preferably oxime sulfonate compounds, are the most preferable examples from the viewpoint of sensitivity, resolution, dielectric constant, dimensional stability, and the like. Can be mentioned.
• Preferred examples of the oxime sulfonate compound that is, the compound having an oxime sulfonate residue include compounds containing an oxime sulfonate residue represented by the formula (b1).
• R 5 represents an alkyl group or an aryl group. Any group may be substituted, and the alkyl group in R 5 may be linear, branched or cyclic. Acceptable substituents are described below.
• the alkyl group for R 5 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
• the alkyl group represented by R 5 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
• the aryl group for R 5 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group.
• the aryl group for R 5 may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.
• the compound containing the oxime sulfonate residue represented by the formula (b1) is an oxime sulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5). Is particularly preferred.
• R 1 represents an alkyl group, an aryl group or a heteroaryl group
• each R 2 independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
• R 6 represents each independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
• X represents O or S
• n represents 1 or 2
• m represents an integer of 0 to 6.
• the alkyl group, aryl group or heteroaryl group in R 1 may have a substituent.
• the alkyl group for R 1 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
• the substituent that the alkyl group in R 1 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.
• alkyl group in R 1 examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group.
• the aryl group for R 1 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
• substituents that the aryl group in R 1 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.
• Sulfonic acid group aminosulfonyl group, alkoxysulfonyl group.
• Examples of the aryl group in R 1 include a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group.
• the heteroaryl group for R 1 is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent.
• substituents that the heteroaryl group in R 1 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl.
• At least one of the heteroaryl groups in R 1 may be a heteroaromatic ring.
• a heteroaromatic ring and a benzene ring are condensed. May be.
• the heteroaryl group for R 1 is selected from the group consisting of optionally substituted thiophene ring, pyrrole ring, thiazole ring, imidazole ring, furan ring, benzothiophene ring, benzothiazole ring and benzimidazole ring. And a group in which one hydrogen atom is removed from the ring.
• R 2 is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
• one or two of R 2 present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
• the alkyl group or aryl group in R 2 may have a substituent. Examples of the substituent that the alkyl group or aryl group in R 2 may have include the same groups as the substituent that the alkyl group or aryl group in R 1 may have.
• the alkyl group for R 2 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and is an alkyl group having 1 to 6 carbon atoms which may have a substituent. It is more preferable.
• Examples of the alkyl group for R 2 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, and chloromethyl group.
• a bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group are preferable.
• a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is preferable.
• the aryl group for R 2 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
• the aryl group in R 2 is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
• the halogen atom for R 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.
• X represents O or S, and is preferably O.
• the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
• n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 is preferable.
• the alkyl group and alkyloxy group in R 6 may have a substituent.
• the alkyl group for R 6 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
• the substituent that the alkyl group in R 6 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .
• alkyl group for R 6 examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl and benzyl are preferred.
• the alkyloxy group for R 6 is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.
• substituents that the alkyloxy group in R 6 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. It is done.
• alkyloxy group in R 6 a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.
• examples of the aminosulfonyl group for R 6 include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group. It is done.
• examples of the alkoxysulfonyl group for R 6 include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.
• m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.
• the compound containing an oxime sulfonate residue represented by the formula (b1) is particularly preferably an oxime sulfonate compound represented by any one of the following formulas (OS-6) to (OS-11). .
• R 1 represents an alkyl group, an aryl group, or a heteroaryl group
• R 7 represents a hydrogen atom or a bromine atom
• R 8 represents a hydrogen atom
• R 9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group
• 10 represents a hydrogen atom or a methyl group.
• R 1 in the formulas (OS-6) to (OS-11) has the same meaning as R 1 in the formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
• R 7 in formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
• R 8 in the formulas (OS-6) to (OS-11) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl
• R 9 in formula (OS-8) and formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
• R 10 in the formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
• the oxime steric structure (E, Z) may be either one or a mixture.
• oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.
• the compound containing an oxime sulfonate residue represented by the formula (b1) is also preferably a compound represented by the formula (OS-1).
• R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl. Represents a group.
• R 2 represents an alkyl group or an aryl group.
• R 21 to R 24 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group or Represents an aryl group. Two of R 21 to R 24 may be bonded to each other to form a ring.
• R 21 to R 24 a hydrogen atom, a halogen atom and an alkyl group are preferable, and an embodiment in which at least two of R 21 to R 24 are bonded to each other to form an aryl group is also preferable. Among these, an embodiment in which R 21 to R 24 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
• the compound represented by the formula (OS-1) is more preferably a compound represented by the following formula (OS-2).
• R 1 , R 2 and R 21 to R 24 have the same meanings as in the formula (OS-1), and preferred examples thereof are also the same.
• an embodiment in which R 1 in the formula (OS-1) and the formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the formula (OS-2), in which R 1 is a cyano group, phenyl
• the embodiment which is a group or a naphthyl group is most preferred.
• the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
• b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.
• the above compound containing an oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the following formula (b2).
• R 5 represents an alkyl group or an aryl group
• X represents an alkyl group, an alkoxy group, or a halogen atom
• m represents an integer of 0 to 3
• m is 2 or 3. In some cases, multiple Xs may be the same or different.
• the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
• the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
• the halogen atom as X is preferably a chlorine atom or a fluorine atom.
• m is preferably 0 or 1. In the formula (b2), m is 1, X is a methyl group, the substitution position of X is the ortho position, R 5 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A compound that is a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
• the compound containing an oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the formula (b3).
• R 5 has the same meaning as R 5 in the formula (b1), X 'is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and L represents an integer of 0 to 5.
• R 5 in the formula (b3) is methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro
• a fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
• X ′ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
• L is preferably from 0 to 2, particularly preferably from 0 to 1.
• Specific examples of the compound represented by the formula (b3) include ⁇ - (methylsulfonyloxyimino) benzyl cyanide, ⁇ - (ethylsulfonyloxyimino) benzyl cyanide, ⁇ - (n-propylsulfonyloxyimino) benzyl.
• preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more.
• Compounds (i) to (viii) can be obtained as commercial products. It can also be used in combination with other types of (C) radiation-sensitive acid generators.
• the content of the photoacid generator is preferably 1 to 30% by mass, more preferably 3 to 20% by mass based on the total solid content of the photosensitive resin composition.
• the acid generator can be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more. *
• sensitizer may be added to the composition of the present invention in order to absorb actinic rays or radiation and promote the decomposition of the sulfonium salt.
• the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
• the sensitizer in an electronically excited state comes into contact with sulfonium, and effects such as electron transfer, energy transfer, and heat generation occur.
• the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
• preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
• Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene
• xanthenes eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
• cyanines eg, thiacarbocyanine, oxacarbocyanine
• merocyanine Eg, merocyanine, carbomerocyanine
• thiazines eg, thionine, methylene blue, toluidine blue
• acridines eg, acridine orange, chloroflavin, acriflavine
• anthraquinones eg, anthraquinone
• squalium eg, , Squalium
• coumarins eg, 7-diethylamino-4-methylcoumarin.
• sensitizer include compounds represented by the following formulas (IX) to (XIV).
• a 1 represents a sulfur atom or NR 50
• R 50 represents an alkyl group or an aryl group
• L 2 forms a basic nucleus of the dye together with adjacent A 1 and an adjacent carbon atom.
• R 51 and R 52 each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R 51 and R 52 may be bonded to each other to form an acidic nucleus of the dye.
• W represents an oxygen atom or a sulfur atom.
• Ar 1 and Ar 2 each independently represent an aryl group and are linked via a bond with —L 3 —.
