WO2007126050A1 - Agent protecteur - Google Patents

Agent protecteur Download PDF

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Publication number
WO2007126050A1
WO2007126050A1 PCT/JP2007/059161 JP2007059161W WO2007126050A1 WO 2007126050 A1 WO2007126050 A1 WO 2007126050A1 JP 2007059161 W JP2007059161 W JP 2007059161W WO 2007126050 A1 WO2007126050 A1 WO 2007126050A1
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WO
WIPO (PCT)
Prior art keywords
atom
alkyl
sulfur atom
oxygen atom
aryl
Prior art date
Application number
PCT/JP2007/059161
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English (en)
Japanese (ja)
Inventor
Hiroshi Matsuoka
Ryo Numazaki
Iwao Hotta
Original Assignee
Kyowa Hakko Chemical Co., Ltd.
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Publication date
Application filed by Kyowa Hakko Chemical Co., Ltd. filed Critical Kyowa Hakko Chemical Co., Ltd.
Priority to JP2008513290A priority Critical patent/JPWO2007126050A1/ja
Publication of WO2007126050A1 publication Critical patent/WO2007126050A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/175—Saturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B51/00—Introduction of protecting groups or activating groups, not provided for in the preceding groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • 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

Definitions

  • the present invention relates to a protective agent useful for uses such as a chemically amplified resist composition, a pharmaceutical synthesis intermediate, a paint, and a protective group of a carboxyl group or a hydroxyl group.
  • Hemiacetal ester or acetal is easily desorbed from alkyl vinyl ethers by heat or acid catalyst, etc., and therefore chemically amplified resist composition, pharmaceutical synthesis intermediate, paint, carboxyl It is useful for applications such as protecting groups of hydroxyl groups.
  • the hemiacetal ester and acetal are usually prepared by reacting a compound having a carboxyl group or a hydroxyl group with an alkyl vinyl ether or a halogenated alkyl ether obtained by adding a hydrogen halide to an alkyl butyl ether as a protective agent. Manufactured from this.
  • alkyl butyl ethers and halogenated alkyl ethers are extremely unstable and easily polymerized.
  • 1 chloroethyl ether produced by the reaction of ethyl butyl ether and hydrogen halide is reacted with a polymer having a carboxyl group or a hydroxyl group
  • 1 chloroethyl ether When ether-derived polymers are by-produced! There was a habit problem.
  • R a , R b and R e are the same or different and represent a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl or a substituted or unsubstituted aralkyl, R a and R b together with the adjacent carbon atom forms a cycloalkyl, X represents a halogen atom
  • Patent Document 1 International Publication No. 2003Z006407 Pamphlet
  • Patent Document 2 International Publication No. 2005Z023880 Pamphlet
  • An object of the present invention is useful for applications such as chemically amplified resist compositions, pharmaceutical synthesis intermediates, paints, protective groups for carboxyl groups and hydroxyl groups, and the adhesion of the protected body to a substrate.
  • Another object of the present invention is to provide a protective agent excellent in wettability with respect to a soldering solution or the like, and a protective body in which a carboxyl group or a hydroxyl group is protected with the protective agent.
  • the present invention provides the following (1) one (21).
  • R 1 and R 2 may be the same or different and represent a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl or a substituted or unsubstituted aralkyl, and R 1 and R 2 together with adjacent carbon atoms.
  • A represents an oxygen atom or a sulfur atom
  • Y 3 represents a bond, an oxygen atom or a sulfur atom
  • R b represents a hydrogen atom, an alkyl, an aryl or an aralkyl.
  • A is a sulfur atom
  • R 3 is an alkyl A protective group for a hydroxyl group or a carboxyl group containing a compound represented by)].
  • R aa (where q is an integer from 1 to 3, and R aa is a hydrogen atom, alkyl, aryl or
  • R e represents a hydrogen atom, an alkyl, Ariru or Araru kill), or a heterocyclic group containing an oxygen atom and Z or sulfur atom of (1) to (3), the deviation The protective agent according to crab.
  • a compound having a hydroxyl group is represented by the general formula (I)
  • R aa (where q is an integer from 1 to 3, and R aa is a hydrogen atom, alkyl, aryl or
  • R represents a hydrogen atom, a halogen atom, hydroxy, substituted or unsubstituted alkoxy, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted aralkyl. All or part of the hydroxyl groups of the polymer having a weight average molecular weight of 1,000-100,000 are represented by the general formula (III)
  • R aa (where q is an integer from 1 to 3, and R aa is a hydrogen atom, alkyl, aryl or
  • R 5 represents a hydrogen atom, a halogen atom, hydroxy, substituted or unsubstituted alkoxy, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted aralkyl
  • R 6 and R 7 are the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted aralkyl. All or part of the hydroxyl groups of the polymer having a weight average molecular weight of 1,000-100,000.
  • R aa (where q is an integer from 1 to 3, and R aa is a hydrogen atom, alkyl, aryl or
  • R 8 represents a hydrogen atom, lower alkyl or hydroxymethyl
  • R aa (where q is an integer from 1 to 3, and R aa is a hydrogen atom, alkyl, aryl or
  • a compound having a group represented by the general formula ( ⁇ ) described in (5) having a weight average molecular weight of 1,000 to 100,000, or represented by the general formula (IV) described in (6) A chemically amplified resist composition comprising a compound having a group and a photoacid generator.
  • a chemically amplified resist composition comprising the polyhydroxystyrene derivative according to (12) or (13) and a photoacid generator.
  • a chemically amplified resist composition comprising the novolak rosin derivative according to (14) or (15) and a photoacid generator.
  • a chemically amplified resist composition comprising the polyacrylic resin derivative or polymethacrylic resin derivative according to (16) or (17) and a photoacid generator.
  • a hydroxyl group or carboxyl group protective agent excellent in adhesion of a protective body to a substrate, wettability with respect to a solder or a staking solution, and the like, and a protective body protected with the protective agent. can do.
  • examples of the alkyl moiety of alkyl and alkoxy include linear, branched, or cyclic ones having 1 to 18 carbon atoms.
