WO2007126050A1

WO2007126050A1 - Protective agent

Info

Publication number: WO2007126050A1
Application number: PCT/JP2007/059161
Authority: WO
Inventors: Hiroshi Matsuoka; Ryo Numazaki; Iwao Hotta
Original assignee: Kyowa Hakko Chemical Co., Ltd.
Priority date: 2006-04-27
Filing date: 2007-04-27
Publication date: 2007-11-08
Also published as: JPWO2007126050A1; TW200745187A

Abstract

Disclosed is a protective agent for a hydroxyl group or a carboxyl group, which is represented by the general formula (0) below (wherein X1 represents a hydrogen atom and X2 represents a halogen atom, or alternatively X1 in combination with X2 represent a bond; R1 and R2 independently represent a substituted or unsubstituted alkyl or the like; A represents an oxygen atom or a sulfur atom; and R3 represents an alkyl wherein a group having an oxygen atom and/or a sulfur atom is substituted or the like). (0)

Description

Specification

Protective agent

Technical field

[0001] 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.

Background art

[0002] 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.

[0003] However, alkyl butyl ethers and halogenated alkyl ethers are extremely unstable and easily polymerized. For example, when 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.

[0004] In order to solve these problems, a method in which an alcohol ether or a halogenated alkyl ether represented by the following formula is used as a protective agent for a carboxyl group or a hydroxyl group in place of the alkyl butyl ether (for example, Patent Document 1). 2) is known.

[0005] [Chemical 1]

[0006] (wherein 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

Disclosure of the invention

Problems to be solved by the invention

[0007] 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. Means for solving the problem

[0008] The present invention provides the following (1) one (21).

(1) General formula (0)

[0009] [Chemical 2]

[0010] [wherein X ¹ represents a hydrogen atom, X ² represents a force representing a halogen atom, and X ¹ and X ² together represent a bond,

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. To form a substituted or unsubstituted alicyclic hydrocarbon ring, A represents an oxygen atom or a sulfur atom,

R ³ is alkyl substituted by a group having an oxygen atom and Z or a sulfur atom, aryl having an oxygen atom and a group having Z or sulfur atom substituted, oxygen atom and Z or Aralkyl substituted by a group having a sulfur atom, or may be substituted by an oxygen atom and a heterocyclic group containing Z or a sulfur atom,-(=) 1 ^ (where Y ¹ is oxygen Represents an atom or a sulfur atom, and R ^A may be substituted by a group having an oxygen atom and / or a sulfur atom, or may be substituted by a group having an alkyl, oxygen atom and Z or a sulfur atom. !, Aryl, an oxygen atom and / or a group having a sulfur atom may be substituted to represent a aralkyl or a heterocyclic group containing an oxygen atom and Z or a sulfur atom) or — S (= Y ² ) Y ³ R ^B (wherein p represents 1 or 2 and Y ² represents an oxygen atom or a sulfur atom)

P

Y ³ represents a bond, an oxygen atom or a sulfur atom, and R ^b represents a hydrogen atom, an alkyl, an aryl or an aralkyl. However, when 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)].

(2) General formula (I)

[0011] [Chemical 3]

[0012] (where

R ² , R ³ and A are as defined above, respectively, or a general formula (II)

[0013] [Chemical 4]

[0014] (where

R ² , R ³ and A are as defined above, and X represents a halogen atom). (3) General formula (I)

[0015] [Chemical 5]

[0016] (wherein RR ² , R ³ and A have the same meanings as described above) or the general formula (II)

[0017] [Chemical 6]

[0018] (where

R ² , R ³ , A and X are the same as defined above), and a carboxyl group-protecting agent containing a halogenated alkyl ether.

(4) Basic force having oxygen atom and Z or sulfur atom, oxo, thixo, Y¾ ^a [where Y ³ represents an oxygen atom or a sulfur atom, is a hydrogen atom, an alkyl,-(CH C

2

HO) — R ^aa (where q is an integer from 1 to 3, and R ^aa is a hydrogen atom, alkyl, aryl or

2 q

Or C (= Y ^aa ) R ^ab (where Y ^aa represents an oxygen atom or a sulfur atom, and R ^ab represents alkyl, aryl or aralkyl)], C (= Y ^b ) R b [wherein Y ^b represents an oxygen atom or sulfur atom, R ^b represents a hydrogen atom, alkyl, Y ^ba R ^ba (where Y ^ba represents an oxygen atom or sulfur atom, R ^ba represents hydrogen Represents atom, alkyl, aryl or aralkyl) or — (OCH CH) — R ^bb (where r is 1)

Represents an integer from 2 2 r to 3,

R ^bb represents hydroxyl, alkyl, aryl or aralkyl)], -S (= Y ^C ) Y ^d R ^e (wherein s represents 1 or 2, ΥΊ represents an oxygen atom or a sulfur atom, Y ^d is a bond s

Represents an oxygen atom or a sulfur atom, 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.

(5) A compound having a hydroxyl group is represented by the general formula (I)

[0019] [Chemical 7]

[0020] (where

R ² , R ³ and A have the same meanings as defined above) or the general formula (II)

[0021] [Chemical 8]

[0022] (wherein

R ² , R ³ , A and X are the same as defined above) and are reacted with a halogenated alkyl ether represented by the general formula (III)

[0023] [Chemical 9]

[0024] A method for producing a compound having a group represented by the formula: wherein R \ R ² , IT and A are as defined above.

(6) A compound having a carboxyl group is represented by the general formula (I)

[0025] [Chemical 10]

[0026] (wherein RR ² , R ³ and A have the same meanings as described above) or the general formula (II)

[0027] [Chemical 11]

[0028] (where

R ² , R ³ , A and X are the same as defined above) and are reacted with a halogenated alkyl ether represented by the general formula (IV)

[0029] [Chemical 12]

[0030] (where

R ² , R ³ and A are the same as defined above).

(7) A compound having a hydroxyl group is represented by the general formula (I)

[0031] [Chemical 13]

, ヽ (I)

[0032] (where

R ² , R ³ and A are the same as defined above) and are reacted with an alkellether represented by the general formula (III)

[0033] [Chemical 14]

R-R ²

(III)

, 0 ',

[0034] (where

R ³ and A are each as defined above).

(8) A compound having a hydroxyl group is represented by the general formula (II)

[0035] [Chemical 15]

[0036] (wherein RR ² , R ³ , A and X are as defined above), and a reaction with a halogenated alkyl ether represented by the general formula (III)

[0037] [Chemical 16]

2 ^ 3

[0038] (wherein, R \ R ^2, R ³ and A are the same meanings as defined above, respectively) preparation of reduction compound having a group represented by.

(9) A compound having a carboxyl group is represented by the general formula (I)

[0039] [Chemical 17]

[0040] (wherein RR ² , R ° and A have the same meanings as described above, respectively).

[0041] [Chemical 18]

[0042] (where

R ² , R ³ and A are the same as defined above).

(10) A compound having a carboxyl group is represented by the general formula (II) [0043] [Chemical 19]

[0044] (wherein RR ² , R ³ , A and X are as defined above), and a reaction with a halogenated alkyl ether represented by the general formula (IV)

[0045] [Chemical 20]

[0046] (where

R ² , IT and A are the same as defined above).

(11) Basic force having oxygen atom and Z or sulfur atom, oxo, thixo, Υ¾ a [where Y ^a represents an oxygen atom or a sulfur atom, is a hydrogen atom, an alkyl,-(CH C

2

2 q

Or C (= Y ^aa ) R ^ab (where Y ^aa represents an oxygen atom or a sulfur atom, and R ^ab represents alkyl, aryl or aralkyl)], C (= Y ^b ) R b [wherein Y ^b represents an oxygen atom or a sulfur atom, R ^b represents a hydrogen atom, alkyl, -Y ^ba R ^ba (where Y ^ba represents an oxygen atom or a sulfur atom, and R ^ba represents (Represents a hydrogen atom, alkyl, aryl or aralkyl) or — (OCH 2 CH 2) — R ^bb (wherein r represents an integer of 1 to 3,

2 2 r

Represents an oxygen atom or a sulfur atom, and represents a hydrogen atom, alkyl, aryl, or aralkyl), or a heterocyclic group containing an oxygen atom and a Z or sulfur atom (5) to (10) The manufacturing method described.

