TW561316B - Positive-type photoresist composition for far violet rays exposure - Google Patents

Abstract

Provided is a positive-type photoresist composition for far violet rays exposure, which is excellent in storage stability with time and furthermore the problem of development defects occur during the development can be solved. A positive-type photoresist composition for far violet rays is characterized in that it comprises a compound which generates acid when irradiated with active rays or radiation; a polymer has a repeating unit of specific structure, a specific repeating unit of specific structure having alicyclic rings in the main chain, and a group which is decomposed by the acid action; and a mixture of solvents having at least one selected from the group consisting of butyl acetate and propylene glycol monoalkyl ether carboxylate and having at least one selected from the group consisting of ethyl lactate and propylene glycol monoalkyl ether.

Description

561316 A7 B7 1. Description of the Invention (Technical Field) The present invention relates to a positive type for far-ultraviolet exposure used in ultra-lithography processes such as ultra-LSI or high-capacity microchip manufacturing or other photoresist application processes. Photoresist composition. More specifically, the present invention relates to a positive photoresist composition for far-ultraviolet exposure using a far-ultraviolet range containing excimer laser light, particularly a wavelength below 250nm, to form a high-definition pattern. [Prior Art] In recent years, in order to further increase the integration degree of integrated circuits, it is necessary to process ultra-fine patterns with a line width of less than half a micrometer in the manufacture of semiconductor substrates such as ultra-LSI. To meet this need, the wavelength of exposure devices used in photolithography has been made shorter, and short-wavelength excimer laser light (XeCl, KrF, ArF, etc.) in far-ultraviolet light is also being reviewed. The pattern forming lithography user in this wavelength range is a chemically amplified resist. Generally speaking, chemically amplified resists can be divided into three categories: two-component system, 2.5-component system, and three-component system. The two-component system is a combination of a compound (hereinafter referred to as a photoacid generator) that generates an acid by photodecomposition and a binder resin. This binder resin is a resin which is decomposed by the action of an acid and has a group (acid-decomposable group) which increases the solubility of the resin in the alkali developing solution in the molecule. The 2.5-component system contains a low-molecular-weight compound having an acid-decomposable group in the 2-component system. The three-component system is one containing a photoacid generator, an alkali-soluble resin, and the aforementioned low-molecular compound. The above chemical amplification system is suitable for ultraviolet or far ultraviolet irradiation. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page). Bureau of Intellectual Property, Ministry of Economic Affairs Printed by the employee consumer cooperative_ ϋ ϋ ϋ i ^ i · 1 ϋ ni ^ i ϋ I «ϋ ί ϋ ϋ i II · ϋ ^ 1 ϋ ϋ ^^ 1 ^ 1 1 n ϋ ^ 1 ^ 1 ϋ ^ 1 ^ 1 * 561316 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention: (Use photoresist, but it must have other characteristics corresponding to the requirements in use.

The photoresist composition system for ArF light sources has been proposed to introduce resins having alicyclic hydrocarbon sites for the purpose of having dry etching resistance. However, the disadvantage of introducing alicyclic hydrocarbon sites is that the system is extremely hydrophobic. It is extremely difficult to develop a tetramethylammonium cyanide (hereinafter referred to as TMAH) aqueous solution, which is a widely used resist imaging liquid, and the phenomenon such as peeling off from a substrate occurs during development. Corresponding to the hydrophobization of the barrier, reviewing the correspondence of organic solvents such as isopropyl alcohol in the developing solution, although the effect can be seen, problems such as the expansion of the barrier film or complicated engineering must be solved. Most of the methods for improving the resistance have adopted a policy of introducing a hydrophilic group to compensate for each of the alicyclic hydrocarbon sites which are hydrophobic. Japanese Unexamined Patent Publication No. 10-10739 discloses a polymer obtained by polymerizing a monopolymer having an alicyclic structure such as an orthospinene ring in the main chain, a maleic anhydride, and a monopolymer having a carboxyl group. Energy-sensitive barrier material. Japanese Patent Application Laid-Open No. 10- 1 1 1 569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic structure in a main chain and a radiation-sensitive acid generator. Japanese Patent Application Laid-Open No. 1 1-202491 discloses a radiation-sensitive resin composition containing a polymer containing an orthospinene derivative and a polymer with an androstane-17-carboxylic acid ester compound. The acid-decomposable group-containing resin used in the positive-type photoresist composition for far-ultraviolet exposure is generally one that contains both aliphatic cyclic hydrocarbon groups in the molecule. Therefore, the resin is hydrophobic, which is the cause of the problem. In order to improve this point and review the above-mentioned various methods, there are still a lot of inadequate points (especially in terms of imaging) in the above-mentioned techniques to improve.