  • a linear or branched alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butynole, pentinole, hexyl, heptyl, octinole, noninore, decinole, dodecyl, octadecyl, Cyclopropyl, cyclopetit Nole, cyclopentinole, cyclohexinole, cycloheptinole, cyclooctenole, cyclodecane, cyclodode force, etc.
  • cycloalkyl adamantyl, tricyclode force, tetracyclodode force, bolol, norbolol, isonorbol -Ruyl, spiroheptyl, spirooctyl, menthyl and other polycyclic alkyls, cyclopropylmethyl, cyclobutylmethyl, cyclopentinoremethinole, cyclohexenoremethinole, cyclopropinoreethinole, cyclobutinoreethyl, cyclopentyl
  • cycloalkylalkyl such as til and cyclohexylethyl, among which alkyl having 16 carbon atoms is preferable, and alkyl having 13 carbon atoms is more preferable.
  • the lower alkyl includes, for example, linear or branched alkyl having 18 carbon atoms, and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec butyl, tert Examples include butyl, pentyl, hexyl, heptyl, octyl and the like.
  • aryls include those having 6 to 14 carbon atoms, and specific examples thereof include phenyl and naphthyl.
  • Examples of the aralkyl include those having 7 to 15 carbon atoms, and specific examples thereof include benzyl, phenethyl, naphthylmethyl, naphthylethyl and the like.
  • Examples of the alicyclic hydrocarbon ring formed by R 1 and R 2 together with adjacent carbon atoms include those having 3 to 8 carbon atoms, and may be saturated or unsaturated.
  • Specific examples of gusset include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclopentene ring, 1,3 cyclopentagen ring, cyclohexene ring, cyclohexagen. Examples include rings.
  • Preferred examples of the heterocyclic group containing an oxygen atom and Z or a sulfur atom include, for example, a furyl group, a tetrahydrofuryl group, a biral group, a tetrahydrobiranyl group, a dixolanyl group, and a dioxanyl group.
  • R e are as defined above), heterocyclic groups containing an oxygen atom and Z or a sulfur atom, and more specifically, oxo, thixo, hydroxy, methoxy, ethoxy, propyloxy, isopropylo Xy, butoxy, cyclopentyloxy, cyclohexyloxy, phenoxy, benzyloxy, mercapto, methanesulfuryl, ethanesulfanyl, propanesulfanyl, isopropanesulfanyl, butanesulfanyl, cyclopentanesulfuryl, cyclohexanesulfur, Benzenesulfuryl, benzylsulfanyl, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isoparelinore, pivaloinor, thioacetinole, thiopropioninore, thiobut
  • Examples of the substituent in the substituted alkyl and the substituted alkoxy include alkoxy, alkanol, nitro-containing nitro, halogen atom, alkoxy carbo yl and the like.
  • Substituents in substituted aryls, substituted aralkyls, and substituted alicyclic hydrocarbon rings formed by R 1 and R 2 together with adjacent carbon atoms include, for example, alkyl, alkoxy, alkanoyl, cyano-containing halo, halogen Atoms, alkoxy carbo and the like.
  • examples of the alkyl moiety of alkyl, alkoxy, and alkoxycarbo yl include those exemplified for the alkyl.
  • Examples of the hydrogen atom and the rogen atom are the same as those exemplified for the halogen atom.
  • Examples of the alkanoyl include straight chain or branched C 2-7, and specific examples thereof include acetyl, propiol, butyryl, isobutyryl, valeryl, isovaleryl, bivaloyl, hexanoyl, Examples include heptanol.
  • Examples of the substituent of the heterocyclic group containing an oxygen atom and Z or a sulfur atom include oxo, thixo, alkyl, alkoxy, alkanoyl, silane-containing nitro, halogen atom, alkoxycarbole and the like.
  • examples of the alkyl moiety of the alkyl, alkoxy, and alkoxycarbo yl include those exemplified for the alkyl.
  • Examples of the halogen atom are the same as those exemplified for the halogen atom.
  • Examples of the alkanoyl include those exemplified for the alkanoyl.
  • the alkyl ether represented by the general formula (I) is represented as a compound (I)
  • the halogenated alkyl ether represented by the general formula ( ⁇ ) is represented as a compound (II)
  • a compound having a group represented by the general formula (III) may be represented as a compound (III)
  • a compound having a group represented by the general formula (IV) may be represented as a compound (IV).
  • a polymer containing a repeating unit represented by the general formula (V) and having a weight average molecular weight of 1,000 to L0 0,000 is represented as a compound (V) and represented by the general formula (VI).
  • a polymer having a weight average molecular weight of 1,000-100,000 is represented as a compound (VI), comprising a repeating unit represented by the general formula (VII), and having a weight
  • a polymer having an average molecular weight of 1,000-100,000 is sometimes referred to as compound (VII).
  • the total carboxyl group of the compound (VII) is preferably 10 to 100%, more preferably 20 to 100% force substituted with a group represented by the general formula (IV).
  • (meth) acrylic acid represents acrylic acid and methacrylic acid
  • other (meth) acrylic acid derivatives! I express it in the same way.
  • Compound (I) may be a commercially available product or a known method [for example, the Chemical Society of Japan, “Experimental Chemistry Course (20th) Organic Synthesis II Alcohol 'Amin”, 4th Edition, pp. 207-208, Maruzen Co., Ltd. (July 6, 1992) etc.] and can be obtained.
  • compound (I) include, for example, the following compound formulas.
  • RR 2 and A have the same meanings as defined above, A ⁇ A 2 and A 3 are the same or different and represent an oxygen atom or a sulfur atom, R 9 represents alkyl, aryl, And m is 1, 2 or 3, n is 1 or 2, and p is 0, 1 or 2).
  • R 9 represents alkyl, aryl and aralkyl are the same as described above.
  • A, A ⁇ A 2 is an oxygen atom or a sulfur atom, and m is 1, 2, or 3.
  • A, A ⁇ A 2 , A 3 are oxygen atoms or sulfur atoms, n is 1 and p is 1 or 2.
  • compound (I) one or more compounds are used.
  • Compound ( ⁇ ) can be produced, for example, by reacting compound (I) with halogenated hydrogen.