(12) General formula (V) [0047] [Chemical 21]

[In the formula, 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)

[0049] [Chemical 22]

R ²

To ヽ

[0050] (where

R ² , R ³ and A are the same as defined above).

(13) Basic force having oxygen atom and Z or sulfur atom oxo, thixo, Υ¾ a [where Y ^a represents an oxygen atom or a sulfur atom, is a hydrogen atom, an alkyl,-(CH C

2

2 q

Or C (= Y ^aa ) R ^ab (where Y ^aa represents an oxygen atom or a sulfur atom, and R ^ab represents alkyl, aryl or aralkyl)], C (= Y ^b ) R b [wherein Y ^b represents an oxygen atom or sulfur atom, R ^b represents a hydrogen atom, alkyl, Y ^ba R ^ba (where Y ^ba represents an oxygen atom or sulfur atom, R ^ba represents hydrogen Represents an atom, alkyl, aryl or aralkyl) or — (OCH 2 CH 2) — R ^bb (wherein r represents an integer of 1 to 3;

2 2 r

R ^bb represents hydroxyl, alkyl, aryl or aralkyl)], -S (= Y ^C ) Y ^d R ^e (wherein s represents 1 or 2, Y ^e represents an oxygen atom or a sulfur atom) , Y ^d is a bond Represents an oxygen atom or a sulfur atom, R ^e is a hydrogen atom, an alkyl, Ariru or an Araru kill), or a heterocyclic group containing an oxygen atom and Z or a sulfur atom (1 2) polyhydroxystyrene derivatives according .

(14) General formula (VI)

[0051] [Chemical 23]

[Wherein, 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, Represents an integer of 0 3 and 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.

[0053] [Chemical 24]

[0054] (wherein, RR ^2, R ³ and A are the same meanings as defined above, respectively) novolak榭脂derivatives substituted with a group represented by.

(15) Basic force having oxygen atom and Z or sulfur atom, oxo, thixo, Υ¾ a [where Y ^a represents an oxygen atom or a sulfur atom, is a hydrogen atom, an alkyl,-(CH C

2

2 q

Or C (= Y ^aa ) R ^ab (where Y ^aa represents an oxygen atom or sulfur atom) Represents a child, R ^ab represents alkyl, aryl or aralkyl)], — C (= Y ^b ) R b [wherein Y ^b represents an oxygen atom or a sulfur atom, R ^b represents a hydrogen atom, alkyl , -Y ^ba R ^ba (where Y ^ba represents an oxygen atom or sulfur atom, R ^ba represents a hydrogen atom, alkyl, aryl or aralkyl) or — (OCH CH) — R ^bb (where r represents an integer of 1 to 3,

2 2 r

And represents a hydrogen atom, alkyl, aryl or aralkyl), or a heterocyclic group containing an oxygen atom and a Z or sulfur atom (14), the novolac rosin derivative according to (14).

(16) General formula (VII)

[0055] [Chemical 25]

[0056] (wherein R ⁸ represents a hydrogen atom, lower alkyl or hydroxymethyl), and a polymer carbocycle having a weight average molecular weight of 1,000-100,000. All or part of the syl group general formula (IV)

[0057] [Chemical 26]

[0058] (wherein, RR ^2, R ³ and A are the same meanings as defined above, respectively) polyacrylic榭脂derivative or polymethacrylic resin derivative substituted with the group represented by.

(17) Basic force having oxygen atom and Z or sulfur atom, oxo, thixo, — Υ¾ a [where Y ^a represents an oxygen atom or a sulfur atom, is a hydrogen atom, an alkyl,-(CH C

2

2 q

2 2 r

R ^bb represents hydroxyl, alkyl, aryl or aralkyl)], -S (= Y ^C ) Y ^d R ^e (wherein s represents 1 or 2, Y ^e represents an oxygen atom or a sulfur atom) , Y ^d is a bond s

Represents an oxygen atom or a sulfur atom, and represents a hydrogen atom, alkyl, aryl or aralkyl), or a heterocyclic group containing an oxygen atom and a Z or sulfur atom (16), Polymethacrylic resin derivative.

(18) A compound having a group represented by the general formula (ΠΙ) 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.

(19) A chemically amplified resist composition comprising the polyhydroxystyrene derivative according to (12) or (13) and a photoacid generator.

(20) A chemically amplified resist composition comprising the novolak rosin derivative according to (14) or (15) and a photoacid generator.

(21) A chemically amplified resist composition comprising the polyacrylic resin derivative or polymethacrylic resin derivative according to (16) or (17) and a photoacid generator.

The invention's effect

[0059] According to the present invention, there are provided 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.

BEST MODE FOR CARRYING OUT THE INVENTION

[0060] In the definition of each group in the general formula, examples of the alkyl moiety of alkyl and alkoxy include linear, branched, or cyclic ones having 1 to 18 carbon atoms. Is 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 Examples thereof include cycloalkylalkyl such as til and cyclohexylethyl, among which alkyl having 16 carbon atoms is preferable, and alkyl having 13 carbon atoms is more preferable.

[0061] 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.

Examples of aryls include those having 6 to 14 carbon atoms, and specific examples thereof include phenyl and naphthyl.

[0062] 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.

[0063] 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. , Cenyl group, Tetrahydrocenyl group, Dithiolanyl group, Dithiosanyl group, Oxathiolanyl group, Thianthrenyl group, Latatonyl group, Thiolatonyl group, 2-oxo-1, 3 Dioxolanyl group, 2 Exo1, 3-oxathioral group, 2 Thixo 1, 3 dioxolanyl group, 2 thixo 1, 3-oxathiolanyl group and the like. [0064] Examples of the nitrogen atom and the rogen atom include fluorine, chlorine, bromine and iodine atoms, and among them, a chlorine atom is preferable.

Examples of the group having an oxygen atom and Z or a sulfur atom include oxo, thixo, — Y¾ ^a [wherein Y ^a and R ^a are as defined above], — C (= Y ^b ) R ^b [formula In which Y ^b and R ^b are as defined above], -S (= Y °) (where s, Y ^c , Y ^d and s

And 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, thiobutyrinole, thiovaleryl, thiol Isovaleryl, thiopivalol, methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butoxycarbonyl, methanolynore, ethanesnorefinore, propanesnorefinore, butansnorefi-nore, benzensenorefi-nore, benzenoles Norefinore, Methanosnorehoninore, Ethansnorehoninore, Prononrehoninore, Butansnorehoninore, Benzenorenoninore, Benzenoresnorenore, Methoxymethoxy, Methoxyethoxy, Furyl, Tetrahydrofuryl, Examples thereof include a biral group, a tetrahydropyranyl group, a dioxoral group, a dioxal group, a chael group, and a tetrahydrochael group.

[0065] 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. In the definition of the substituent, 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.

[0066] 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. In the definition of the substituent, 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.

[0067] In the following, the alkyl ether represented by the general formula (I) is represented as a compound (I), and the halogenated alkyl ether represented by the general formula (Π) is represented as a compound (II). A compound having a group represented by the general formula (III) may be represented as a compound (III), and a compound having a group represented by the general formula (IV) may be represented as a compound (IV).

Further, 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).

[0068] In the polyhydroxystyrene derivative described in the above (12), preferably 0.2 to 90%, more preferably 10 to 60% of the total hydroxyl group of the compound (V) is represented by the general formula (III). Substituted with the group represented.

In addition to the novolak rosin derivative described in (14), preferably 0.2 to 90%, more preferably 10 to 60% of the total hydroxyl groups of the compound (VI) are represented by the general formula (III). Is substituted with a group.

[0069] In addition to the polyacrylic resin derivative and the polymethacrylic resin derivative described in (16), 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).

In the present specification, (meth) acrylic acid represents acrylic acid and methacrylic acid, and other (meth) acrylic acid derivatives! I express it in the same way.

[0070] <Compound (1)>

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.

Preferable specific examples of compound (I) include, for example, the following compound formulas.

[0071] [Chemical 27]

[0072] (wherein 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). Here, the alkyl, aryl and aralkyl are the same as described above.