• L 3 represents —O— or —S—.
• W is synonymous with that shown in Formula (IX).
• a 2 represents a sulfur atom or NR 59
• L 4 represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A 2 and a carbon atom
• R 53 , R 54 , R 55 , R 56 , R 57 and R 58 each independently represent a monovalent nonmetallic atomic group
• R 59 represents an alkyl group or an aryl group.
• a 3 and A 4 each independently represent —S—, —NR 62 — or —NR 63 —, and R 62 and R 63 each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L 5 and L 6 each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A 3 , A 4, and adjacent carbon atoms, and R 60 , R 61 each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.
• R 66 represents an aromatic ring or a hetero ring which may have a substituent
• a 5 represents an oxygen atom, a sulfur atom or ⁇ NR 67
• R 64 , R 65 and R 67 each independently represent a hydrogen atom or a monovalent non-metallic atomic group
• R 67 and R 64 , and R 65 and R 67 each represent an aliphatic or aromatic ring. Can be combined to form.
• R 68 and R 69 each independently represent a hydrogen atom or a monovalent nonmetallic atomic group.
• R 70 and R 71 each independently represent a monovalent nonmetallic atomic group, and n represents an integer of 0 to 4. When n is 2 or more, R 70 and R 71 can be bonded to each other to form an aliphatic or aromatic ring.
• an anthracene derivative is particularly preferable.
• the sensitizer as described above may be a commercially available one or may be synthesized by a known synthesis method.
• the content of the sensitizer is preferably 1 to 30% by mass, more preferably 3 to 20% by mass based on the total solid content of the photosensitive resin composition.
• composition according to the present invention preferably contains a basic compound in order to reduce a change in performance over time from exposure to heating.
• Preferred examples of the basic compound include compounds having a structure represented by the following formulas (A) to (E).
• R 200 , R 201 and R 202 may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein R 201 and R 202 may combine with each other to form a ring.
• R 203 , R 204 , R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
• the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
• the alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
• Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
• Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like.
• Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undecar 7-ene and the like.
• Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris ( t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like.
• the compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.
• Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
• aniline compounds include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
• alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine.
• aniline derivatives having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
• Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
• amine compound a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
• the amine compound is more preferably a tertiary amine compound.
• the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms).
• 6 to 12 carbon atoms may be bonded to the nitrogen atom.
• the amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
• the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
• an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
• ammonium salt compound a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
• the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
• the ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
• the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
• an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
• Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
• the halogen atom is particularly preferably chloride, bromide or iodide
• the sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms.
• Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
• the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups.
• substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups.
• Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.
• Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring and an anthracene ring.
• the benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
• linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like.
• substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.
• An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound.
• the phenoxy group may have a substituent.
• the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group.
• the substitution position of the substituent may be any of the 2-6 positions.
• the number of substituents may be any in the range of 1 to 5.
• oxyalkylene group between the phenoxy group and the nitrogen atom.
• the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
• an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
• the sulfonic acid ester group may be any of alkyl sulfonic acid ester, cycloalkyl group sulfonic acid ester, and aryl sulfonic acid ester.
• the alkyl group has 1 to 20 carbon atoms
• the cycloalkyl group has 3 to 20 carbon atoms
• the aryl group has 6 carbon atoms.
• Alkyl sulfonic acid ester, cycloalkyl sulfonic acid ester, and aryl sulfonic acid ester may have a substituent.
• substituents include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, and a sulfonic acid.
• An ester group is preferred.
• oxyalkylene group between the sulfonate group and the nitrogen atom.
• the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
• an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
• the following compounds are also preferable as the basic compound.
• the composition according to the present invention may or may not contain a basic compound. However, when it is contained, the content of the basic compound is usually 0.001 to on the basis of the total solid content of the composition. It is 10% by mass, preferably 0.01-5% by mass.
• the acid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
• the present invention may contain a thermal acid generator.
• the thermal acid generator is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C. to 250 ° C., preferably 150 ° C. to 220 ° C., for example, sulfonic acid, It is a compound that generates a low nucleophilic acid such as carboxylic acid or disulfonylimide.
• sulfonic acid, alkyl substituted with an electron withdrawing group or arylcarboxylic acid having a strong pKa of 2 or less, disulfonylimide substituted with an electron withdrawing group, and the like are preferable.
• the electron withdrawing group examples include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
• the thermal acid generator is required not to be decomposed during storage time or in a pre-baking process after applying the composition, but to be quickly decomposed in a heat-curing process after patterning. Therefore, the thermal decomposition point is preferably 100 ° C to 300 ° C. More preferably, it is 120 ° C to 250 ° C, and further preferably 150 ° C to 200 ° C.
• a photoacid generator that generates an acid by the above-described exposure can be applied.
• Examples thereof include onium salts such as sulfonium salts and iodonium salts, N-hydroxyimide sulfonate compounds, oxime sulfonates, o-nitrobenzyl sulfonates and the like.
• Preferred examples of the sulfonium salt include compounds represented by the following general formulas (TA-1) to (TA-3).
• R T1 to R T5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
• R T6 and R T7 each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.
• R T8 and R T9 each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
• R T1 to R T5 , R T6 and R T7, and R T8 and R T9 may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom, a ketone A bond, an ester bond, or an amide bond may be included.
• Examples of the group formed by combining any two or more of R T1 to R T5 , R T6 and R T7, and R T8 and R T9 include a butylene group and a pentylene group.
• X ⁇ represents a non-nucleophilic anion, and has a strong pKa of 2 or less as described above, a sulfonic acid or an alkyl or aryl carboxylic acid substituted with an electron withdrawing group, or a disulfonylimide substituted with an electron withdrawing group.
• Etc. are preferable.
• the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
• R T10 and R T11 each independently represent an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
• R T10 and R T11 may be bonded to each other to form a ring structure, and this ring structure may contain an oxygen atom, a sulfur atom, a ketone bond, an ester bond, or an amide bond.
• Examples of the group formed by combining R T10 and R T11 include a butylene group and a pentylene group.
• R T12 to R T16 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a thioalkoxy group, or a hydroxyl group, and two or more of them are bonded to each other to form a naphthalene ring, an anthracene ring, etc.
• a polycyclic aromatic ring may be formed.
• X ⁇ represents a non-nucleophilic anion.
• R T17 represents an alkyl group (straight chain or branched) or a cycloalkyl group, preferably a straight chain and branched alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms (for example, a methyl group, Ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).
• cycloalkyl group examples include not only a monocyclic cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group, but also a cyclic alkyl group having a bridging site such as a norbornyl group, a tricyclodecanyl group, and an adamantyl group. it can.
• R T18 and R T19 each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.
• R T20 and R T21 each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
• R T18 and R T19 and R T20 and R T21 may be bonded to each other to form a ring structure, and this ring structure may contain an oxygen atom, a sulfur atom, a ketone bond, an ester bond, or an amide bond. Good.
• Examples of the group formed by combining R T18 and R T19 and R T20 and R T21 include a butylene group and a pentylene group.
• X ⁇ represents a non-nucleophilic anion.
• the alkyl group as R T1 to R T17 may be linear or branched.
• a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms for example, Methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).
• the cycloalkyl group as R T1 to R T17 is meant to include a monocyclic alkyl group as well as a polycyclic and cyclic alkyl group having a bridging site, and the cycloalkyl group as R T12 to R T16 is preferably Is a cycloalkyl group having 3 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group).
• the cycloalkyl group as R T17 has a cycloalkyl group having 3 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group) and a cyclic group having a bridging site such as a norbornyl group, a tricyclodecanyl group, or an adamantyl group. Also preferred are alkyl groups.