  • a gaseous substance particularly a salty hydrogen gas is preferably used.
  • the amount of halogenated hydrogen used is preferably 1 mol or more per 1 mol of compound (I).
  • the reaction temperature is preferably 0 to 20 ° C.
  • the compound ( ⁇ ) can be prepared by a known method [for example, “New Experimental Chemistry Course (No. 14) Synthesis and Reaction of Organic Compounds (1)” edited by the Japan Society of Chemical Engineering, 590-591, Maruzen Co., Ltd. 1/20/60) etc.] and can be obtained.
  • a ⁇ A 2 is an oxygen atom or a sulfur atom, and m is 1, 2 or 3.
  • a and A 1 are oxygen atoms or sulfur atoms, and n is 1 Or 2.
  • the compound (1) one or more compounds are used.
  • those containing at least one sulfur atom are preferable from the viewpoint of adhesion of the protector to the substrate.
  • Y is preferably an oxygen atom.
  • Examples of the compound having a hydroxyl group include alcohols and phenols.
  • alcohols examples include monoalcohols such as methanol, ethanol, propanol, isopropyl alcohol, n -butanol, isobutanol, sec butyl alcohol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, and benzyl alcohol.
  • the phenols include phenol, resorcinol, hydroquinone, pyrocatechol, bisphenol A, dihydroxydiphenol methane (bisphenol F), bisphenol S, tetrabromobisphenol A, 1,3 bis (4 hydroxyphenol).
  • the proportion of hydroxystyrene in the copolymer obtained by copolymerizing hydroxystyrene with another monomer copolymerizable therewith is not particularly limited, but is preferably 0.2-90 mol 0 / 0, more preferably 0. 2 60 mol 0/0.
  • Examples of the other monomer copolymerizable with hydroxystyrene include a polymerizable unsaturated monomer having a carboxyl group or another monomer copolymerizable therewith.
  • Examples of the polymerizable unsaturated monomer having a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, 2-hydroxymethyl-2-propenoic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride. An acid or its acid anhydride is mentioned.
  • Examples of other monomers copolymerizable with the polymerizable unsaturated monomer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate.
  • Monomers having an epoxy group such as fluorine-containing butyl monomer, aryl glycidyl ether, glycidyl (meth) acrylate, styrene, a-methylol styrene, p-methylol styrene, dimethyl styrene, di-vinylol Styrene monomers such as Nzen, butyl methyl ether, bulet Ethers, bi - Bulle ethers such as Louis Seo ether, fumaric acid, maleic acid, maleic anhydride Esters of polybasic unsaturated carboxylic acids such as acids or their mono- or polyhydric alcohols, allylic alcohols, allylic alcohol esters, butyl chloride, vinylidene chloride, trimethylolpropane tri (meth) acrylate, Examples include butyl acetate and propionate. These monomers may be used alone or in combination of two or more. These monomers may be used alone or
  • compound (V) is preferred.
  • novolak greaves are commercially available.
  • an acidic catalyst for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, organic acids such as p-toluenesulfonic acid.
  • the above phenols and aldehydes can be used alone or in combination of two or more.
  • Compound (VI) is preferred as the novolak rosin.
  • polymer which has a hydroxyl group commercially available resin can also be used.
  • the weight average molecular weight of the polymer having a hydroxyl group is 1,000 to 100,000 force S preferred ⁇ , 1,000 to 50,000 preferred force S ⁇ , and even ⁇ 1, More preferably, it is from 000 to 20,000.
  • the polymer having a hydroxyl group can be purified and used as a solid. Further, when a solvent is used in the production, it can be used as a solution.
  • Examples of the compound having a carboxyl group include formic acid, acetic acid, propionic acid, propiolic acid, butyric acid, isobutyric acid, hexanoic acid, heptanoic acid, octylic acid, nonanoic acid, isononanoic acid, decanoic acid, dodecanoic acid, stearin.
  • Acid benzoic acid, cinnamic acid, 2-naphthoic acid, nicotinic acid, isonicotinic acid, amino oil fatty acid, tall oil fatty acid, soybean oil fatty acid, Monocarboxylic acid such as mash oil fatty acid, succinic acid, dartaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, compound having decamethylene dicarboxyl group, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, Polyhydric carboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid and methylhexahydrophthalic acid, hydroxycarboxylic acids such as lactic acid, citrate, hydroxypivalic acid, 12-hydroxystearic acid and malic acid, acrylic acid, methacrylic acid ⁇ , j8-unsaturated monomer having carboxyl group such as acid, itaconic
  • a homopolymer of a polymerizable unsaturated monomer containing a carboxyl group or a polymerizable unsaturated monomer containing a carboxyl group and other monomers copolymerizable therewith is preferred.
  • Examples of the polymerizable unsaturated monomer containing a carboxyl group and other monomers copolymerizable therewith include those described above. These monomers may be used alone or in combination of two or more.
  • Polymerization of a polymerizable unsaturated monomer containing a carboxyl group and copolymerization of a polymerizable unsaturated monomer containing a carboxyl group with another monomer copolymerizable therewith are carried out by known methods. It can be carried out.
  • the polymer containing a carboxyl group a commercially available resin can also be used.
  • the ratio of the carboxyl group in the polymer containing a carboxyl group is not particularly limited, but is preferably an acid value. 20-200, more preferably 40-160.
  • the acid value is the number of mg of sodium hydroxide required to neutralize the carboxyl group contained in the polymer lg.
  • the weight average molecular weight of the polymer containing a carboxyl group is preferably 1,000 to 100,000, more preferably ⁇ is 3,000 to 50,000, and further preferably ⁇ is 3, 000— 3 0,000.
  • compound (VII) is preferred.
  • the polymer containing a carboxyl group can be purified and used as a solid. Further, when a solvent is used in the production, it can be used as a solution.
  • Compound (I) or Compound (IV) easily reacts with the hydroxyl group of a compound having a hydroxyl group or the carboxyl group of a compound having a carboxyl group to give Compound (III) or Compound (IV).