[0073] Among these, the following compounds are more preferable.

(a) A compound in which A and A \ A ² are oxygen atoms or sulfur atoms and m is 1, 2 or 3 in the compounds (1) and (2).

(b) In the compounds (3) to (6), A, A \ A ² is an oxygen atom or a sulfur atom, and m is 1, 2, or 3.

(c) In the compounds (7) to (11), A, A \ A ² , A ³ are oxygen atoms or sulfur atoms, n is 1 and p is 1 or 2.

(d) The compound (12) or (13), wherein A and A ¹ are an oxygen atom or a sulfur atom, n is 1 or 2, and p is 0 or 1.

[0074] As compound (I), one or more compounds are used.

Compound (Π) can be produced, for example, by reacting compound (I) with halogenated hydrogen.

As the hydrogen halide, 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).

[0075] The reaction temperature is preferably 0 to 20 ° C.

In addition, the compound (Π) 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.

Specific examples of the compound (Π) include the following compound formulas.

[0076] [Chemical 28]

(40) (wherein, RR ² , R ⁹ , A, A \ A ² , A ³ , m, n and p are as defined above), among which the following compounds are More preferred.

(a) The compound (21) or (22), wherein A, A \ A ² is an oxygen atom or a sulfur atom, and m is 1, 2 or 3.

(b) In the compounds (23) to (26), A, A \ A ² is an oxygen atom or a sulfur atom, and m is 1, 2 or 3.

(c) A compound in which A, A \ A ² and A ³ are an oxygen atom or a sulfur atom, n is 1 and p is 1 or 2 in compounds (27) to (31).

(d) In the compounds (32) and (33), A and A ¹ are oxygen atoms or sulfur atoms, and n is 1 Or 2. A compound wherein p is 0 or 1.

[0078] As the compound (1), one or more compounds are used.

In the compound (I) or the compound (i), those containing at least one sulfur atom are preferable from the viewpoint of adhesion of the protector to the substrate.

In S (= Y) B or S (= Y) B, Y is preferably an oxygen atom.

2

Yes.

[0079] <Compound having hydroxyl group>

Examples of the compound having a hydroxyl group include alcohols and phenols.

Examples of alcohols include monoalcohols such as methanol, ethanol, propanol, isopropyl alcohol, _n -butanol, isobutanol, sec butyl alcohol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, and benzyl alcohol. Ethylene glycol, 1,3 propylene glycol, 1,2-propylene glycol, 1,4 butanediol, 1,3 butanediol, 1,5 pentanediol, 3-methyl-1,5 pentanediol, 1,6 hexanediol 1,8 octanediol, 2,4 jetyl 1,5 pentanediol, 2 butyl-2-ethyl 1,3 propanediol, 2,2 jetyl 1,3 propanediol, dodecanediol, neopentyl glycol, trimethylolpropane, Penta Examples thereof include polyhydric alcohols such as erythritol, dipentaerythritol, and glycerin.

[0080] The phenols include phenol, resorcinol, hydroquinone, pyrocatechol, bisphenol A, dihydroxydiphenol methane (bisphenol F), bisphenol S, tetrabromobisphenol A, 1,3 bis (4 hydroxyphenol). -L) cyclohexane, 4,4'-dihydroxy 3,3, -dimethyldiphenylmethane, 4,4'-dihydroxybenzophenone, tris (4-hydroxyphenol) methane, bis (4-hydroxyphenol) ) Low molecular weight phenolic compounds such as ether, novolak phenol, novolak cresol, bis (3,5-dimethyl-4-hydroxyphenol) sulfone, bis (4-hydroxyphenol) sulfone, hydroxystyrene, novolac resin, poly Hydroxystyrene, other copolymerizable with hydroxystyrene Having a hydroxyl group such as a copolymer copolymerized with other monomers Examples thereof include polymers. Examples of other monomers copolymerizable with hydroxystyrene include those described below.

[0081] 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.

[0082] 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. , Butyl (meth) acrylate, isobutyl (meth) acrylate, tert butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Alkyl (meth) acrylates, cyclohexyl (meth) acrylates, benzyl (meth) acrylates, isobornyl (meth) acrylates obtained from alcohols with 1 18 carbon atoms and (meth) acrylic acid , (Meth) acrylates such as adamantyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Hydroxyalkyl (meth) acrylates such as lopyr (meth) acrylate, monoglycerol (meth) acrylate, glycol di (meth) such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate Nitrogen-containing units such as acrylates, (meth) acrylamide, (meth) acrylonitrile, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, etc. 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 in combination of two or more.

[0083] As polyhydroxystyrene, compound (V) is preferred.

Most of the novolak greaves are commercially available. For example, m-cresol, ρ-cresol, 2,3 xylenol, 2,4 xylenol, 2,5 xylenore, 2,6 xylenole, 3, 4-hydroxylenole, 3, 5 xylenenole, 2, 3, 4 卜 dimethylphenol, 2, 3, 5 trimethylphenol, 3, 4, 5 These aldehydes may be produced by polycondensation in the presence of 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.

[0084] Compound (VI) is preferred as the novolak rosin.

Moreover, as a 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 ί 1, More preferably, it is from 000 to 20,000.

[0085] 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 Α, j8-unsaturated monomer having carboxyl group such as acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, etc., polyunsaturated unsaturated monomer having carboxyl group such as poly (meth) acrylic resin Polymeric unsaturated monomers having a carboxyl group and other unsaturated monomers copolymerizable therewith Polymers containing carboxyl groups, such as copolymers with monomers, polyester resins having carboxylic groups, alkyd resins, urethane resins, polyamic acid resins, epoxy resins, carboxy group-modified epoxy resins. Among them, 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 A copolymer with is preferred.

[0086] 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.

[0087] In addition, as 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. Here, the acid value is the number of mg of sodium hydroxide required to neutralize the carboxyl group contained in the polymer lg.

[0088] 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.

As the compound having a carboxyl group, 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.

[0089] <Protecting agent for hydroxyl group or carboxyl group containing compound (I) or compound (Π)>

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). In addition, the partial structure derived from the compound (I) or the compound (Π) is easily detached from the compound (ΠΙ) 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 (Π) 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.

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.

[0091] 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.

[0092] The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, and further preferably 0 to 50 ° C.

When using compound (I), it is preferable to use 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. In the production method of the present invention, the target product can be produced in a high yield with few side reactions regardless of which acid catalyst is used. Moreover, you may use an organic solvent as needed. Examples of 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. One or more types are used.

[0093] After completion of the reaction, compound (III) or compound (IV) can also be obtained by purification by a known method such as washing with water or distillation as necessary.

<Method for protecting hydroxyl group or carboxyl group using compound (基)> The method for protecting hydroxyl group or carboxyl group using compound (Π) is also a method for producing compound (ΠΙ) or compound (IV), respectively.

[0094] By reacting the compound (保護) with a compound having a hydroxyl group or a compound having a carboxyl group, the hydroxyl group or the carboxyl group can be protected.

When the compound (Π) is used, the equivalent ratio (molar ratio) of the compound (Π) 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.

[0095] The reaction temperature is preferably 0-100 ° C, more preferably 0-50 ° C, more preferably 0-20 ° C! /.

When using compound (Π), it is preferable to add a base to the reaction system. 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 (化合物) 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. Examples of 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; Examples include aprotic polar solvents such as dimethylacetamide, Ν, Ν-dimethylformamide, dimethylsulfoxide, etc., and one or more are used.

[0096] After completion of the reaction, 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.

When 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.

[0097] In addition, 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.

[0098] When heat treatment is performed, it is preferably performed at 160 to 250 ° C.

In the case of treatment with an acid, 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 (Π) 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). In addition, when water is added, the temperature during the treatment with acid is preferably 20 to 80 ° C.

[0099] When the structure derived from compound (I) or compound (II) is eliminated, an organic solvent may be used. Examples of 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.

In addition, 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.

[0100] As described above, the compound (I) or the compound (できる) 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 (ΠΙ) 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. Preferably, the polyhydroxystyrene derivative in which the hydroxyl group of the compound (V) is substituted with a group represented by the general formula (ΠΙ), and the hydroxyl group of the compound (VI) is represented by the general formula (ΠΙ). And a poly (meth) acrylic resin in which the carboxyl group of compound (VII) is substituted with the general formula (IV), and a photoacid generator.