• the alkoxy group as R T1 to R T5 and R T12 to R T16 may be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 1 carbon atoms. 5 linear and branched alkoxy groups (for example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), cyclic alkoxy groups having 3 to 8 carbon atoms (for example, , Cyclopentyloxy group, cyclohexyloxy group).
• the thioalkoxy group as R T12 to R T16 may be linear, branched or cyclic, for example, a thioalkoxy group having 1 to 10 carbon atoms, preferably a linear or branched group having 1 to 5 carbon atoms.
• a thioalkoxy group for example, a thiomethoxy group, a thioethoxy group, a linear or branched thiopropoxy group, a linear or branched thiobutoxy group, a linear or branched thiopentoxy group
• a cyclic thioalkoxy group having 3 to 8 carbon atoms for example, thiocyclopentyl) Oxy group, thiocyclohexyloxy group).
• the non-nucleophilic anion as X ⁇ is preferably an organic anion, and particularly preferably an organic anion represented by the following general formula.
• Rc 1 represents an organic group.
• the organic group for Rc 1 include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these optionally having a substituent is a single bond, —O. -, - CO 2 -, - S -, - SO 3 -, - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.
• Rd 1 represents a hydrogen atom or an alkyl group.
• Rc 2 represents 1-position an alkyl group substituted with a fluorine atom or a fluoroalkyl group.
• Rc 3 and Rc 4 each independently represents an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group. Preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. Rc 3 and Rc 4 may be bonded to each other to form a ring. Examples of the group formed by combining Rc 3 and Rc 4 include an alkylene group, a cycloalkylene group, and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred.
• Preferred examples of the iodonium salt include compounds represented by the following general formula (TA-4).
• R 41 and R 42 each have a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituent.
• An alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent, a nitro group, a halogen atom, a hydroxyl group Represents a carboxyl group.
• a represents 1 to 5
• b represents 1 to 5.
• R 41 and R 42 has an alkyl group having 5 or more carbon atoms, which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent.
• X represents R—SO 3
• R represents an aliphatic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group which may have a substituent.
• alkyl group for R 41 and R 42 an optionally substituted methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, Examples thereof include those having 1 to 25 carbon atoms such as hexyl group, heptyl group, octyl group, t-amyl group, decanyl group, dodecanyl group and hexadecanyl group.
• the cycloalkyl group has 3 to 25 carbon atoms which may have a substituent, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecanyl group, cyclohexadecanyl group and the like. Things.
• the alkoxy group may have a substituent such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group or t-butoxy group, pentyloxy group, t Examples thereof include those having 1 to 25 carbon atoms such as -amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecanoxy group and the like.
• alkoxycarbonyl group a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group or t which may have a substituent.
• Those having 2 to 25 carbon atoms such as -butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecanoxycarbonyl group, etc. Can be mentioned.
• the acyl group may have a substituent and has 1 carbon atom such as formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group, t-amylcarbonyl group and the like. Up to 25 can be mentioned.
• acyloxy group an acetoxy group, propionyloxy group, butyryloxy group, t-butyryloxy group, t-amylyloxy group, n-hexanecarbonyloxy group, n-octanecarbonyloxy group, which may have a substituent
• substituent examples thereof include those having 2 to 25 carbon atoms such as n-dodecane carbonyloxy group, n-hexadecane carbonyloxy group, and the like.
• halogen atom there can be mentioned a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
• an alkoxy group having 1 to 4 carbon atoms a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, An alkoxycarbonyl group, a nitro group, etc. can be mentioned.
• R 1 and R 2 has 5 or more carbon atoms and may have a substituent, a cycloalkyl group that may have a substituent, An alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent .
• substituent having 5 or more carbon atoms include those having 5 to 25 carbon atoms in the above specific examples.
• examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and n-pentyl.
• Group, t-amyl group, n-hexyl group, n-octyl group and decanyl group are preferable, and the cycloalkyl group is preferably a cyclohexyl group, cyclooctyl group or cyclododecanyl group which may have a substituent.
• alkoxy group which may have a substituent
• a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, a pentyloxy group, a t-amyloxy group, n -Hexyloxy group, n-octyloxy group and n-dodecanoxy group are preferable
• the alkoxycarbonyl group may be a methoxy group which may have a substituent.
• Carbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbonyl group, n -Octyloxycarbonyl group and n-dodecanoxycarbonyl group are preferred, and the acyl group may have a substituent, formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butyl A carbonyl group and a t-amylcarbonyl group are preferable, and the acyloxy group may have an acetoxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group
• the alkyl group having 5 or more carbon atoms and optionally having a substituent is preferably an n-pentyl group, a t-amyl group, an n-hexyl group, an n-octyl group or a decanyl group.
• the cycloalkyl group having 5 or more carbon atoms and optionally having a substituent is preferably a cyclohexyl group, a cyclooctyl group or a cyclododecanyl group.
• the alkoxy group having 5 or more carbon atoms and optionally having a substituent is preferably a pentyloxy group, a t-amyloxy group, a hexyloxy group, an n-octyloxy group, or a dodecanoxy group.
• Examples of the alkoxycarbonyl group having 5 or more carbon atoms which may have a substituent include a pentyloxycarbonyl group, a t-amyloxycarbonyl group, a hexyloxycarbonyl group, an n-octyloxycarbonyl group, and dodecaneoxycarbonyl. Groups are preferred.
• the acyl group having 5 or more carbon atoms and optionally having a substituent is preferably a valeryl group, a hexanoyl group, an octanoyl group or a t-amylcarbonyl group.
• Substituents for these groups include methoxy group, ethoxy group, t-butoxy group, chlorine atom, bromine atom, cyano group, hydroxyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group Groups are preferred.
• the iodonium compound represented by formula (TA-4) used in the present invention uses sulfonic acid having a specific structure as described above as its counter anion, X ⁇ .
• X ⁇ its counter anion
• examples of the aliphatic hydrocarbon group which may have an R substituent in the counter anion include a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group.
• R can mention the aromatic group which may have a substituent.
• alkyl group for R examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, and 2-ethylhexyl, which may have a substituent. And those having 1 to 20 carbon atoms such as a group, a decyl group and a dodecyl group.
• Examples of the cyclic alkyl group include an optionally substituted cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, adamantyl group, norbornyl group, camphor group, tricyclodecanyl group, menthyl group and the like. Can do.
• Examples of the aromatic group include a phenyl group and a naphthyl group, which may have a substituent.
• alkyl group which may have a substituent of R, a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, n- Propyl group, n-butyl group, nonafluorobutyl group, n-pentyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, decyl group, dodecyl group, cyclic alkyl group A cyclopentyl group, a cyclohexyl group, and a camphor group can be mentioned.
• substituents include a methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, and 6-hydroxy-2-naphthyl group.
• R 41 and R 42 are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, t- Amyl group, n-hexyl group, n-octyl group, cyclohexyl group, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, hexyloxy group, n -Octyloxy group, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, formyl group, acetyl group,
• more preferable groups having 5 or more carbon atoms include n-pentyl group, t-amyl group, n-hexyl group, n-octyl group, decanyl group, cyclohexyl group, pentyloxy group, t-amyloxy group, Hexyloxy group, n-octyloxy group, dodecaneoxy group, pentyloxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, dodecanoxyoxycarbonyl group, valeryl group, hexanoyl group, octanoyl group A t-amylcarbonyl group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octenecarbonyloxy group.