  • the partial structure derived from the compound (I) or the compound ( ⁇ ) is easily detached from the compound ( ⁇ ) or the compound (IV), and the carboxyl group is removed from the compound (III) force hydroxyl group force or compound (IV). Reproduce. Therefore, Compound (I) or Compound ( ⁇ ) is useful as a hydroxyl group or carboxyl group protecting agent.
  • the method for protecting a hydroxyl group or a carboxyl group using compound (I) is also a method for producing compound (IV) or compound (IV), respectively.
  • compound (I) By reacting compound (I) with a compound having a hydroxyl group or a compound having a carboxyl group, the hydroxyl group or the carboxyl group can be protected.
  • the equivalent ratio (molar ratio) of the compound (I) to the compound having a hydroxyl group or the compound having a carboxyl group is not particularly limited, but the substitution ratio in the compound having a hydroxyl group or the compound having a carboxyl group is not limited. It is preferably 0.9-2 mol, more preferably 0.9-1.5 mol, and more preferably 1-1. Two moles are more preferred.
  • the reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, and further preferably 0 to 50 ° C.
  • an acid catalyst for the purpose of accelerating the reaction.
  • the acid catalyst is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as p-toluenesulfonic acid. Among them, p-toluenesulfonic acid Is preferred.
  • One or two or more acid catalysts are used.
  • the amount of the acid catalyst to be added is not particularly limited, but is preferably 0.0001 to 0.5 equivalent (molar ratio) relative to the raw material compound having a hydroxyl group. 1 equivalent (molar ratio) is more preferable.
  • the target product can be produced in a high yield with few side reactions regardless of which acid catalyst is used.
  • an organic solvent as needed.
  • the organic solvent include hydrocarbon solvents such as hexane, toluene and xylene, ether solvents such as dioxane and tetrahydrofuran, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and the like.
  • hydrocarbon solvents such as hexane, toluene and xylene
  • ether solvents such as dioxane and tetrahydrofuran
  • ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and the like.
  • One or more types are used.
  • compound (III) or compound (IV) can also be obtained by purification by a known method such as washing with water or distillation as necessary.
  • the method for protecting hydroxyl group or carboxyl group using compound ( ⁇ ) is also a method for producing compound ( ⁇ ) or compound (IV), respectively.
  • the equivalent ratio (molar ratio) of the compound ( ⁇ ) to the compound having a hydroxyl group or the carboxyl group is not particularly limited, but the compound having a hydroxyl group or the carboxyl group is contained.
  • 1 mol per mole of hydroxyl group or carboxyl group to be substituted in the compound is preferably 10 mol, more preferably 15 mol, more preferably 2-4 mol. preferable.
  • the reaction temperature is preferably 0-100 ° C, more preferably 0-50 ° C, more preferably 0-20 ° C! /.
  • the base is not particularly limited, and examples thereof include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as ethylamine, jetylamine, and triethylamine, among which triethylamine is preferable.
  • the amount of the base added is not particularly limited, but the compound ( ⁇ ) 1 mol It is more preferably 1 to 3 mol, more preferably 1 to 3 mol per mol. Moreover, you may use an organic solvent as needed.
  • organic solvent examples include hydrocarbon solvents such as hexane, toluene and xylene; ether solvents such as dioxane and tetrahydrofuran; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Examples include aprotic polar solvents such as dimethylacetamide, ⁇ , ⁇ -dimethylformamide, dimethylsulfoxide, etc., and one or more are used.
  • the compound (III) or the compound (IV) can also be obtained by purification by a known method such as washing with water or distillation as necessary.
  • compound (IV) or compound (IV) is a compound having a polymerizable unsaturated double bond, if necessary, it is polymerized alone or with other polymerizable unsaturated monomers by a known method. You may let them.
  • compound (III) or compound (IV) is excellent in heat resistance and has a high transition point.
  • Examples of the method for removing the protecting group include a method of treating compound (IV) or compound (IV) with heat or acid.
  • heat treatment When heat treatment is performed, it is preferably performed at 160 to 250 ° C.
  • examples of the acid to be used include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and the like, and among them, p-toluenesulfonic acid is preferable.
  • the amount of the acid used is preferably 0.01 to 50 mol with respect to 1 mol of the structure derived from the compound (I) or compound ( ⁇ ) to be eliminated.
  • the temperature during the treatment with the acid is preferably 80-160 ° C. Water may be added when treating with acid.
  • the amount of water used is preferably 0.1 to 100% by weight with respect to compound (III) or compound (IV).
  • the temperature during the treatment with acid is preferably 20 to 80 ° C.
  • an organic solvent may be used.
  • the organic solvent are the same as described above, and the amount used is preferably 10 to 100% by weight with respect to compound (III) or compound (IV), preferably 20 to 95% by weight. Is more preferable.
  • compound (IV) or compound (IV) and a photoacid generator coexist to emit light to the photoacid generator. It is possible to regenerate the hydroxyl group or the carboxyl group by irradiating a line or the like, generating an acid, deprotecting it.
  • the compound (I) or the compound ( ⁇ ⁇ ⁇ ) can be used for the protection and deprotection of the carboxyl group of the compound having a hydroxyl group or the hydroxyl group of the compound having a hydroxyl group. Therefore, compound (IV) or compound (IV) can be used as a component of a chemically amplified resist composition or the like.
  • the chemically amplified resist composition of the present invention comprises a compound ( ⁇ ) or compound (IV) (hereinafter sometimes referred to as a base polymer) having a weight average molecular weight of 1,000-100,000, and photoacid generation.
  • a compound ( ⁇ ) or compound (IV) hereinafter sometimes referred to as a base polymer
  • the polyhydroxystyrene derivative in which the hydroxyl group of the compound (V) is substituted with a group represented by the general formula ( ⁇ )
  • the hydroxyl group of the compound (VI) is represented by the general formula ( ⁇ ).
  • a poly (meth) acrylic resin in which the carboxyl group of compound (VII) is substituted with the general formula (IV), and a photoacid generator.
  • the base polymer is represented by the group represented by the general formula ( ⁇ ) or the general formula (IV) of the hydroxyl group or carboxyl group power of the compound ( ⁇ ) or the compound (IV). It may not be substituted with a group.