In other words, the above-mentioned extreme ultraviolet light, short-wavelength light source, such as A rF -4- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the back ^ precautions before filling in the page) ^ = ° 561316 A7 B7 V. Description of the invention (4) (Please read the phonetic entries on the back, and then excimer laser (193nm) as the exposure light source, the image development still needs to be improved. Specifically, in the body fluid barrier There are still improvements in storage stability. For example, when the chemically amplified photoresist is stored in a liquid state, the resin and the photoacid generator have poor compatibility, particles are generated in the liquid, and the barrier property is not good. Other problems exist (poor storage stability of barrier fluids). [Disclosure of the invention] f The purpose of the present invention is to provide a method for using the far-ultraviolet light, especially ArF excimer laser light, to solve the above-mentioned low-light compositional processing original performance. The subject of improvement is to provide a positive photoresist composition for far-ultraviolet exposure with excellent storage stability. The inventors have repeatedly studied the results of reviewing the resist composition of the positive chemical amplification system, Now, the purpose of the present invention can be achieved by using at least two specific acid-decomposable resins. In other words, the above-mentioned object is achieved by the following constitution. (1) A positive-type light for extreme ultraviolet exposure A resist composition comprising (A) a compound that generates an acid by irradiation with active light or radiation, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and (B) having at least one selected from the following general formula (ia) and The resin having the repeating unit represented by the general formula (ib) and the repeating unit represented by the following general formula (II) and having a group (acid-decomposable group) decomposed by an acid action is characterized in that 2 types of resins with different content (mole%) of repeating units containing acid-decomposable groups in all repeating units. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 ^ A7 __ _ B7 4 / IV Instructions CICIXIAIR2 cn cl XI A— RT = ο ο

ο

C C

ο

Iaz (please read the note i6lR1 (\ —p ^-丨 R1 1 / 1- actually climb the term and then fill in the page)) (in formula (la), 'R! And R2 are not independent chlorine atoms, cyanide Group, hydroxyl group, -COOH, -COOR5, -CO-NH-R6, -C0-NH-S02-R6, optionally substituted alkyl, alkoxy or cyclic hydrocarbon group, or the following -γ group; X series Represents an oxygen atom, a sulfur atom, -NΗ ·, -NHS02- or NHS02NH-; wherein R5 represents a substituted alkyl group, a cyclic hydrocarbon group or the following -Y group; 1 ^ 6 represents a substituted alkyl Or cyclic hydrocarbon group; A is a single bond or a divalent linking group; -Y is

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R21 ~ R3Q each represents an independent hydrogen atom or an alkyl group which may have a substituent, a and b represent 1 or 2); In formula Ub), Z2 represents -〇-or -N (R3)-; -6- This paper size applies to Chinese National Standard (CNS) A4 (210 x 297 mm) 561316 A7 V. Description of the invention (,) R3 means hydrogen atom, hydroxyl or -0S02-R4; R4 represents an alkyl group, a halogenated group, a circular group or a clavyl residue; in the formula (II),

R11 is a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent; Z is a cycloaliphatic structure which contains two depleted atoms (CC) to form a substituent. (Atomic group) (2) The positive-type photoresist composition for far-ultraviolet exposure according to the above (1), wherein the resin (B) is a double layer containing two types of acid-decomposable groups having all repeating units The difference in unit content is 5 to 30 mol%. (3) The positive-type photoresist composition for far-ultraviolet exposure as described in the above (1) to (2), wherein “Z” in the general formula (11) contains two carbon atoms (CC), In order to form an atomic group having a bridged alicyclic structure which may have a substituent. (4) The positive photoresist composition for far-ultraviolet exposure according to the above (1) to (2), wherein the general formula (II) is the following general formula or general formula (II-B).