[0101] The base polymer is represented by the group represented by the general formula (ΠΙ) or the general formula (IV) of the hydroxyl group or carboxyl group power of the compound (ΠΙ) 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.

[0102] <Photoacid generator>

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.

[0103] 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-butoxycarboxylmethyloxyphenyl) ) Sulfone, (4-tert butoxyphenol) bis (4-dimethylaminophenol) sulfone , Tris (4-dimethylaminophenol) sulfone, 2-naphthyl diphenyl sulfone, dimethyl 2-naphthyl sulfone, 4-hydroxyphenol dimethyl sulfone, 4-methoxyphenol Examples thereof include dimethyl sulfone, trimethyl sulfone, 2-oxocyclohexyl cyclohexyl methyl sulfone, trinaphthyl sulfone, tribenzyl sulfone and the like. Examples of the sulfonate include trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2, 2, 2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4 trifluoromethylolene. Benzene sulphonate, 4-fluorobenzene benzene sulphonate, tonolene sulphonate, benzene sulphonate, 4-1 (4-toluene sulpho-loxy) benzene sulphonate, naphthalene sulphonate, camphor sulphonate, octane sulphonate, dodecyl benzene Examples thereof include sulfonate, butane sulfonate, methane sulfonate and the like. Jordonium salt is a salt of odonium cation and sulfonate. For example, dihydro-deuterium, bis (4 tert-butyl-feole) feudon, (4-tert-butoxy-feule) fe-ureo-de-neum, (4-methoxy-feole) feoleo-de-neum, etc. For example, a danium cation. Examples of sulfonates 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.

[0105] Examples of the sulfo-diazomethane 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) ) One (4 methyl phenol sulfo) diazomethane, (2 Naph thyl sulfo) benzoyl diazo Bissulfol-diazo such as methane, (4-methylphenylsulfol) mono (2-naphthoyl) diazomethane, methylsulfol-benzoyldiazomethane, (tert-butoxycarbonyl)-(4-methylphenolsulfol) diazomethane Examples thereof include methane and sulfocarbodiazomethane.

[0106] Examples of 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- ( 4-methoxyphenyl) acetonitrile (PAI-101, manufactured by Midori Chemical Co., Ltd.) and the like.

[0107] Examples of the N-sulfonyloxyimide-type photoacid generator include succinimide, naphthalene dicarboxylic imide, phthalic imide, cyclohexyl dicarboxylic imide, 5-norbornene 1,2,3 dicarboxylic acid Imido, 7-oxabicyclo [2. 2. 1] — 5 Heptene —2, 3-dicarboxylic imide and other imide skeletons, trifluoromethanesulfonate, and nonaflu Olobutane sulfonate, heptadecafluorooctane sulfonate, 2, 2, 2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4 trifluoromethyl benzene sulphonate, 4-fluoro benzene sulphonate, Examples thereof include compounds having a combination force such as tonorenosulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, and the like.

[0108] Examples of the benzoin sulfonate photoacid generator include benzoin tosylate, benzoin mesylate, and benzoin butane sulfonate.

Examples of pyrogallol trisulfonate photoacid generators include, for example, all of hydroxyl groups such as pyrogallol, fluoroglycine, catechol, resorcinol, hydroquinone, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorootatansulfonate. 2, 2, 2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4 trifluoromethylbenzene sulfonate, 4-phenolobenzene benzene sulfonate, tonolene sulfonate, benzene sulfonate, naphthalene sulfonate Examples thereof include compounds substituted with strong phosphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate, and the like.

[0109] Examples of the nitrobenzil sulfonate photoacid generator 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. Benzenesulfonate, 4-trifluoromethylenobenzenebenzenesulfonate, 4-phenolobenzene benzenesulfonate, tonorenosulfonate, benzenesulfonate, naphthalenesulfonate, camphorssulfonate, otatansulfonate, dodecylbenzene Sulfonate, butane sulfonate, methanesulfur Sulfonate, and the like. 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.

[0110] 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.

[0111] Examples of the dalioxime derivative-type photoacid generator include bis-O- (ptoluenesulfurol) _-a -dimethyldarioxime, bis-O- (ptoluenesulfol) α-diphenyldaroxime. , Bis-Ο- (ρ Toluenesulfol) H-dicyclohexyl glyoxime, Bis-Ο- (ρ Toluenesulfol) 2, 3 Pentanedioloxime, Bis-one Ο— (ρ Toluenesulfol) 2-Methyl 3, 4 Pentanedione Glyoxime, Bis Ο— (η Butansnorehoninole) a-Dimethyloleglyoxime, Bis O- (n-Butanesulfol) α-Diphenylglyoxime, Bis Ο— ( η-butanesulfonyl) _-α -dicyclohexylglyoxime, bis-l-O- (n-butanesulfol) -2,3 pentanedione glyoxime, bis-l-O- (n-butanesulfol) 2-methi Lu 3, 4—Pentanedione Glyoxime, Bis-O— (Methanesulfol) α-Dimethylglyoxime, Bis— Ο— (Trifluoromethanesulfol) OC—Dimethyldarioxime, Bis— Ο— (1 , 1, 1-trifluoroethanesulfol) — α-dimethyldarioxime, bis—O— (tert-butanesulfol) at-dimethyldarioxime, bis—O— (perfluorooctanesulfo- _Α ) Dimethyldarioxime, bis Ο (Cyclohexylsulfonyl) _-α — Dimethyldarioxime, bis—O— (Benzenesulfol) a—Dimethyldarioxime, bis— O— (p Fluorobenzene Sulfo-l) α-Dimethyldarioxime, Bis-O— (p-tert Butylbenzenesulfol) α-Dimethylglyoxime, Bis-Ο— (Xylenesulphol) OC-Dimethyldari Oxime, bis - 0 - (camphorsulfonyl - Le) (X chromatography dimethyl Dali oxime and the like.

[0112] 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.

[0113] The chemically amplified resist composition of the present invention may further contain a photosensitizer, for example, anthracenes, anthraquinones, coumarins, and pyromethenes as necessary. The amplification type resist composition may contain an organic solvent as necessary.

Examples of the organic solvent 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. Monoethylenoatenore, Ethyleneglycolenomonoethylenoate, Ethyleneglycolenomonoethylenotel, Diethyleneglycolmonomethinoreether, Diethyleneglycolenomethenoreether, Propyleneglycoldimethylether, Ethyleneglycoldimethyl Ether, diethylene glycol dimethyl ether, 3-methoxybutanol, glycol ethers such as 3-methyl-3-methoxybutanol, propylene glycol monomethyl ether -Glycol ether acetates such as teracetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, butyl acetate, amyl acetate, cyclohexyl acetate, Tert-butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl acetate acetate, ethyl acetate, methyl lactate, ethyl lactate, propyl lactate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, tert-butyl propionate , Esters such as methyl β-methoxyisobutyrate, hydrocarbons such as hexane, toluene, xylene, cyclic ethers such as dioxane, tetrahydrofuran, γ-petit-mouth ratatones, Ν, Ν-dimethylformamide, Ν- Examples include methyl pyrrolidone and dimethyl sulfoxide. The organic solvents may be used alone or in combination of two or more.

[0114] By incorporating an organic solvent into the chemically amplified resist composition of the present invention, 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.

[0115] Furthermore, 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.

[0116] 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.

By including a basic compound in the chemically amplified resist composition of the present invention, 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.

[0117] 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.

Furthermore, the chemically amplified resist composition of the present invention may contain a surfactant as necessary.

Examples of surfactants 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.

[0118] By incorporating a surfactant into the chemically amplified resist composition of the present invention, the coating properties of the chemically amplified resist composition can be improved.

Furthermore, 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. You may contain a storage stabilizer, antifoaming agents, such as a silicone type and a wax type.

[0119] In addition, 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.

[0120] Other types of resin are not particularly limited. For example, 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.

[0121] The modifier is not particularly limited. For example, polyethylene glycol, polypropylene glycol, polybutadiene polyol and polyolefin polyol, OC-hydroxyethyl- _ω -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. Also, the weight average molecular weight of these fats is more preferable than 300 to 30,000 Rhizomu 500 to 10 000!