  • the weight average molecular weight of the base positive mer is 1,000 to 100,000, preferably ⁇ 100,000 to 50,000, more preferably ⁇ 1,000 to 30,000.
  • Photoacid generators include sulfo-um salt, ododonium salt, sulfo-diazomethane, N
  • —Sulphonyloxyimido or imide type acid generator benzoin sulfonate type photoacid generator, pyrogallol trisulfonate type photoacid generator, nitrobenzyl sulfonate type photoacid generator, sulfone type photoacid generator, darioxime Derivative-type photoacid generators and the like can be mentioned, and among them, sulfo-um salt, iodine-um salt, sulfo-diazomethane, N-sulfo-oxyximino, imide-type acid generator and the like are preferable.
  • the sulfo-um salt is a salt of a sulfo-cation and a sulfonate.
  • Sulfo-sulfur power Thiones include, for example, triphenyl sulfone, (4 tert-butoxyphenyl) dithiol.
  • Hue-Nolesnorephonium Bis (4-tert-Butoxyphene-Nole) Hue-Nolesnorehonium, Tris (4-Tert-Butoxyphene) sulfo-um, (3-Tert-Butoxyphene- ) Diphenyl sulfone, bis (3-tert-butoxyphenyl) phenol sulfone, tris (3-tert-butoxyphenyl) sulfo-sulfur, (3,4-di-tert-butoxyphenol) ) Diphenyl, bis (3,4-di-tert-butoxyphenyl) phenol sulfone, tris (3,4-di-tert-butoxyphenol) sulfo-sulfur, diphenyl (4 -Thiophenoxyphenyl) sulfol, (4 tert-butoxycarboxylmethyloxyphenyl) diphenylsulfur, tris (4 tert-butoxycarbox
  • sulfonate examples include trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2, 2, 2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4 trifluoromethylolene.
  • Jordonium salt is a salt of odonium cation and sulfonate.
  • dihydro-deuterium bis (4 tert-butyl-feole) furdon, (4-tert-butoxy-feule) fe-ureo-de-neum, (4-methoxy-feole) feoleo-de-neum, etc.
  • a danium cation examples include trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2, 2, 2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4 trifluoromethyl.
  • Benzene sulfonate 4-phenolobenzene benzene sulfonate, tonole sulfonate, benzene sulfonate, 4 (4 Toluenesulfo-loxy) benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate and the like.
  • sulfo-diazomethane examples include bis (ethylsulfol) diazomethane, bis (1-methylpropylsulfol) diazomethane, bis (2-methylpropylsulfol) diazomethane, and bis (1,1-dimethyl).
  • Ethylsulfo) diazomethane bis (cyclohexylsulfol) diazomethane, bis (perfluoroisopropylsulfol) diazomethane, bis (phenolsulfol) diazomethane, bis (4-methylphenolsulfo) -L) diazomethane, bis (2,4 dimethylphenylsulfol) diazomethane, bis (2 naphthylsulfonyl) diazomethane, (4-methylphenol) sulfolbenzoyldiazomethane, (tert butyl carbonate) )
  • N sulfo-luoximino-type photoacid generators include [5- (4 methylphenylsulfo-luoxyimino) -5H thiophene-2-ylidene]-(2-methylphenol) acetonitrile, (5 propylsulfonyl) Oxyimino 5H thiophene-2-ylidene)-(2-methylphenol) acetonitrile, (5-camphorsulfo-oxyximino 5 H thiophene-2-ylidene)-(2-methylphenol) acetonitrile, 2— (9 —Camphorsulfo-Luximino)-2- (4-Methoxyphenyl) acetonitrile, 2— (4-Methylphenylsulfo-Luximino) —2 Phenylacetonitrile, 2— (4-Methylphenylsulfo-Luximino)-2- (
  • N-sulfonyloxyimide-type photoacid generator examples include succinimide, naphthalene dicarboxylic imide, phthalic imide, cyclohexyl dicarboxylic imide, 5-norbornene 1,2,3 dicarboxylic acid Imido, 7-oxabicyclo [2. 2.
  • benzoin sulfonate photoacid generator examples include benzoin tosylate, benzoin mesylate, and benzoin butane sulfonate.
  • pyrogallol trisulfonate photoacid generators include, for example, all of hydroxyl groups such as pyrogallol, fluoroglycine, catechol, resorcinol, hydroquinone, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorootatansulfonate.
  • nitrobenzil sulfonate photoacid generator examples include 2,4-dinitrobenzenolesnolefonate, 2-trobenzinoresnolefonate, and 2,6 dinitrobenzenolesnorefo.
  • Specific examples of sulfonates include trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2, 2, 2 trifluoroethane sulfonate, and pentafluoro.
  • a compound in which the -tro group on the benzyl side is replaced with a trifluoromethyl group can also be used in the same manner.
  • Examples of the sulfone-type photoacid generator include bis (phenolsulfol) methane, bis (4-methylphenolsulfurol) methane, bis (2-naphthylsulfol) methane, 2, 2 —Bi (Phenylsulfur) pronone, 2,2bis (4-methylphenolsulfol) propan, 2,2-bis (2-naphthylsulfol) propane, 2-methyl-2- (p Toluenesulfol) propiophenone, 2- (cyclohexylcyclohexyl) -2- (ptoluenesulfol) propane, 2,4 dimethyl-2- (ptoluenesulfol) pentane-3-one, etc. can give.
  • Examples of the dalioxime derivative-type photoacid generator include bis-O- (ptoluenesulfurol) -a -dimethyldarioxime, bis-O- (ptoluenesulfol) ⁇ -diphenyldaroxime.
  • the photoacid generators may be used alone or in admixture of two or more.
  • the amount of the photoacid generator in the chemically amplified resist composition of the present invention is not particularly limited, but is preferably a force of 0.001 to 50 weight percent with respect to 100 weight percent of the base positive polymer, preferably 0.01 to 30. Part by weight is more preferred, and 0.1-10 parts by weight is more preferred. Yes.
  • the chemically amplified resist composition of the present invention may further contain a photosensitizer, for example, anthracenes, anthraquinones, coumarins, and pyromethenes as necessary.