• the more preferable sulfonic acid substituent R include methyl group, trifluoromethyl group, ethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, n-butyl group, nonafluorobutyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, camphor group, phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-fluorophenyl group, p-chlorophenyl group P-methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, 6-hydroxy-2-naphthyl group.
• the total number of carbon atoms of the acid generated is preferably 1-30. More preferably, the number is 1 to 28, and still more preferably 1 to 25. If the total number of carbon atoms is less than 1, troubles such as poor resolution due to volatilization may occur, and if it exceeds 30, the development residue may be generated.
• Specific examples of the compound represented by formula (TA-4) are shown below, but are not limited thereto. These compounds are used alone or in combination of two or more.
• Examples of the imide sulfonate compound preferable as the thermal acid generator include compounds of the following general formula.
• C 1 (carbon atom) and C 2 (carbon atom) are bonded by a single bond or a double bond
• R 51 or R 52 may be the same or different
• the following (1) to (4) Represents one of the following: (1) each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, and (2) a monocyclic or polycyclic ring that may contain one or more heteroatoms together with C 1 and C 2 .
• (3) represents a residue containing (4) N-sulfonyloxyimide that forms a condensed aromatic ring containing C 1 and C 2 .
• R 53 represents an alkyl group, a halogenated alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a camphor group.
• the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a tert-butyl group.
• the cycloalkyl group include those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like.
• aryl group examples include those having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group, and naphthyl group.
• R 51 and R 52 correspond to the case (2), for example, the following partial structure can be given.
• R 51 and R 52 correspond to the case of (3), for example, the following partial structure can be given.
• R 55 and R 56 each represents a hydrogen atom or a methyl group.
• M represents an integer of 1 to 4.
• Examples of the alkyl group for R 53 include linear or branched alkyl groups having 1 to 20 carbon atoms. Preferred is a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferred is one having 1 to 12 carbon atoms. In the case of an alkyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable.
• Examples of the halogenated alkyl group include those in which one or two or more hydrogen atoms of the alkyl group are halogenated. Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• a fluorine atom a chlorine atom and a bromine atom
• particularly preferred is a fluorine atom
• the halogen atom to be substituted may be plural types per molecule.
• the cyclic alkyl group include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group, and polycyclic substituents such as norbornyl group, adamantyl group, and tricyclodecanyl group. I can give you.
• the alkenyl group include linear or branched alkenyl groups having 2 to 20 carbon atoms.
• a straight-chain or branched alkenyl group having 2 to 16 carbon atoms is preferable, and one having 2 to 12 carbon atoms is more preferable. In the case of an alkenyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable.
• Examples of the aryl group of R 53 include a phenyl group and a naphthyl group, and examples of the aralkyl group include a benzyl group.
• Examples of the substituent of the aryl group and the aralkyl group include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a phenyl group, a toluyl group, Aryl groups such as xylyl and mesityl groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, sec-butoxy groups, tert-butoxy groups and other lower alkoxy groups, vinyl groups, allyl groups, propenyl groups, butenyl groups, etc.
• an acyl group such as alkenyl group, formyl group and acetyl group, and halogen atoms such as hydroxy group, carboxy group, cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom.
• a lower alkyl group such as a methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, cyclohexyl group, phenyl group, toluyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec-butoxy Group, lower alkoxy group such as tert-butoxy group, halogen atom such as cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom.
• substituents on the aryl group and the aralkyl group may be used. Specific examples of these compounds are shown below, but are not limited thereto.
• Preferred oxime sulfonate compounds as thermal acid generators include compounds of the following general formula.
• R 61 and R 62 are an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, substituted group which may have a substituent having 1 to 16 carbon atoms.
• R 61 and R 62 are an alkylene chain, alkenylene chain, alkynylline chain, which may have a substituent having 2 to 8 carbon atoms, or phenylene, freelen, thienylene, which may have a substituent, It may be bonded to R 61 or R 62 of the compound represented by another general formula (TA-6) through a linking chain containing —O—, —S—, —N—, and —CO—. . That is, the compound represented by the general formula (TA-6) includes those having two or three oxime sulfonate structures via a linking chain.
• R 63 represents an alkyl group, a cycloalkyl group, or an aryl group which may have a substituent, which may have a substituent having 1 to 16 carbon atoms.
• alkyl group having 1 to 16 carbon atoms in R 61 to R 63 examples include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a t-butyl group, a t-amyl group, alkyl groups such as n-hexyl group, n-octyl group, i-octyl group, n-decyl group, undecyl group, dodecyl group, hexadecyl group, trifluoromethyl group, perfluoropropyl group, perfluorobutyl group, perfluoro-t- Examples thereof include a butyl group, a perfluorooctyl group, a perfluoroundecyl group, and a 1,1-bistrifluoromethylethyl group.
• alkenyl group for R 61 and R 62 examples include allyl group, methallyl group, vinyl group, methylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 5-hexenyl group, Examples include 2-oxo-3-pentenyl group, decapentaenyl group, 7-octenyl group and the like.
• alkynyl group in R 61 and R 62 examples include ethynyl group, propargyl group, 2-butynyl group, 4-hexynyl group, 2-octynyl group, phenylethynyl group, cyclohexylethynyl group and the like.
• Examples of the cycloalkyl group in R 61 to R 63 include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
• Examples of the cycloalkenyl group for R 61 and R 62 include a cyclobutenyl group, a cyclohexenyl group, a cyclopentadienyl group, a bicyclo [4.2.4] dodeca-3,7-dien-5-yl group, and the like.
• Examples of the aryl group in R 61 to R 63 include those having 6 to 14 carbon atoms, such as phenyl group, tolyl group, methoxyphenyl group, and naphthyl group, which may have a substituent.
• the above substituents include alkyl groups, cycloalkyl groups, alkoxy groups, halogen atoms (fluorine atoms, chlorine atoms, iodine atoms), cyano groups, hydroxy groups, carboxy groups, nitro groups, aryloxy groups, alkylthio groups, aralkyls. And groups represented by the following general formula (1A).
• the alkyl group and the cycloalkyl group have the same meanings as described above.
• the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group.
• the aralkyl group include a benzyl group, a naphthylmethyl group, a furyl group, and a thienyl group.
• R 61 and R 62 have the same meanings as R 61 and R 62 in formula (TA-6).
• Preferred examples of the oxime sulfonate-based acid generator as the thermal acid generator include compounds having at least one group represented by the following general formula (TA-7).
• R 70a and R 70b each independently represents an organic group.
• the organic group of R 70a and R 70b is a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)) You may have.
• As the organic group for R 70a a linear, branched, or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent.
• the substituent is not particularly limited, and examples thereof include a fluorine atom and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.
• “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms.
• a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable.
• the partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms.
• the aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
• a partially or completely halogenated aryl group is particularly preferable.
• the partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms.
• R 70a is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.
• R 70b a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable.
• the alkyl group and aryl group for R 70b the same alkyl groups and aryl groups as those described above for R 70a can be used.
• R 70b is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.
• a compound represented by the following general formula (TA-7a) or (TA-7b) is preferably used because of its high acid generation efficiency against electron beam irradiation.
• m ′ is 0 or 1;
• X is 1 or 2;
• R 71 is a phenyl group, a heteroaryl group, or an alkyl group having 1 to 12 carbon atoms, or When m ′ is 0, an alkoxycarbonyl group having 2 to 6 carbon atoms, a phenoxycarbonyl group, CN (cyano group);
• R 72 is synonymous with R 71 ;
• R 73 ′ is 1 to 1 carbon atoms when X is 1;
• R 74 and R 75 are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms;
• A is —S— , -O-, -N (R 76 )-.