[0122] 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.

[0123] <Method for Preparing Chemically Amplified Resist Composition>

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.

[0124] 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.

[0125] 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 μm, more preferably 0.1-100 m.

[0126] Examples of the film used as the support include polyethylene terephthalate, polypropylene, polyethylene, polyester, and polybutyl alcohol. When 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 | cover with a film. 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.

[0127] Further, 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.

[0128] 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.

As a method of applying the chemically amplified resist composition of the present invention on a substrate, when 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 μm, more preferably 0.1-100 m.

[0129] When 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.

After applying the chemically amplified resist composition of the present invention to the substrate, the substrate is heated. When the chemically amplified resist composition of the present invention is a solution, examples of 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.

[0130] When the chemically amplified resist composition of the present invention is a dry film, this step can be omitted if heating is performed during lamination.

After heating, the coating film is irradiated with radiation using a photomask, a reduction projection exposure machine, a direct drawing machine or the like. Examples of 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. In the part irradiated with radiation or the like, the photoacid generator is decomposed to generate acid.

[0131] After the irradiation, the substrate is heated. Examples of the heating method include those used for heating after coating. By heating, compound (I) or compound is converted from compound (ΠΙ) or compound (IV). The structure derived from the compound (Π) is eliminated, and the hydroxyl group or carboxyl group is regenerated. The heating temperature is preferably 80-160 ° C.

After the heating, when a dry film is used, the support is removed, and when a dry film is not used, a positive resist pattern is obtained by developing with an alkaline developer as it is. Examples of the developing method include known methods such as an immersion method, a paddle method, and a spray method. Examples of 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. Tilgetylamine, dimethylethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrrole, piperidine, 1,8 diazabicyclo [5.4.0] —7 undecene, 1,5 Diazabicyclo [4.3.0] Alkaline aqueous solution obtained by dissolving a basic substance such as 5-nonane. Basic substances may be used alone or in admixture of two or more. In addition, 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.

[0132] After development, 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.

4 2 2

It can attach | subject to well-known processes, such as.

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

[0133] Hereinafter, the present invention will be described more specifically with reference to synthesis examples, test examples, examples and comparative examples.

The structure of the compound in the examples was determined by 1 H-NMR spectrum (400 MHz, measuring instrument: JEOL GSX-400, measuring solvent: heavy chloroform).

The weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. (GPC analysis conditions)

Equipment: HLC 8120GPC [Tosoichi Co., Ltd.]

Column: TSKgel SuperHM—M [manufactured by Tosohichi Corporation]

Mobile phase: Tetrahydrofuran (flow rate 0.5mlZ min)

Column oven: 40 ° C

Detector: 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.

(Synthesis Example 1) 1 Synthesis of 1- (2-acetylethylethoxy) 2-methylpropene

4 Hydroxy-2-butanone In 88. lg, 0.05 g of p-toluenesulfonic acid monohydrate was dissolved, and 18.0 g of isobutyraldehyde was added dropwise while cooling to 20 ° C or lower. Washing with 100 g of a 1% aqueous sodium carbonate solution and distillation of the oil layer obtained by liquid separation under reduced pressure gave 66 g of isobutyraldehyde bis (2acetoxyl) acetal. 0.06 g of p-toluenesulfonic acid monohydrate was dissolved and heated to 200 ° C. 13 g of the distilled liquid was collected, washed with 10 g of a 1% aqueous sodium carbonate solution, and the oil layer obtained by liquid separation was distilled under reduced pressure to obtain 8 g of a colorless transparent liquid. From the NMR ^ vector, it was confirmed that the liquid was 1- (2-acetylethylethoxy) 2-methylpropene.

'H-NMR δ 5.82 (1H, m), 3.55-3.48 (1H, m), 1.88-1.77 (2H, m), 1.77-1.66 (2H, m), 1.62 (3H, m), 1.54 (3H, m), 1.54—1.21 (6H, m)

(Synthesis Example 2) Synthesis of 1-chloro-1 1- (2-acetylethyl) 1 2-methylpropane

1- (2 Acetylethoxy) 2-methylpropene (8 g) was cooled to 5 ° C., and hydrogen chloride gas (2.05 g) was blown into the solution for 20 minutes to obtain 9.9 g of a colorless transparent liquid. From the “より -NMR spectrum”, it was confirmed that the liquid was 1-chloro-1-mono (2-acetylethyl) -2-methylpropane.

'H-NMR δ 5.59 (1H, m), 3.77-3.72 (1H, m), 2.14-2.08 (1H, m), 1.85 (2H, m), 1.72 (2H, m), 1.52—1.23 (6H, m), 1.03 (6H, d, J = 6 .6Hz)

(Synthesis Example 3) Synthesis of 1- (2 ethylthioethoxy) 2 methylpropene

In 106.2 g of 2-ethylthioethanol, 0.05 g of p-toluenesulfonic acid monohydrate was dissolved, and 18. Og of isobutyraldehyde was added dropwise while cooling to 20 ° C or lower. Washing with 100 g of 1% aqueous sodium carbonate solution and distillation of the oil layer obtained by separation under reduced pressure gave 80 g of isobutyraldehyde bis (2-ethylthioethoxy) acetal. To this, 0.0 g of p-toluenesulfonic acid monohydrate was dissolved and heated at 200 ° C. 16 g of the distilled liquid was collected, washed with 10 g of a 1% aqueous sodium carbonate solution, and the oil layer obtained by separation was distilled under reduced pressure to obtain 10 g of a colorless transparent liquid. From the ^ -NMR ^ vector, it was confirmed that the liquid was 1- (2-ethylthioethoxy) 2-methylpropene.

'H-NMR δ 5. 82 (1H, m), 3. 55- 3. 48 (1H, m), 1. 88- 1. 77 (2H, m), 1. 77- 1. 66 (2H, m), 1.62 (3H, m), 1.54 (3H, m), 1.54—1.21 (6H, m)

(Synthesis Example 4) Synthesis of 1-chloro-1-1 (2-ethylthioethoxy) 1-2 methylpropane

1- (2 ethylthioethoxy) 2-methylpropene (10 g) was cooled to 5 ° C., and hydrogen chloride gas (2.3 g) was blown into the liquid over 20 minutes to obtain 12. 1 lg of a colorless transparent liquid. ^{From the 1} H-NMR spectrum, it was confirmed that the liquid was 1 chloro-1-mono (2-ethylthioethoxy) -2-methylpropane.

'H-NMR δ 5.59 (1H, m), 3. 77- 3.72 (1H, m), 2. 14- 2. 08 (1H, m), 1. 85 (2H, m), 1 72 (2H, m), 1. 52—1.23 (6H, m), 1.03 (6H, d, J = 6.6Hz)

Synthesis Example 5 Synthesis of 1-methoxy-2-methylpropene

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. Collect 12 g of distilled liquid, wash with 10 g of 1% aqueous sodium carbonate solution, and distill the oil layer obtained by liquid separation under reduced pressure to obtain a colorless transparent liquid. 8g body was obtained. From the 1H-NMR ^ vector, it was confirmed that the liquid was 1-methoxy-2-methylpropene.

(Synthesis Example 6) Synthesis of 1 chloro-1-methoxy-2-methylpropane

1-Methoxy-2-methylpropene 8. Og was cooled to 5 ° C, and 3.7 g of hydrogen chloride gas was blown into the liquid for 1 hour to obtain 11.4 g of a colorless transparent liquid. From the 1H-NMR spectrum, it was confirmed that the liquid was 1 chloro-1-methoxy-2-methylpropane.

Example 1

[0134] Protection of the carboxyl group of methacrylic acid by 1- (2-acetylethyl) -1-2 methylpropene

43. Og of methacrylic acid and 99.5 g of 1- (2 acetylethyl) -2-methylpropene were reacted in the presence of 0.02 mol% of toluenesulfonic acid monohydrate at room temperature for 1.5 hours. . The reaction solution was washed with a 1% aqueous sodium carbonate solution, and the oil layer obtained by liquid separation was concentrated under reduced pressure to obtain 99 g of a colorless transparent liquid. From the ^ -NMR spectrum, it was confirmed that the liquid methacrylic acid 11- (2-acetylethoxy) 2-methylpropyl was used.