  • a photosensitizer for example, anthracenes, anthraquinones, coumarins, and pyromethenes as necessary.
  • the amplification type resist composition may contain an organic solvent as necessary.
  • organic solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclohexanone, cyclopentanone and other ketones, propylene glycolanol monomethylol ether, propylene glycolol.
  • the viscosity of the chemically amplified resist composition can be adjusted.
  • the amount of the organic solvent in the chemically amplified resist composition of the present invention is not particularly limited, but is preferably 100 to 4000 parts by weight, more preferably 20 to 100 parts by weight of the base polymer. 0-3000 parts by weight, more preferably ⁇ 300-2000 parts by weight.
  • the chemically amplified resist composition of the present invention may contain a basic compound as required.
  • Examples of the basic compound include primary, secondary or tertiary aliphatic amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, and sulfole groups. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, amide derivatives, imide derivatives and the like.
  • the basic compounds may be used alone or in admixture of two or more.
  • the amount of the basic compound in the chemically amplified resist composition of the present invention is not particularly limited.
  • the force is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the base polymer. Or 0.01 to 5 parts by weight.
  • the acid diffusion rate in the chemically amplified resist composition is suppressed, and the exposure margin and pattern profile file are improved.
  • the influence of the substrate and the environment on the resist film can be reduced.
  • the storage stability of the chemically amplified resist composition can be improved by adding a basic compound to the chemically amplified resist composition of the present invention.
  • the chemically amplified resist composition of the present invention may contain a surfactant as necessary.
  • surfactants examples include polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid ester non-ionic surfactants, and fluorine-based surfactants.
  • surfactant, organosiloxane polymer and the like can be mentioned.
  • Surfactants may be used alone or in admixture of two or more.
  • the coating properties of the chemically amplified resist composition can be improved.
  • the chemically amplified resist composition of the present invention can be prepared by using a dissolution regulator such as a phenolic compound, an ultraviolet absorber such as a hydroxyphenol, a hindered phenol, etc., if necessary.
  • a dissolution regulator such as a phenolic compound, an ultraviolet absorber such as a hydroxyphenol, a hindered phenol, etc.
  • You may contain a storage stabilizer, antifoaming agents, such as a silicone type and a wax type.
  • the chemically amplified resist composition of the present invention may contain other resin modifiers or plasticizers as necessary!
  • the chemical amplification resist composition of the present invention contains other resin modifiers or plasticizers, thereby improving the flexibility of the chemical amplification resist composition and imparting toughness to the resist film. can do.
  • resins are not particularly limited.
  • homopolymers or copolymers of the above-mentioned polymerizable unsaturated monomers adipic acid, phthalic acid, trimellitic acid, etc.
  • Polyester resin obtained by condensation reaction of a polyacid base such as basic acid and dallicol, trimethylolpropane, etc. phenol resin obtained by condensation reaction of the above-mentioned phenol or talesol and aldehyde, polyurethane obtained from polyol and isocyanate
  • examples include rosin, epoxy rosin having a cyclic or acyclic alkyl group, and derivatives thereof. These coffins can be used alone or in combination of two or more. Further, the weight average molecular weight of these coconuts is more preferably 1,000 to 1,000,000, 3,000 to 600,000.
  • the modifier is not particularly limited.
  • polyethylene glycol, polypropylene glycol, polybutadiene polyol and polyolefin polyol, OC-hydroxyethyl- ⁇ -hydroxymethylpoly (1 ethoxyethylene) (Manufactured by Kyowa Hakko Chemical Co., Ltd.), polytetramethylene ether glycol, polymer polyol, polyester polyol, poly force prolatathone polyol, polycarbonate polyol and other polybasic acid oligomers such as polybutadiene dicarboxylic acid.
  • These oligomers can be used alone or in admixture of two or more.
  • the weight average molecular weight of these fats is more preferable than 300 to 30,000 Rhizomu 500 to 10 000!
  • the plasticizer is not particularly limited, but examples thereof include phthalic acid plasticizers such as dioctyl phthalate, diisonol phthalate, diisodecyl phthalate, and ditridecyl phthalate, dibutyl adipate, dioctyl adipate, and the like. Adipic acid plasticizers, polybasic acid esters such as succinic acid and 2,4-jetyldartalic acid.
  • the blending amount of the other resin modifier or plasticizer is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, based on the chemically amplified resist composition of the present invention.
  • the chemically amplified resist composition of the present invention comprises a base polymer, a photoacid generator and, if necessary, a photosensitizer, an organic solvent, a basic compound, a surfactant, a dissolution regulator, an ultraviolet absorber, and storage stability. It can be prepared as a solution by mixing additives such as an agent and an antifoaming agent. The order and method of mixing are not particularly limited.
  • the chemically amplified resist composition of the present invention may be a dry film.
  • the dry film can be prepared, for example, by applying the above solution onto a support such as metal or polyethylene terephthalate, drying, and then peeling off the support. Further, when the support is a film of polyethylene terephthalate or the like, it can be used as it is as the chemically amplified resist composition of the present invention.
  • Examples of a method for applying the chemically amplified resist composition of the present invention on a support include known methods such as spin coating, rhono coating, flow coating, dip coating, spray coating, and doctor one coating. can give.
  • the thickness of the applied film is a force that can be set according to the application, preferably 0.05-200 ⁇ m, more preferably 0.1-100 m.
  • Examples of the film used as the support include polyethylene terephthalate, polypropylene, polyethylene, polyester, and polybutyl alcohol.
  • the chemically amplified resist composition of the present invention is a dry film, the chemically amplified resist composition is protected as necessary for the purpose of protecting the chemically amplified resist composition from scratches, dust, chemicals, and the like. You may coat
  • Examples of the protective film include a polyethylene film and a polypropylene film, and those having an adhesive force with the chemically amplified resist composition of the present invention smaller than that of the support are preferred.
  • a release layer may be provided between the protective film and the chemically amplified resist composition of the present invention.
  • the dry film may be wound up into a roll.
  • ⁇ Pattern formation method> The step of applying the chemically amplified resist composition of the present invention onto a substrate, the step of heating the substrate, the step of exposing the coating film on the substrate to radiation or the like, the step of heating the substrate after exposure, and then alkaline A pattern can be formed using the chemically amplified resist composition of the present invention by the step of developing the substrate using a developer.