• R76 represents an alkyl group, an aryl group or an aral
• R 71 ′ is an alkylene group having 2 to 12 carbon atoms; R 72 , R 74 , R 75 and A are as defined above; R 73 is an alkyl group having 1 to 18 carbon atoms. . ]
• the following thiolene-containing oxime sulfonate is particularly preferable.
• Preferred examples of the general formula of nitrobenzyl sulfonate include compounds represented by the general formula (TA-9).
• Z in this formula is alkyl group, aryl group, alkylaryl group, halogen-substituted alkyl group, halogen-substituted aryl group, halogen-substituted alkylaryl group, nitro-substituted aryl group, nitro-substituted
• Q m (NO ) is selected from groups having 2, R represents a hydrogen atom or a methyl group, R 'are selected from hydrogen atoms and methyl groups, and nitro substituted aryl groups, each Q is a hydrocarbon group, hydrocarbonoxy carboxymethyl Independently selected from the group, NO 2 , halogen atoms and organosilicon groups, the value of m being 0, 1
• sulfonic acid esters can be used.
• a sulfonic acid ester represented by the following general formula (TA-1) can be given.
• R ′ and R ′′ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or an optionally substituted carbon group having 6 carbon atoms.
• Preferable specific examples of the sulfonic acid ester include the following.
• TA-2 a compound represented by the following general formula (TA-2) is more preferable from the viewpoint of heat resistance.
• the molecular weight of the sulfonate ester is generally 230 to 1000, preferably 230 to 800.
• A represents an h-valent linking group.
• R 0 represents an alkyl group, an aryl group, an aralkyl group, or a cyclic alkyl group.
• R 0 ′ represents a hydrogen atom, an alkyl group, or an aralkyl group.
• h represents an integer of 2 to 8.
• the h-valent linking group as A includes, for example, an alkylene group (eg, methylene, ethylene, propylene, etc.), a cycloalkylene group (eg, cyclohexylene, cyclopentylene, etc.), an arylene group (1,2-phenylene, 1,3). -Phenylene, 1,4-phenylene, naphthylene, etc.), an ether group, a carbonyl group, an ester group, an amide group, and a group obtained by removing h-2 arbitrary hydrogen atoms from a divalent group combining these groups. Can be mentioned.
• the carbon number of the h-valent linking group as A is generally 1 to 15, preferably 1 to 10, and more preferably 1 to 6.
• the alkyl group for R 0 and R 0 ′ is generally an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. is there. Specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl and the like.
• the aralkyl group for R 0 and R 0 ′ is generally an aralkyl group having 7 to 25 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 15 carbon atoms. is there.
• the cyclic alkyl group for R 0 is generally a cyclic alkyl group having 3 to 20 carbon atoms, preferably a cyclic alkyl group having 4 to 20 carbon atoms, more preferably a cyclic alkyl group having 5 to 15 carbon atoms. is there. Specific examples include cyclopentyl, cyclohexyl, norbornyl, camphor group and the like.
• the linking group as A may further have a substituent.
• the substituent is an alkyl group (an alkyl group having 1 to 10 carbon atoms, specifically, methyl, ethyl, propyl, butyl, hexyl). Octyl, etc.), aralkyl groups (aralkyl groups having 7 to 15 carbon atoms, specifically benzyl, toluylmethyl, mesitylmethyl, phenethyl, etc.), aryl groups (aryl groups having 6 to 10 carbon atoms, specifically Are phenyl, toluyl, xylyl, mesityl, naphthyl, etc.), an alkoxy group (the alkoxy group may be linear, branched or cyclic, and has 1 to 10 carbon atoms, specifically, Methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentoxy, cyclopentyloxy, cyclohexy
• R 0 is preferably an alkyl group or an aryl group.
• R 0 ′ is preferably a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom.
• Examples of the sulfonic acid ester of the present invention include the following specific compounds, but are not limited thereto.
• sulfonic acid ester of the present invention a commercially available one may be used, or one synthesized by a known method may be used.
• the sulfonic acid ester of the present invention can be synthesized, for example, by reacting sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
• the content of the thermal acid generator is preferably 1 to 20% by mass, more preferably 3 to 10% by mass based on the total solid content of the photosensitive resin composition.
• composition of the present invention may contain a compound containing at least one of alkoxymethyl group and acyloxymethyl group. Even in the low-temperature curing process, it is possible to prevent melting and thermal shrinkage of the pattern during curing.
• an alkoxymethyl group or an acyloxymethyl group a compound in which an alkoxymethyl group or an acyloxymethyl group is substituted directly on an aromatic group or a nitrogen atom of the following urea structure on a triazine
• the alkoxymethyl group or acyloxymethyl group of the compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
• the total number of alkoxymethyl groups and acyloxymethyl groups possessed by the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
• the molecular weight of the compound is preferably 1500 or less, and preferably 180 to 1200.
• R 100 represents an alkyl group or an acyl group.
• R 101 and R 102 independently represent a monovalent organic group, and may be bonded to each other to form a ring.
• Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include compounds having the following general formula.
• X represents a single bond or a divalent organic group
• each R 104 independently represents an alkyl group or an acyl group
• R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, Or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated by the action of an acid, a group represented by —C (R 4 ) 2 COOR 5 (R 4 is a hydrogen atom or a carbon number) Represents an alkyl group of 1 to 4, and R 5 represents a group capable of leaving by the action of an acid))).
• R 105 each independently represents an alkyl group or an alkenyl group
• a, b and c are each independently 1 to 3
• d is 0 to 4
• e is independently 0 to 3.
• the group capable of decomposing by the action of an acid to generate an alkali-soluble group, the group leaving by the action of an acid, and the group represented by —C (R 4 ) 2 COOR 5 are the same as those in the general formula (1). is there.
• Examples of the compound having an alkoxymethyl group include the following structures.
• Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group.
• Examples of the compound having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
• the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available product or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
• the addition amount of these compounds is preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the total amount of the resin of the present invention.
• composition of the present invention may contain a compound containing methacryloyl group or acryloyl group.
• the compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. Since these compounds are insoluble in an alkaline developer, they have a function of suppressing the alkali solubility of the composition, and are useful for good image formation in order to suppress film loss in unexposed areas.
• the molecular weight of components constituting the composition partially increases due to the reaction of the acrylic group or methacrylic group with the compound in the composition at the stage of the cure reaction.
• the film properties are improved. Therefore, it is preferable to use a compound having two or more acryloyl groups and methacryloyl groups in one molecule, more preferably four or more functional groups, because this compound can exhibit a function as a crosslinking compound.
• EO ethylene oxide
• PO propylene oxide
• NK-10 series made by Shin-Nakamura Chemical Co., Ltd., monofunctional AMP-10G, AMP-20GY, AM30G, AM90G, AM230G, ACB-3, A-BH, A-IB, A-SA, A -OC-18E, 720A, S-1800A, ISA, AM-130G, LA, M-20G, M-90G, M230G, PHE-1G, SA, CB-1, CB-3, CB-23, TOPOLENE-M , S-1800M, IB, OC-18E, S, bifunctional A-200, A-400, A-600, A-1000, ABE-300, A-BPE-4, A-BPE-10, A- BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A-B1206PE, A-HD-N A-NOD-N, APG-100, APG-200
• the addition amount of the compound containing a methacryloyl group or an acryloyl group in the molecule of the present invention is 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin having a repeating unit represented by the general formula (1). Is preferred. More preferably, they are 1 mass part or more and 20 mass parts or less, Most preferably, they are 2 mass parts or more and 15 mass parts or less.