'H-NMR δ 6.16 (1H, s), 5. 79 (1H, d, J = 5.4 Hz), 5. 58 (1H, m), 3. 56-3. 49 (1H, m) , 1. 96 (3H, s), 1, 94—1.12 (11H, m), 0. 96 (3H, d, J = 6. 8Hz), 0. 93 (3H, d, J = 6. 6Hz)

Example 2

[0135] Protection of the carboxyl group of methacrylic acid with 1— (2 ethylthioethoxy) 2 methylpropene

Methacrylic acid 43. Og and 1- (2 ethylthioethoxy) -2-methylpropene 112.2g were reacted in the presence of 0.02 mol% toluenesulfonic acid monohydrate at room temperature for 1.5 hours. It was. After washing the reaction solution with 1% aqueous sodium carbonate solution, the oil layer obtained by the liquid separation was concentrated under reduced pressure to obtain 108 g of a colorless transparent liquid. From the ^ -NMR spectrum, it was confirmed that the liquid catalyst was 11- (2-ethylthioethoxy) 2-methylpropyl. NMR-NMR δ 6.16 (1H, s), 5. 79 (1H, d, J = 5.4 Hz), 5. 58 (1H, m), 3. 56-3. 49 (1H, m), 1.96 (3H, s), 1.94—1.12 (11H, m), 0. 96 (3H, d, J = 6.8 Hz), 0.93 (3H, d, J = 6.6 Hz )

(Comparative Example 1) Synthesis of 1-methoxy-2-methylpropyl methacrylate

Methacrylic acid 43. Og and 1-methoxy-one 2-methylpropene 86. lg, 0. 02 mol ^_0/0 p-toluenesulfonic acid monohydrate presence of was reacted at room temperature for 1.5 hours. After neutralizing the reaction solution with a 1% aqueous sodium carbonate solution, the oil layer obtained by the liquid separation was concentrated under reduced pressure to obtain 103 g of 1-methoxy-2-methylpropyl methacrylate.

Example 3

[0136] Synthesis of polymethacrylic resin

Add 100 g of propylene glycol monomethyl ether acetate into a flask equipped with a dripping device, stirring device, thermometer, cooling tube and nitrogen gas introduction tube, heat to 80 ° C, and stir in a nitrogen atmosphere. — (2-Acetylethoxy) —2—Methylpropyl 28.8 g, Methylmetatalylate 57.7 7 g, Butylmetatalylate 13.5 g and Azobisisobutyoxy-tolyl (AIBN) 10. Og uniformly dissolved Was dropped from the dropping device over 4 hours. After completion of the dropping, a mixed solution of AIBNZ propylene glycol monomethyl acetate = 0.15 g / 0.3 g was added twice every 30 minutes and aged at 80 ° C. for 2 hours to complete the polymerization reaction. The obtained rosin solution was purified by reprecipitation with hexane to obtain 80 g of a white solid. The weight average molecular weight of the solid was 7,600. This solid is designated as resin P-1. Example 4

[0137] Synthesis of polymethacrylic resin

Add 100 g of propylene glycol monomethyl ether acetate into a flask equipped with a dripping device, stirring device, thermometer, cooling tube and nitrogen gas introduction tube, heat to 80 ° C, and stir in a nitrogen atmosphere. — (2-Ethylthioethoxy)-2-methylpropyl 28.8 g, methyl metatalylate 57.7 g, butyl metatalylate 13.5 g and azobisisobutyoxy-tolyl (AIBN) 10.0 g uniformly dissolved The product was added dropwise from a dropping device over 4 hours. After the completion of dripping, twice every 30 minutes, AIBNZ propylene glycol A mixed solution of nomethyl acetate = 0.15 g / 0.3 g was added and aged at 80 ° C. for 2 hours to complete the polymerization reaction. The obtained rosin solution was purified by reprecipitation with hexane to obtain 80 g of a white solid. The weight average molecular weight of the solid was 8,600. This solid is designated as resin P-2.

(Synthesis Example 7) Synthesis of polymethacrylic resin

Into a flask equipped with a dripping device, a stirring device, a thermometer, a cooling tube and a nitrogen gas introduction tube, propylene glycol monomethyl ether acetate lOOg was charged, heated to 80 ° C, and stirred under a nitrogen atmosphere. —Methoxy-2-methylpropyl (18.4 g), methinoremethalate (57.7 g), butinolemethalate (23.9 g), and azobisisobutylate-tolyl (AIBN) (10.0 g) were uniformly dissolved from the dropping device. It was dripped over time. After the completion of the dropwise addition, a mixed solution of AIBNZ propylene glycol monomethyl acetate = 0.2g / 0.3g was added twice every 30 minutes and aged at 80 ° C. for 2 hours to complete the polymerization reaction. The obtained rosin solution was purified by reprecipitation with hexane to obtain 80 g of a white solid. The weight average molecular weight of the solid was 8,400. This solid is designated as resin P-3.

Example 5

[0138] Protection of the hydroxyl group of phenol novolac rosin with 1 chloro-1 1 (2 acetyl ethoxy) 2 methylpropane

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. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isopropyl ketone, the solvent was distilled off, and then added dropwise to 500 ml of pure water to cause reprecipitation, whereby a pale yellow solid 4 Obtained 0 g. H- from NMR spectra, ivy is divided substituted with 40 mol ^_0/0 force S1- (2 § cetyl ethoxy) 2-methylpropoxy group of the hydroxyl group. The target product had a weight average molecular weight of 4,320. This solid is designated as resin P-4. Example 6

[0139] 1 Chloro 1 1 (2 ethylthioethoxy) 2 Methylpropane phenol Protection of hydroxyl group of Polak resin

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. 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 to give a pale yellow solid 4. 2g was obtained. From the iH-NMR spectrum, it was found that 36 mol% of the hydroxyl group was substituted with 1- (2-ethylthioethoxy) 2-methylpropoxy group. The target product had a weight average molecular weight of 4,200. This solid is designated as Fatty Acid P-5.

(Synthesis Example 8) Protection of hydroxyl group of phenol novolac resin with 1 chloro-1-methoxy-2-methylpropane

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. 3.6 g of solid was obtained. From ¹ H-NMR ^ vector, 30 mole ^_0/0 of the hydroxyl groups of 1-methoxy one 2 - I that is substituted with a methyl propoxy group ChikaraTsuta. The target product had a weight average molecular weight of 4,100. This solid is designated as rosin P-6.

Example 7

1—Black mouthpiece 1— (2-Acetylethoxy) Protection of hydroxyl group of polyhydroxystyrene with 2-methylpropane

Polyhydroxystyrene with a weight average molecular weight of 20,000 (Aldrich) 2. 7g was dissolved in 17.5ml of N, N-dimethylacetamide. Tilethoxy) -2-methylpropane 1. Add 97g and stir to dissolve completely. While stirring, 2.23 g of triethylamine was added dropwise over about 30 minutes. After completion of dropping, the mixture was stirred for about 3 hours. Next, add 20 times the amount of pure water to the resulting solution, extract with methyl isobutyl ketone, distill off the solvent, drop it into 500 ml of pure water and reprecipitate it to obtain a pale yellow solid 3. 5 g was obtained. From the NMR ^ vector, it was found that 35 mol% of the hydroxyl group was substituted with 1- (2-acetylethyl) -1-2-methylpropoxy group. The target product had a weight average molecular weight of 25,000. This solid is designated as 榭脂 Ρ-7.

Example 8

1 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. Dissolve 7g in 5, N-dimethylacetamide (17.5ml). Ruthioethoxy) -2-methylpropane 2.16 g was added and completely dissolved by stirring. Then, 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, the solvent was distilled off, and then dropped into 500 ml of pure water and reprecipitated to obtain 3.6 g of a pale yellow solid. Got. From the H-NMR ^ vector, it was found that 32 mol% of the hydroxyl groups were substituted with 1 (2-ethylthioethoxy) 2-methylpropoxy group. The target product had a weight average molecular weight of 26,000. This solid is designated as resin P8.