  • the substrate is not particularly limited, and examples thereof include metal plates such as aluminum, zinc, gold, silver, and nickel, copper foil laminate plates, glass plates, and silicon wafers.
  • the chemically amplified resist composition of the present invention is a solution, for example, spin coating, roll coating, flow coating, dip coating, spray coating. And known methods such as doctor coating
  • the thickness of the applied film is a force that can be set according to the application, preferably 0.05-200 ⁇ m, more preferably 0.1-100 m.
  • the chemically amplified resist composition of the present invention is a dry film and there is a protective film, after the protective film is peeled off, the chemically amplified resist composition layer is applied so as to be in direct contact with the substrate. And a laminating method. When laminating, setting the temperature to 80-160 ° C makes it possible to omit the next heat treatment.
  • the substrate After applying the chemically amplified resist composition of the present invention to the substrate, the substrate is heated.
  • the heating method include known methods such as heating with a hot plate or an oven.
  • the organic solvent evaporates when heated.
  • the heating temperature is preferably 80-160 ° C.
  • the chemically amplified resist composition of the present invention is a dry film, this step can be omitted if heating is performed during lamination.
  • the coating film is irradiated with radiation using a photomask, a reduction projection exposure machine, a direct drawing machine or the like.
  • radiation include near infrared rays such as far infrared rays, visible rays, g rays, h rays, i rays, KrF excimer lasers, ArF excimer lasers, DUV (far ultraviolet rays), EUV (extreme ultraviolet rays), electron beams, X-rays etc.
  • the photoacid generator is decomposed to generate acid.
  • the substrate is heated.
  • the heating method include those used for heating after coating.
  • compound (I) or compound is converted from compound ( ⁇ ) or compound (IV).
  • the structure derived from the compound ( ⁇ ) is eliminated, and the hydroxyl group or carboxyl group is regenerated.
  • the heating temperature is preferably 80-160 ° C.
  • a positive resist pattern is obtained by developing with an alkaline developer as it is.
  • the developing method include known methods such as an immersion method, a paddle method, and a spray method.
  • the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasilicate, ammonia, ethylamine, n-propylamine, jetylamine, di-n-propylamine, triethylamine, methacrylic acid.
  • Basic substances may be used alone or in admixture of two or more.
  • a water-soluble organic solvent for example, alcohols such as methanol and ethanol, and surfactants can be added to the developer and used in an appropriate amount.
  • the substrate may be washed with water or dried by heating, if necessary.
  • the pattern formed on the substrate is, for example, dry etching of the substrate with a chlorine-based gas, a fluorine-based gas (CF 2 ZCH F mixed gas, etc.) or an oxygen-based gas using the pattern as a mask.
  • the chemically amplified resist composition of the present invention is excellent in stability during the heating process of the coating film and long-term storage stability, has good lithographic properties, adherence to the substrate, soldering solution, etc. Excellent wettability with respect to
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. (GPC analysis conditions)
  • RI RI 8000 (manufactured by Tosohichi Corporation)]
  • the acid value was determined by neutralization titration with a 0.1 mol / L KOH alcohol solution.
  • the contact angle was measured using a FACE contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd.
  • the film thickness was measured using an optical interference type film thickness gauge manufactured by Nospec.
  • 0.19 g of p-toluenesulfonic acid monohydrate was dissolved in 128.2 g of methanol, and 72. lg of isobutyraldehyde was added dropwise while cooling to 20 ° C or lower. Washing with 200 g of a 1% aqueous sodium carbonate solution and distillation of the oil layer obtained by liquid separation at atmospheric pressure gave 35 g of isobutyl aldehyde dimethylacetal. To this, 0.06 g of p-toluenesulfonic acid monohydrate was dissolved and heated to 200 ° C.
  • Phenolic novolak resin with a weight average molecular weight of 3,220 [manufactured by Showa High Polymer Co., Ltd.] 2. Dissolve 7 g in 17.5 ml of methyl ethyl ketone, and add 1-black mouth 1- (2-acetyl ethoxy) into this solution. —2—Methylpropane (2.23 g) was added and stirred until completely dissolved. Then, 2.53 g of triethylamine with stirring force S was added dropwise over about 30 minutes. After completion of dropping, the mixture was stirred for about 3 hours.
  • Phenolic novolak resin with a weight average molecular weight of 3,220 [manufactured by Showa Kogyo Co., Ltd.] 2. Dissolve 7 g in 17.5 ml of methyl ethyl ketone, and add 1-black mouth 1- (2 ethylthioethoxy) in this solution. 2.46 g of 2-methylpropane was added and stirred to dissolve completely, then 2.53 g of triethylamine was added dropwise over about 30 minutes while stirring. After completion of dropping, the mixture was stirred for about 3 hours.
  • Phenolic novolak resin with a weight average molecular weight of 3,220 [manufactured by Showa Polymer Co., Ltd.] 2. Dissolve 7 g in 17.5 ml of methyl ethyl ketone, and add 1-chloro 1-methoxy 2-methyl in this solution. After adding 1.53 g of tilpropane and stirring to dissolve completely, 2.53 g of triethylamine was added dropwise over about 30 minutes with stirring. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, the solvent was distilled off, and then dropped into 500 ml of pure water to cause reprecipitation.
  • Chloro-1-1 (2-Ethylthioethoxy) 2-Methylpropane protects the hydroxyl group of polyhydroxystyrene
  • Polyhydroxystyrene with a weight average molecular weight of 20,000 (Aldrich) 2. 7g was dissolved in 17.5ml of N, N-dimethylacetamide. After adding 1.35 g of methylpropane and stirring to completely dissolve, 2.23 g of triethylamine was added dropwise over about 30 minutes with stirring. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, and the solvent was distilled off. 3.4 g of solid was obtained.
  • an aluminum plate, a gold-plated steel plate, a silver-plated steel plate, and a chromium nickel substrate were used.