• an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent for imparting adhesion may be added as necessary.
• an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent for imparting adhesion may be added as necessary. Examples of these are, for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl.
• an adhesion promoter it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin of the present invention.
• (G) Solvent The solvent is not particularly limited as long as it can dissolve the composition of the present invention. However, in order to prevent the solvent from evaporating more than necessary at the time of coating and precipitating the solid content of the composition at the time of coating, Solvents with the above boiling points are preferred. For example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound (preferably carbon And organic solvents such as alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, and amide solvents.
• alkylene glycol monoalkyl ether carboxylate examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
• alkylene glycol monoalkyl ether examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
• alkyl lactate examples include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
• alkyl alkoxypropionate examples include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.
• cyclic lactone examples include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and ⁇ -octano.
• Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone
• alkylene carbonate examples include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
• alkyl alkoxyacetates examples include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
• Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
• amide solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, and 1,3-dimethyl-2-imidazolidinone.
• dimethyl sulfoxide and sulfolane are preferable.
• N-methylpyrrolidone (NMP), ⁇ -butyrolactone (GBL), N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI) are more preferable solvents.
• N, N-dimethylformamide (DMF) cyclopentanone, cyclohexanone, cycloheptanone and the like.
• the total solid concentration in the photosensitive resin composition of the present invention is generally 10 to 40% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 30% by mass.
• [Relief pattern manufacturing method] As a method for producing a relief pattern using the photosensitive resin composition of the present invention, (a) the photosensitive resin composition of the present invention is coated on an appropriate substrate to form a photosensitive film, and (b) The coated substrate is baked (pre-baked), (c) exposed with actinic light or radiation, (d) developed with an aqueous developer, and (e) cured to form a cured relief pattern. be able to.
• —CO 2 R 3 in the general formula (1) is decomposed by the action of an acid to generate an alkali-soluble group, which is developed so as to be removed with an aqueous alkaline developer.
• a positive cured relief pattern can be obtained.
• the coated and exposed substrate can be baked at a high temperature (post-exposure baking) prior to development. Further, the developed substrate may be rinsed before curing.
• the photosensitive resin composition of the present invention is applied on a semiconductor element so that the thickness after heat curing becomes a predetermined thickness (for example, 0.1 to 30 ⁇ m), prebaked, exposed, developed, and heat cured.
• a predetermined thickness for example, 0.1 to 30 ⁇ m
• the photosensitive resin composition of the present invention is coated on a suitable substrate.
• the substrate is for example a semiconductor material such as a silicon wafer or a ceramic substrate, glass, metal or plastic.
• Coating methods include, but are not limited to, spray coating, spin coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and dip coating.
• the coating film is baked at a temperature of about 70 to 150 ° C. for several minutes to half an hour in order to evaporate the residual solvent. Subsequently, the resulting film is exposed to actinic rays or radiation through a mask.
• actinic ray or radiation X-ray, electron beam, ultraviolet ray, visible ray or the like can be used.
• the most preferred radiation is one having a wavelength of 365 nm (i-line) or 436 nm (g-line).
• the exposed substrate is preferably heated at a temperature of about 70-150 ° C. Usually, it is heated at a predetermined temperature for several tens of seconds to several minutes. This method is referred to as post-exposure baking.
• post-exposure baking a polyamic acid is produced from the polyamic acid ester in the general formula (1) as shown in the following scheme.
• the coating film can be developed with an aqueous developer to obtain a relief pattern.
• aqueous developer include inorganic alkali (eg, potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amine (eg, ethylamine, n-propylamine), secondary amine (eg, diethylamine, di-n-propyl). Amines), tertiary amines (eg, triethylamine), alcohol amines (eg, triethanolamine), quaternary ammonium salts (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide), and alkaline solutions such as mixtures thereof Is mentioned.
• the most preferred developer is one containing tetramethylammonium hydroxide.
• an appropriate amount of a surfactant may be added to the developer. Development can be carried out by dipping, spraying, paddling, or other similar development methods.
• the relief pattern may be rinsed using deionized water.
• polyimide is produced from the polyamic acid ester by heat-curing the relief pattern as shown in the following scheme.
• baking at a glass transition temperature Tg or higher of the polymer is preferable in order to obtain a polyimide having high heat resistance.
• the heat curing temperature is preferably about 200 to 400 ° C, particularly preferably 250 to 400 ° C.
• GPC measurement in the following is performed by directly connecting three HPC-8220GPC (manufactured by Tosoh), guard column: TSKguardcolumn SuperAW-H, column: TSKgel SuperAWM-H, column temperature of 50 ° C., and sample concentration of 0.5 mass%. Inject 20 ⁇ l of -2-pyrrolidone solution, and flow N-methyl-2-pyrrolidone solution (containing LiBr (10 mM) and H 3 PO 4 (10 mM)) as an elution solvent at a flow rate of 0.35 ml / min. This was done by detecting the sample peak with a detector. Mw and Mn were calculated using a calibration curve prepared using standard polystyrene.
• reaction solution was added to 1267 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 23.6 g of the desired product (resin P-3) as a white solid.
• the solid was dissolved in deuterated DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 96%.
• reaction solution was added to 1175 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 20.2 g of the desired product (resin P-8) as a white solid.
• the solid was dissolved in heavy DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 64%.
• reaction solution was added to 947 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 13.5 g of the desired product (resin P-11) as a white solid.
• the solid was dissolved in deuterated DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 73%.
• reaction solution was added to 940 g of acetonitrile, and the precipitated solid was collected by filtration and dried to obtain 16.5 g of the desired product (resin P-16) as a white solid.
• the solid was dissolved in heavy DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 69%.
• Polyamic acid was synthesized in the same manner as P-1, and 79.19 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 39.18 g of NMP was added, and 19.92 g of the vinyl ether was added. 0.72 g of 10-camphorsulfonic acid was sequentially added. After reacting at 25 ° C. for 5 hours, the reaction solution was added to 705 g of acetonitrile, and the precipitated solid was collected by filtration and dried to obtain 15.1 g of the desired product (resin P-26) as a white solid.
• Polyamic acid was synthesized in the same manner as P-1, and 79.19 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, 39.18 g of NMP was added, and 19.36 g of the vinyl ether was added. 0.72 g of 10-camphorsulfonic acid was added sequentially. After reacting at 25 ° C. for 5 hours, the reaction solution was added to 705 g of acetonitrile, and the precipitated solid was collected by filtration and dried to obtain 17.6 g of the desired product (resin P-26) as a white solid.
• Polyamic acid was synthesized in the same manner as P-1, and 132.8 g of this polyamic acid solution was added to a 500 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 65.68 g of NMP was added and cooled to 0 ° C. or lower. 25.58 g of the above solution was added followed by 23.25 g of N, N-diisopropylethylamine. After reacting at 0 ° C. or lower for 4 hours, the reaction solution was added to 1182 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 29.19 g of the desired product (resin P-29) as a white solid.
• the reaction solution was added to 700 ml of methanol, and the precipitated solid was collected by filtration and further reslurried with 1000 ml of acetonitrile.
• the solid was dissolved in 100 ml of NMP, 0.89 g of phthalic anhydride was added, and the mixture was stirred at 50 ° C. for 1 hour.
• the reaction solution was added to 800 ml of methanol / 200 ml of water and dried to obtain 15.6 g of the desired product (resin P-31) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• the mixture was allowed to cool, neutralized with 600 ml of 1M hydrochloric acid, extracted with 1000 ml of ethyl acetate, and the organic layer was washed successively with saturated brine twice and water twice.