(Synthesis Example 9) Protection of hydroxyl group of polyhydroxystyrene with 1 chloro-1-methoxy-2-methylpropane

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. H-NMR ^ than vector, I be 30 mole ^_0/0 of the hydroxyl group is substituted with 1-methoxyethanol one 2-methylpropoxy group ChikaraTsuta. The weight average molecular weight of the target product was 22,000. This solid is designated as resin P-9.

(Test Example 1) Evaluation of adhesion of protective body to substrate

Examples 3, 4, 5, 6, 7 and 8 and the protected form lg obtained in Synthesis Examples 7, 8 and 9 and 4 g of propylene glycol monomethyl ether acetate (manufactured by Kyowa Hakko Chemical Co., Ltd.) were mixed, respectively. It was. Each solution was subjected to a cross cut test according to JIS K 5400 to evaluate the adhesion of each protector to the substrate.

[0142] As the substrate, an aluminum plate, a gold-plated steel plate, a silver-plated steel plate, and a chromium nickel substrate were used.

The evaluation criteria are as shown in the table below. The higher the score, the better the adhesion to the substrate. [0143] [Table 1]

¾ 1

[0144] [Table 2] Table 2 Evaluation Results (Evaluation Score)

Resin substrate

Aluminum Gold Silver

P— 1 1 0 1 0 1 0 1 0

P-2 1 0 1 0 1 0 1 0

P-3 6 8 8 6

P— 4 1 0 1 0 1 0 1 0

P-5 1 0 1 0 1 0 1 0

P-6 4 6 6 6

P-7 1 0 1 0 1 0 1 0

P 8 1 0 1 0 1 0 1 0

P— 9 4 6 6 6 [0145] The protectors obtained in Examples 3, 4, 5, 6, 7 and 8 (resin P-1, P-2, P-4, P-5, P-7 and P-8) Compared with the protective bodies (Resin P-3, P-6, and P-9) obtained in Synthesis Examples 7, 8, and 9, the adhesion to the substrate is excellent.

(Test Example 2) Wetability evaluation of protector

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.

[0146] [Table 3] Table 3: Evaluation results (contact angle)

[0147] The protectors obtained in Examples 3, 4, 5, 6, 7 and 8 (resin P-1, P-2, P-4, P-5, P-7 and P-8) Compared to the protectors obtained in Synthesis Examples 7, 8, and 9 (Resin P-3, P-6, and P-9), the hydrophilicity is high and the wettability with respect to the soldering solution and the like is excellent. Example 9

[0148] According to Table 4, a resin, a resin, a photoacid generator and an organic solvent were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to obtain Composition 1.

Example 10

[0149] According to Table 4, a resin, a resin, a photoacid generator and an organic solvent were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to obtain Composition 2. Example 11

[0150] According to Table 4, a resin, a resin, a photoacid generator and an organic solvent were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to obtain Composition 3.

Example 12

[0151] According to Table 4, a resin, a resin, a photoacid generator and an organic solvent were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to obtain Composition 4.

Example 13

[0152] According to Table 4, a resin, a resin, a photoacid generator and an organic solvent were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to obtain Composition 5.

Example 14

[0153] According to Table 4, a resin, a resin, a photoacid generator and an organic solvent were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to obtain Composition 6.

(Comparative Example 2)

According to Table 4, rosin, photoacid generator and organic solvent were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to obtain composition 7.

(Comparative Example 3)

According to Table 4, rosin, photoacid generator and organic solvent were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to obtain composition 8.

(Comparative Example 4)

According to Table 4, rosin, photoacid generator and organic solvent were mixed. The resulting solution was filtered through a 0.2 μm membrane filter to obtain composition 9.

[0154] [Table 4] Composition Composition Composition Composition Composition Composition Composition Composition Composition String Table 1 2 3 4 5 6 7 8 9

Four

Oil P— 1 2 0

P-2 2 0

P-3 2 0

P-4 2 0

P-5 2 0

P-6 2 0

P-7 2 0

P-8 2 0

P 9 2 0 photoacid precursor 1 1 1 1 1 1 1 1 1 machine 5 7 5 7 5 7 5 7 5 7 5 7 5 7 5 7 5 7

[0155] PAI-101 (manufactured by Midori Chemical Co., Ltd.) was used as the photoacid generator.

As the organic solvent, propylene glycol monomethyl ether acetate (manufactured by Kyowa Hakko Chemical Co., Ltd.) was used.

In Table 4, each numerical value represents part by weight.

(Test Example 3)

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. Next, 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 μm line and space pattern.

[0156] 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.

[0157] [Table 5] Table 5

[0158] From Table 5, it can be seen that the chemically amplified resist compositions (Compositions 1 to 6) obtained in Examples 9 to 14 have good pattern shapes.

Industrial applicability

[0159] According to the present invention, there are provided 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.

Claims

The scope of the claims

[1] General formula (o)

[Chemical 29]

R ¹ X ¹ AR ³

(0)

R ² X ²

[Where X ¹ represents a hydrogen atom, X ² represents a force representing a halogen atom, X ¹ and X ² together represent a bond,

R ³ is alkyl substituted with a group having an oxygen atom and Z or a sulfur atom, aryl substituted by a group having an oxygen atom and Z or sulfur atom, aralkyl substituted by a group having an oxygen atom and Z or sulfur atom, substituted A heterocyclic group containing an oxygen atom and Z or a sulfur atom,-(=) 1 ^ (wherein Y ¹ represents an oxygen atom or a sulfur atom, and R ^A represents A group having an oxygen atom and / or a sulfur atom may be substituted with V, or an alkyl, oxygen atom and a group having a Z or sulfur atom may be substituted with! /, Aryl, an oxygen atom and / or A group having a sulfur atom may be substituted to represent a heterocyclic group containing aralkyl or an oxygen atom and Z or a sulfur atom), or — S (= Y ² ) Y ³ R ^B (wherein p represents 1 or 2, Y ² represents an oxygen atom or a sulfur atom

P

Y ³ represents a bond, an oxygen atom or a sulfur atom, and R ^B represents a hydrogen atom, an alkyl, an aryl or an aralkyl. (However, when A is a sulfur atom, R ³ is alkyl. A protective group for a hydroxyl group or a carboxyl group containing a compound represented by)].

[2] General formula (I)

[Chemical 30]

(Wherein RR ² , R ³ and A are as defined above, respectively), or a general formula (II)

[Chemical 31]

(Wherein R ¹ R ² , R ³ and A are as defined above, and X represents a halogen atom), a hydroxyl group-protecting agent containing a halogenated alkyl ether.

[3] General formula (I)

[Chemical 32]

(Where

[Chemical 33]

(Wherein, RR ² , R ³ , A and X are as defined above), a protective agent for a carboxyl group containing a halogenated alkyl ether.

[4] A group having an oxygen atom and a Z or sulfur atom is oxo, thixo, Y¾ ^A [wherein Y ³ represents an oxygen atom or a sulfur atom, R ^A represents a hydrogen atom, an alkyl,-(CH CH

twenty two O) — R ^aa (wherein q represents an integer of 1 to 3, R ^aa represents a hydrogen atom, alkyl, aryl or aralkyl) or C (= Y ^aa ) R ^ab (where Y ^aa is oxygen Represents an atom or a sulfur atom, R ^ab represents alkyl, aryl or aralkyl), C (= Y ^b ) R ^b [wherein Y ^b represents an oxygen atom or a sulfur atom, and R ^b represents a hydrogen atom , Alkyl, Y ^ba R ^ba (where Y ^ba represents an oxygen atom or sulfur atom, R ^ba represents a hydrogen atom, alkyl, aryl or aralkyl) or — (OCH CH) — R ^bb (where r represents an integer of 1 to 3, R

2 2 r

b ^b represents hydroxyl, alkyl, represents) the Ariru or Ararukiru], -S (= Y ^C)

Y ^d R ^e (wherein s represents 1 or 2, Y represents an oxygen atom or a sulfur atom, Y ^d represents a bond, an oxygen atom or a sulfur atom, and represents a hydrogen atom, alkyl, aryl or aralkyl. Or a heterocyclic group containing an oxygen atom and Z or a sulfur atom.