  • Test Example 1 Each solution of Test Example 1 was applied to a 2-inch silicon wafer with a spin coater (rotation speed: 2000 rpm, 60 seconds) and heated on a hot plate (100 ° C, 5 minutes) to obtain a film thickness of 2 / zm. A membrane was created. Distilled water (droplet diameter: 1.5 mm) was dropped onto each membrane at 20 ° C, and the contact angle after 2 minutes was measured.
  • composition 7 According to Table 4, rosin, photoacid generator and organic solvent were mixed. The resulting solution was filtered through a 0.2 ⁇ m membrane filter to obtain composition 7.
  • composition 8 According to Table 4, rosin, photoacid generator and organic solvent were mixed. The resulting solution was filtered through a 0.2 ⁇ m membrane filter to obtain composition 8.
  • composition 9 According to Table 4, rosin, photoacid generator and organic solvent were mixed. The resulting solution was filtered through a 0.2 ⁇ m membrane filter to obtain composition 9.
  • composition Composition Composition Composition String Table 1 2 3 4 5 6 7 8 9
  • PAI-101 manufactured by Midori Chemical Co., Ltd. was used as the photoacid generator.
  • propylene glycol monomethyl ether acetate manufactured by Kyowa Hakko Chemical Co., Ltd. was used.
  • a pattern was formed by the following method, and the pattern shape was evaluated.
  • compositions 1-6 were respectively applied to a 4-inch silicon wafer with a spin coater (rotation speed: 2000 rpm, 60 seconds) and heated with a hot plate (100 ° C., 5 minutes). The film thickness became.
  • the i-line was exposed to 20 mjZcm 2 using a mask aligner (MA-4 manufactured by SUSS Microtec). After the exposure, it was heated on a hot plate (120 ° C, 2 minutes) and developed with a 38% aqueous solution of tetramethylammonium hydroxide (25 ° C, 120 seconds). Finally, it was washed with pure water to obtain a 5 ⁇ m line and space pattern.
  • the pattern shape was evaluated by observing the front surface and the cross section of the pattern obtained by an optical microscope and a scanning electron microscope. Regarding the pattern shape, the case of a rectangle was determined as “ ⁇ ”, and the case of a non-rectangular shape was determined as “X” when the head was round, for example.
  • a hydroxyl group or carboxyl group protective agent excellent in adhesion of a protective body to a substrate, wettability with respect to a solder or a staking solution, etc., and a protective body protected with the protective agent. can do.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne un agent protecteur pour un groupe hydroxyle ou un groupe carboxyle, qui est représenté par la formule générale (0) (dans laquelle X1 représente un atome d'hydrogène et X2 représente un atome d'halogène, ou en variante X1 en combinaison avec X2 représente une liaison ; R1 et R2 représentent indépendamment un groupe alkyle ou analogue substitué ou non substitué ; A représente un atome d'oxygène ou un atome de soufre ; et R3 représente un groupe alkyle où un groupe possédant un atome d'oxygène et/ou un atome de soufre est substitué ou analogue). (0)
PCT/JP2007/059161 2006-04-27 2007-04-27 Agent protecteur WO2007126050A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009081852A1 (fr) * 2007-12-20 2009-07-02 Kyowa Hakko Chemical Co., Ltd. Agent protecteur
WO2013141376A1 (fr) * 2012-03-23 2013-09-26 富士フイルム株式会社 Protecteur, procédé de fabrication d'un composé protégé par le protecteur, résine protégée par le protecteur, composition de résine photosensible contenant la résine protégée par le protecteur, matière de formation de motif, film photosensible, motif en relief durci, son procédé de fabrication et dispositif semi-conducteur
JP2017181895A (ja) * 2016-03-31 2017-10-05 東京応化工業株式会社 化学増幅型ポジ型感光性樹脂組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000226340A (ja) * 1999-02-04 2000-08-15 Mitsubishi Chemicals Corp 水酸基が保護されたフェノール性化合物の製造方法及びポジ型感放射線組成物
WO2003006407A1 (fr) * 2001-07-13 2003-01-23 Kyowa Yuka Co., Ltd. Procédé de production de composé d'éther
WO2005023880A1 (fr) * 2003-09-03 2005-03-17 Kyowa Hakko Chemical Co., Ltd. Procede de production d'un compose contenant un groupe labile en milieu acide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000226340A (ja) * 1999-02-04 2000-08-15 Mitsubishi Chemicals Corp 水酸基が保護されたフェノール性化合物の製造方法及びポジ型感放射線組成物
WO2003006407A1 (fr) * 2001-07-13 2003-01-23 Kyowa Yuka Co., Ltd. Procédé de production de composé d'éther
WO2005023880A1 (fr) * 2003-09-03 2005-03-17 Kyowa Hakko Chemical Co., Ltd. Procede de production d'un compose contenant un groupe labile en milieu acide

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009081852A1 (fr) * 2007-12-20 2009-07-02 Kyowa Hakko Chemical Co., Ltd. Agent protecteur
WO2013141376A1 (fr) * 2012-03-23 2013-09-26 富士フイルム株式会社 Protecteur, procédé de fabrication d'un composé protégé par le protecteur, résine protégée par le protecteur, composition de résine photosensible contenant la résine protégée par le protecteur, matière de formation de motif, film photosensible, motif en relief durci, son procédé de fabrication et dispositif semi-conducteur
JP5696254B2 (ja) * 2012-03-23 2015-04-08 富士フイルム株式会社 保護剤、該保護剤により保護された化合物の製造方法、該保護剤により保護された樹脂、該保護剤により保護された樹脂を含有する感光性樹脂組成物、パターン形成材料、感光性膜、硬化レリーフパターン、その製造方法、及び半導体装置
JP2017181895A (ja) * 2016-03-31 2017-10-05 東京応化工業株式会社 化学増幅型ポジ型感光性樹脂組成物
KR20170113113A (ko) * 2016-03-31 2017-10-12 도오꾜오까고오교 가부시끼가이샤 화학 증폭형 포지티브형 감광성 수지 조성물
KR102464514B1 (ko) * 2016-03-31 2022-11-07 도오꾜오까고오교 가부시끼가이샤 기판 상에 배선 또는 단자를 형성하는 방법

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