• 500 ml of 1M NaOH was added, and the aqueous layer was extracted and washed with 300 ml of ethyl acetate.
• the aqueous layer was neutralized with 500 ml of 1M-hydrochloric acid and extracted with 500 ml of ethyl acetate, and the organic layer was washed successively with saturated brine twice and with water twice.
• the extract was dried over sodium sulfate and concentrated under reduced pressure to obtain 76.4 g of a dicarboxylic acid having the following structure.
• reaction solution was added to 1267 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 34.07 g of the desired product (resin P-34) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• a polyamic acid was synthesized in the same manner as P-1, and 142.3 g of this polyamic acid solution was added to a 500 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 70.38 g of NMP was added. 37.76 g of halide and 16.60 g of N, N-diisopropylethylamine were added. After reacting at room temperature for 7 hours, the reaction solution was added to 1267 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 36.97 g of the desired product (resin P-36) as a brown solid.
• Polyamic acid was synthesized in the same manner as P-1, and 133.10 g of this polyamic acid solution was added to a 500 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, 65.87 g of NMP was added, and the above was performed at 0 ° C. or lower. 36.46 g of halide and 15.65 g of N, N-diisopropylethylamine were added. After reacting at room temperature for 8 hours, the reaction solution was added to 1186 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 41.21 g of the desired product (resin P-39) as a brown solid.
• reaction solution was added to 1308 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 31.8 g of the desired product (resin P-47) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• reaction solution was added to 1047 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 20.5 g of the desired product (resin P-52) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• Polyamic acid was synthesized in the same manner as P-41, and 88.13 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 74.20 g of NMP was added, and 9.63 g of the vinyl ether was added. 0.73 g of 10-camphorsulfonic acid was sequentially added. After reacting at 25 ° C. for 5 hours, the reaction solution was added to 786 g of acetonitrile, and the precipitated solid was collected by filtration and dried to obtain 12.6 g of the desired product (resin P-55) as a white solid.
• reaction solution was added to 1218 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 26.1 g of the desired product (resin P-93) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• Polyamic acid was synthesized in the same manner as P-41, and 125.8 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 62.3 g of NMP was added and cooled to 0 ° C. or lower. Then, 17.71 g of N, N-diisopropylethylamine was added, followed by 27.69 g of the transparent liquid for the compound represented by the structure (b5-1). After reacting at 0 ° C.
• the obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain 97.2 g of a transparent liquid.
• 97.2 g of a transparent liquid After adding 97.2 g of the above solution, 43.0 g of acetyl chloride, and 10 mg of zinc chloride in a 300 mL flask equipped with a thermometer, a stirrer, and a calcium chloride tube, the mixture was reacted at room temperature for 8 hours, and then concentrated under reduced pressure. 93.8 g of a compound represented by the structure (b5-2) was obtained as a transparent liquid.
• Polyamic acid was synthesized in the same manner as P-41, and 125.8 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 62.3 g of NMP was added and cooled to 0 ° C. or lower. 16.60 g of N, N-diisopropylethylamine was added, followed by 33.07 g of the transparent liquid for the compound represented by the structure (b5-2). After reacting at 0 ° C.
• the reaction solution was added to 1.5 L of methanol, and the precipitated solid was collected by filtration and dried to obtain 23.86 g of the desired product (resin P-111) as a white solid.
• the solid was dissolved in deuterated DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 99%.
• the endothermic peak top temperature was 210 ° C.
• the weight reduction rate was 42%. This weight reduction rate corresponds to the weight of R 3 in the repeating unit represented by the general formula (1), and it can be seen that the thermal decomposition temperature of R 3 is 210 ° C.
• a polyamic acid was synthesized in the same manner as P-41, and 260.4 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 129.2 g of NMP was added and cooled to 0 ° C. or lower.
• N, N-diisopropylethylamine (36.55 g) was added, followed by 216.87 g of the transparent liquid for the compound represented by the structure (b5-3). After reacting at 0 ° C.
• Polyamic acid was synthesized in the same manner as P-41, and 125.8 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 62.3 g of NMP was added and cooled to 0 ° C. or lower.
• N, N-diisopropylethylamine (16.60 g) was added, followed by 43.66 g of the clear liquid for the compound represented by the structure (b5-4). After reacting at 0 ° C.
• the reaction solution was added to 1.5 L of methanol, and the precipitated solid was collected by filtration and dried to obtain 26.40 g of the desired product (resin P-113) as a white solid.
• the solid was dissolved in deuterated DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, and it was 88%.
• differential thermal balance analysis of the resin P-113 was performed, the endothermic peak top temperature was 177 ° C., and the weight loss rate was 46%. This weight reduction rate corresponds to the weight of R 3 in the repeating unit represented by the general formula (1), and it can be seen that the thermal decomposition temperature of R 3 is 177 ° C.
• the obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and concentrated under normal pressure to obtain 58.3 g of a transparent liquid.
• a 500 mL flask equipped with a thermometer, a stirrer, and a calcium chloride tube 58.3 g of the above solution, 42.0 g of acetyl chloride, and 10 mg of zinc chloride were added and reacted at 50 ° C. for 24 hours, and represented by the following structure (b5-5) 81.0 g of the resulting compound was obtained as a clear liquid.
• Polyamic acid was synthesized in the same manner as P-41, and 125.8 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 62.3 g of NMP was added and cooled to 0 ° C. or lower. Then, 22.14 g of N, N-diisopropylethylamine was added, followed by 33.16 g of the transparent liquid for the compound represented by the structure (b5-5). After reacting at 0 ° C.
• the reaction solution was added to 1.5 L of methanol, and the precipitated solid was collected by filtration and dried to obtain 20.12 g of the desired product (resin P-114) as a white solid.
• the solid was dissolved in deuterated DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, and found to be 91%.
• the endothermic peak top temperature was 163 ° C.
• the weight reduction rate was 32%. This weight reduction rate corresponds to the weight of R 3 in the repeating unit represented by the general formula (1), and it can be seen that the thermal decomposition temperature of R 3 is 163 ° C.
• Polyamic acid was synthesized in the same manner as P-41, and 125.8 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 62.3 g of NMP was added and cooled to 0 ° C. or lower. Then, 22.14 g of N, N-diisopropylethylamine was added, followed by 35.80 g of the transparent liquid for the compound represented by the structure (b5-6). After reacting at 0 ° C.
• the reaction solution was added to 1.5 L of methanol, and the precipitated solid was collected by filtration and dried to obtain 19.76 g of the desired product (resin P-115) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured.
• the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• the endothermic peak top temperature was 164 ° C.
• the weight loss rate was 42%. This weight reduction rate corresponds to the weight of R 3 in the repeating unit represented by the general formula (1), and it can be seen that the thermal decomposition temperature of R 3 is 164 ° C.
• a polyamic acid was synthesized in the same manner as P-41, and 250.0 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 124.0 g of NMP was added and cooled to 0 ° C. or lower. Then, 28.51 g of N, N-diisopropylethylamine was added, followed by 40.82 g of the transparent liquid for the compound represented by the structure (b5-9). After reacting at 0 ° C.
• the reaction solution was added to 2.7 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 66.54 g of the desired product (resin P-118) as a white solid.
• the solid was dissolved in deuterated DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 99%.
• the endothermic peak top temperature was 165 ° C.
• the weight loss rate was 44%. This weight reduction rate corresponds to the weight of R 3 in the repeating unit represented by the general formula (1), and it can be seen that the thermal decomposition temperature of R 3 is 165 ° C.