Compounds having a hydroxyl group are represented by the general formula (I)

[Chemical 34]

(Wherein RR ² , R ° and A have the same meanings as defined above) or the general formula (II)

[Chemical 35]

(Wherein RR ² , R ³ , A and X are as defined above, respectively), which is reacted with a halogenated alkyl ether represented by the general formula (III)

[Chemical 36]

(Where

R ² , R ³ and A are the same as defined above).

[6] A compound having a carboxyl group is represented by the general formula (I)

[Chemical 37]

(Where

R ² , R ° and A have the same meanings as defined above) or the general formula (II)

[Chemical 38]

(Where

[Chemical 39]

(Wherein, R \ R ² , R ³ and A are as defined above, respectively).

[7] A compound having a hydroxyl group is represented by the general formula (I)

[Chemical 40]

(Wherein RR ² , R ³ and A have the same meanings as described above, respectively), and is reacted with an alkenyl ether represented by the general formula (III)

[Chemical 41]

R ²

0 ")

R ³

ヽ. Eight Z

(Wherein RR ² , R ³ and A are as defined above, respectively).

Compounds having a hydroxyl group are represented by the general formula (II)

[Chemical 42]

(")

[Chemical 43]

(Wherein R ¹ R ² , R ³ and A have the same meanings as described above, respectively).

Compounds having a carboxyl group are represented by the general formula (I)

[Chemical 44]

(Where

R ² , R ³ and A are the same as defined above, respectively),

[Chemical 45]

(Where

R ² , R ³ and A are the same as defined above).

[10] A compound having a carboxyl group is represented by the general formula (II)

[Chem 46]

(Wherein RR ² , R ³ , A and X have the same meanings as described above, respectively).

[Chemical 47]

(Where

R ² , R ³ and A are the same as defined above).

[11] A group having an oxygen atom and Z or a sulfur atom is oxo, thixo, Y¾ ^A [wherein Y ³ represents an oxygen atom or a sulfur atom, is a hydrogen atom, an alkyl, (CH 2 CH 2 O) — R ^aa (wherein q represents an integer of 1 to 3, R ^aa represents a hydrogen atom, alkyl, aryl or aralkyl) or C (= Y ^aa ) R ^ab (where Y ^aa is oxygen Represents an atom or a sulfur atom, R ^ab represents alkyl, aryl or aralkyl), C (= Y ^b ) R ^b [wherein Y ^b represents an oxygen atom or a sulfur atom, and R ^b represents a hydrogen atom , Alkyl, Y ^ba R ^ba (where Y ^ba represents an oxygen atom or sulfur atom, R ^ba represents a hydrogen atom, alkyl, aryl or aralkyl) or — (OCH CH) — R ^bb (where r represents an integer of 1 to 3, R

2 2 r

Y ^d R ^e (wherein s represents 1 or 2, Y represents an oxygen atom or a sulfur atom, Y ^d represents a bond, an oxygen atom or a sulfur atom, and represents a hydrogen atom, alkyl, aryl or aralkyl. Or a heterocyclic group containing an oxygen atom and a Z or sulfur atom. The production method according to any one of claims 5 to LO.

Formula (V)

[Chemical 48]

(Wherein R ⁴ 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, k represents 0— All or a part of the hydroxyl groups of the polymer having a weight average molecular weight of 1,000 to 100,000 are represented by the general formula (III)

[Chemical 49]

(Wherein R \ R ² , R ³ and A have the same meanings as described above, respectively).

[13] A group having an oxygen atom and Z or a sulfur atom is oxo, thixo, Y¾ ^a [wherein Y ³ represents an oxygen atom or a sulfur atom, R ^a represents ^a hydrogen atom, an alkyl,-(CH CH

twenty two

O) — R ^aa (wherein q represents an integer of 1 to 3, R ^aa represents a hydrogen atom, alkyl, aryl or aralkyl) or C (= Y ^aa ) R ^ab (where Y ^aa is oxygen Represents an atom or a sulfur atom, R ^ab represents alkyl, aryl or aralkyl), C (= Y ^b ) R ^b [wherein Y ^b represents an oxygen atom or a sulfur atom, and R ^b represents a hydrogen atom , Alkyl, Y ^ba R ^ba (where Y ^ba represents an oxygen atom or sulfur atom, R ^ba represents a hydrogen atom, alkyl, aryl or aralkyl) or — (OCH CH) — R ^bb (where r represents an integer of 1 to 3, R

2 2 r

Y ^d R ^e (wherein s represents 1 or 2, Y represents an oxygen atom or a sulfur atom, Y ^d represents a bond, an oxygen atom or a sulfur atom, and represents a hydrogen atom, alkyl, aryl or aralkyl. 13. The polyhydroxystyrene derivative according to claim 12, which is a heterocyclic group containing an oxygen atom and Z or a sulfur atom.

[14] General formula (VI)

[Chemical 50]

(Wherein 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, and k represents 0 3 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 containing units and having a weight average molecular weight of 1,000-100,000 Is the general formula (III)

[Chemical 51]

(Wherein R \ R ² , R ³ and A are as defined above), and a novolac rosin derivative substituted with a group represented by:

[15] A group having an oxygen atom and a Z or sulfur atom is oxo, thixo, Y¾ ^a [wherein Y ³ represents an oxygen atom or a sulfur atom, R ^a represents ^a hydrogen atom, an alkyl,-(CH CH

twenty two

2 2 r

Y ^d R ^e (wherein s represents 1 or 2, Y represents an oxygen atom or a sulfur atom, Y ^d represents a bond, an oxygen atom or a sulfur atom, and represents a hydrogen atom, alkyl, aryl or aralkyl. ), Or a heterocyclic group containing an oxygen atom and a Z or sulfur atom.

[16] General formula (VII)

[Chemical 52]

(Wherein R ⁸ represents a hydrogen atom, lower alkyl or hydroxymethyl), and a polymer carbocycle having a weight average molecular weight of 1,000 to 100,000. All or part of the syl group general formula (IV)

[Chemical 53]

(Wherein R \ R ² , IT and A are as defined above) and a polyacrylic resin derivative or a polymethacrylic resin derivative substituted with a group represented by:

[17] A group having an oxygen atom and Z or a sulfur atom is oxo, thixo, Y¾ ^a [wherein Y ³ represents an oxygen atom or a sulfur atom, R ^a represents ^a hydrogen atom, an alkyl,-(CH CH

twenty two

O) — R ^aa (wherein q represents an integer of 1 to 3, R ^aa represents a hydrogen atom, alkyl, aryl or aralkyl) or C (= Y ^aa ) R ^ab (where Y ^aa is oxygen Represents an atom or a sulfur atom, R ^ab represents alkyl, aryl or aralkyl), C (= Y ^b ) R ^b [wherein Y ^b represents an oxygen atom or a sulfur atom, and R ^b represents a hydrogen atom , Alkyl, Y ^ba R ^ba (where Y ^ba represents an oxygen atom or sulfur atom, R ^ba represents a hydrogen atom, alkyl, aryl, or aralkyl) or — (OCH CH) — R ^bb (where, r represents an integer of 1 to 3, R

2 2 r

Y ^d R ^e (wherein s represents 1 or 2, Y represents an oxygen atom or a sulfur atom, Y ^d represents a bond, an oxygen atom or a sulfur atom, and represents a hydrogen atom, alkyl, aryl or aralkyl. Or a polyacrylic resin derivative or a polymethacrylic resin derivative according to claim 16, which is a heterocyclic group containing an oxygen atom and a Z or sulfur atom.

[18] A compound having a group represented by general formula (III) according to claim 5 or a general formula (IV) according to claim 6, which has a weight average molecular weight of 1,000 to 100,000. A chemically amplified resist composition comprising a compound having a group and a photoacid generator.

[19] A chemically amplified resist composition comprising the polyhydroxystyrene derivative according to claim 12 or 13 and a photoacid generator.

[20] A chemically amplified resist composition comprising the novolak rosin derivative according to claim 14 or 15, and a photoacid generator.

[21] The polyacrylic resin or polymethacrylic resin derivative according to claim 16 or 17 And a chemically amplified resist composition containing a photoacid generator.