• Polyamic acid was synthesized in the same manner as P-41, and 125.0 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, and 62.0 g of NMP was added and cooled to 0 ° C. or lower. 16.45 g of N, N-diisopropylethylamine was added, followed by 68.97 g of the clear liquid for the compound represented by the structure (b5-10). After reacting at 0 ° C.
• the reaction solution was added to 1.5 L of methanol, and the precipitated solid was collected by filtration and dried to obtain 29.96 g of the desired product (resin P-120) as a white solid.
• the solid was dissolved in deuterated DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 96%.
• the endothermic peak top temperature was 162 ° C., and the weight loss rate was 50%.
• This weight reduction rate corresponds to the weight of R 3 in the repeating unit represented by the general formula (1), and it can be seen that the thermal decomposition temperature of R 3 is 162 ° C. Furthermore, an endothermic peak that was considered to be an imide ring closure at 198 ° C. was also observed.
• a polyamic acid was synthesized in the same manner as P-41, and 260.4 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 129.2 g of NMP was added and cooled to 0 ° C. or lower.
• N, N-diisopropylethylamine (36.55 g) was added, and then 173.21 g of the transparent liquid for the compound represented by the structure (b5-11) was added. After reacting at 0 ° C.
• the reaction solution was added to 3 L of methanol, and the precipitated solid was collected by filtration and dried to obtain 64.02 g of the desired product (resin P-122) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• the endothermic peak top temperature was 163 ° C., and the weight reduction rate was 54%.
• This weight reduction rate corresponds to the weight of R 3 in the repeating unit represented by the general formula (1), and it can be seen that the thermal decomposition temperature of R 3 is 163 ° C. Furthermore, an endothermic peak that was considered to be imide ring closure at 206 ° C. was also observed.
• the obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and then concentrated under normal pressure to obtain 82.1 g of a transparent liquid.
• a 200 mL flask equipped with a thermometer, a stirrer, and a calcium chloride tube 76.6 g of the above solution, 17.0 g of acetyl chloride and 10 mg of zinc chloride were added and reacted at 50 ° C. for 12 hours, and represented by the following structure (b5-14) 112.0 g of the resulting compound was obtained as a clear liquid.
• Polyamic acid was synthesized in the same manner as P-41, and 125.8 g of this polyamic acid solution was added to a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introducing tube, and 62.3 g of NMP was added and cooled to 0 ° C. or lower. Then, 17.71 g of N, N-diisopropylethylamine was added, followed by 51.47 g of the transparent liquid for the compound represented by the structure (b5-14). After reacting at 0 ° C.
• the reaction solution was added to 1.5 L of methanol, and the precipitated solid was collected by filtration and dried to obtain 15.27 g of the desired product (resin P-127) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• differential thermal balance analysis of the resin P-127 was performed, the endothermic peak top temperature was 230 ° C., and the weight reduction rate was 37%. This weight reduction rate corresponds to the weight of R 3 in the repeating unit represented by the general formula (1), and it can be seen that the thermal decomposition temperature of R 3 is 230 ° C.
• reaction solution was added to 2.6 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 62.92 g of the desired product (resin P-130) as a white solid.
• the solid was dissolved in deuterated DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 99%.
• reaction solution was added to 3.1 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 70.16 g of the desired product (resin P-131) as a white solid.
• the solid was dissolved in deuterated DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 99%.
• reaction solution was added to 3 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 71.19 g of the desired product (resin P-133) as a white solid.
• the solid was dissolved in deuterated DMSO, 1 H-NMR spectrum was measured, and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 99%.
• reaction solution was added to 3.2 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 73.07 g of the desired product (resin P-141) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• reaction solution was added to 3.2 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 72.50 g of the desired product (resin P-143) as a white solid.
• the solid was dissolved in heavy DMSO, and the 1 H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester to the carboxylic acid, which was 100%.
• the prepared photosensitive resin composition was spin-coated on a 4 inch silicon wafer and pre-dried at 120 ° C. for 3 minutes on a hot plate to obtain a film having a thickness of 5.0 ⁇ m.
• pattern exposure was performed using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon, Inc.) using a 1-30 ⁇ m via hole repeating pattern mask. Subsequently, it was heated at 120 ° C. for 3 minutes, subjected to paddle development with a 2.38 mass% TMAH aqueous solution, and rinsed with pure water. Thereafter, heating was performed on a hot plate at 100 ° C. for 2 minutes.
• the obtained pattern film was observed with a length measuring SEM (Hitachi Ltd. S-8840), and the resolved via hole had a minimum dimension of less than 3 ⁇ m A, 3 ⁇ m to 5 ⁇ m B, 5 ⁇ m to 10 ⁇ m C 10 ⁇ m or more was designated as D.
• ⁇ Sensitivity> The obtained pattern film was observed with a length measurement SEM (Hitachi, Ltd. S-8840), and the exposure amount obtained by resolving the via hole having the smallest dimension was defined as sensitivity.
• a less than 250 mJ / cm 2 was A, 250 mJ / cm 2 or more.
• the prepared photosensitive resin composition was spin-coated on a 4 inch silicon wafer and pre-dried at 120 ° C. for 3 minutes on a hot plate to obtain a film having a thickness of 5.0 ⁇ m. Subsequently, the polyimide film was obtained by heat curing at 250 ° C. for 60 minutes under nitrogen. ⁇ Stress> The cured film was measured for stress at 25 ° C. with a thin film stress measuring device (FLX-2320, manufactured by Tencor). A smaller stress value means a smaller amount of wafer warpage.
• the numerical value in parentheses when using a solvent together represents a mass ratio.
• DIA 2,6-diisopropylaniline
• PEA N-phenyldiethanolamine
• DBU 1,8-diazabicyclo [5.4.0] undec-7-ene
• EOA amine having the following structure
• GPTMS 3-glycidyloxypropyltrimethoxysilane
• MAPTMS 3-methacryloxypropyltrimethoxysilane
• TESPEC triethoxysilylpropyl ethyl carbamate
• GBL ⁇ -butyrolactone
• NMP N-methylpyrrolidone
• CX cyclohexanone
• CP cycloheptanone
• DMI 1,3-dimethyl-2-imidazolidinone
• DPHA Dipentaerythritol hexaacrylate
• Comparative Example 1 having an acid-decomposable group as R 3 in the general formula (1) but not having an alicyclic group as R 2 has a solubility in an alkali developer. It can be seen that sufficient results cannot be obtained with respect to image performance such as resolution and sensitivity. It can also be seen that the wafer is warped due to the large stress. Comparative Example 2 having an alicyclic group as R 2 but not having an acid-decomposable group as R 3 does not reveal even a latent image, and gives satisfactory results for image performance such as resolution and sensitivity. I can't understand. It can also be seen that the wafer is warped due to the large stress.
• Comparative Example 3 having an acid-decomposable group as R 3 in the general formula (1) but not having an alicyclic group as R 2 , the image performance such as resolution and sensitivity is relatively good, but the stress is large. It can be seen that wafer warpage can occur.
• Examples 1 to 146 using the resin (a) satisfying the requirement of the general formula (1) are excellent in image performance such as resolution and sensitivity, have small stress, and can suppress the occurrence of wafer warpage. .
• a surface protective film for semiconductor devices an interlayer insulating film, an interlayer insulating film for display devices, has lithography performance with excellent resolution and sensitivity, and has low stress in low-temperature curing.
• a relief pattern forming material a photosensitive film, a polyimide film, a cured relief pattern, a manufacturing method thereof, and a semiconductor device including the cured relief pattern, which have excellent characteristics and can form a cured relief pattern that prevents warpage of the wafer. can do.

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