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

(Wherein the formulas (Π-A) and (ΙΙ · Β),

Rl3 ~ Rl6 are hydrogen, halogen, cyano,

This paper size applies to China National Standard (CNS) A4 specifications (210 X -7- 561316 A7 B7) V. Description of the invention (Heart (Please read the note of C on the back and fill in -COOH,-邙 (^ 5 (1Series Synonymous with the above), a group decomposed by the action of acid, -C (di0) -XA-R17, or an alkyl or cyclic meridian which may have a substituent; and at least 2 of R13 ~ R16 are bonded to form Ring; η represents 0 or 1; here, X and A are each synonymous with the above; R17 is -C00H, _C0〇R5, -CN, cyano, alkoxy which may have a substituent, -C0-NH -R6, -c〇-nh-so2-r6 (r5, r6; each has the same meaning as above) or the above-Y group) (5) Far-ultraviolet exposure as described in any one of (1) to (4) above A positive-type photoresist composition containing a nitrogen-containing basic compound. (6) The positive-type photoresist composition for far-ultraviolet exposure as described in the above (5), wherein the nitrogen-containing basic compound is At least one selected from 1,5-diazobicyclo [4.3.0] -5-nonene, 1,8-diazobicyclo [5.4.0] • 7-undecene, 1,4-di Azobicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethyl Imidazolines, pyrroles, imidazoles, trazines, pyrimidines, tertiary morpholines, and hindered amine compounds having a hindered piperidine structure. [Embodiments of the Invention] The present invention will be described in detail below. Compounds used (A) Compounds that produce acid by irradiation with active light or radiation Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The photoacid generator used in the present invention is a compound that generates acid by irradiation with active light or radiation The compounds used in the present invention to generate acid by irradiation with active light or radiation can be appropriately selected using a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for pigments, and Conventional light used in color-changing agents, or micro-resistors (ultraviolet rays of 400-200 nm, this paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 public love) 561316 A7 ^ ____ B7__ V. Description of the invention (7 ) (Please read the notes on the back before filling this page) Especially g-line, h-line I-line, KrF excimer laser light), Ar * F excimer laser light, electron line, X-ray, molecule Or ion beam to generate acid compounds and appropriately select these mixtures. In addition, other compounds used in the present invention to generate acid by irradiation with active light or radiation, such as SIschlesinger, Photogr.Sci.Eng., 18,387 (1974) 'TSBal et al, Polymer, 21, 423 (1980) and other diazo iron salts, U.S. Patent No. 4,069,055, same as 4,069,056, same as Re27,992, and Japanese Patent Application No. 3-140140 And other ammonium salts, DCNecker et al, Macromolecules, 17,2468 (1984), CS, Wen et al, The, Proc. Conf. Rad Curing ASIA, p.478 Tokyo, Oct (1 988), U.S. patent Ferrophosphonium salts described in Nos. 4.069,055 and 4,069,056, JVCrivello et al, Macromoreccules, 10 (6), 1 307 (1 977), Chem. &Amp; Eng.News, Nov. 28, p, 3 1 (1 988), European Patent No. 1 04,1 43, same as 339,049, same as 410,201, Japanese Patent Laid-Open No. 2-1 50848, Japanese Patent Laid-open No. 2- 2965 1 4 and the like, JVCrivello et al, Polymer J. 17, 73 (1985), JV Crivello et al, J. Org. Chem., 43, 3055 (1978) 'Intellectual Property of the Ministry of Economic Affairs Printed by an employee consumer cooperative WR Watt et al, J. Po1ymer. Sci., Po1ymer Chem. Ed., 22,1789 (1984) 'JVCrivello et al, Polymer Bull., 1 4,279 (1 985)' JVCrivello et al , Macromorecu1es, 14 (5) J 1141 (1981) '' JVCrivello et al, J. Polymer.

Sci ·, Polymer Chem. Ed., 17,287 7 (1979), European Patent Nos. 370,693, same as 161,811, same as 410,201, and 339,049-9- This paper standard applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention ((Please read the note of backing and then fill in the 4 contentions, the same as 23 3,567, the same as 297,443, the same as 297,442, the US patent 3,092,114, the same as 4,933, No. 3 77, No. 4,760,0 1 No. 3, No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626, No. 3,604,580, No. 2,604,58 1, No. 7-28237, No. 8-27102, etc. The recorded Yuyan, J.V. Crivello et al, Macromoreculers, 10 (6), 1307 (1977) 印 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 'JVCrivello et a 1, J. Po1ymer, Sci., Selenium selenium salts described in Po1ymer Chem. Ed., 17, 1047 (1 979), CS, Wenetal, The, Proc. Conf. Rad, Curing ASIA, p. 478 Tokyo. Oct (1 988), etc. Iron salts such as salt, U.S. Patent No. 3,905,8-15, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-3628, Japanese Patent Application No. 1 55-32070, JP Sho 60-2 39736, JP Sho 6 1-1 69835, JP Sho 6 1-1 698 37, JP Sho 62- 58241, JP Sho 62-212401 , Organic halogen compounds described in JP 63-70243, JP 63- 2983 39, etc., K. Meier et al, J. Rad. Curing, 1 3 (4), 26 (1 986) 'TP Gi11 et a 1, I norg. Chem., 19,3007 (1980), D. Astruc, Acc · Chem. Res., 19 (12), 377 (1 896), JP 2-1 6 1 445, etc. Documented organometallic / organohalides, S. Hayase et al, J. Polymer Sci., 25,753 (1 987), E. Re ichman is et a 1, J. Polymer Chem. Ed., 23, K 1 985 ) > QQZhu et a 1, J. Photochem., 36, 85, 39, 3 1 7 (1 987), B. Amit et al, Tetrahedron Lett., (24) 2205 (1 973) > DHRBarton et a 1, J. Chem. Soc., 357 1 (1 965), PMCollins et al, J. Chem. Soc. 'Perkin I, 1695 -10- This paper size applies to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) 561316 A7 B7 V. Description of the invention (9) (1975) 'M.Rudinstein et al, Tetrahedon Lett., (17) (Please read first Reconsideration of the noticeable items, 1 445 (1 975) 'JWWalker et a 1, J. Am. Chem. Soc., 110, 7170 (1988)' SC Busman et al, J. Imaging Technol., 1 1 (4), 1 91 (1 985) 'HM Houlihan et al »Macromolecules? 21, 2001 (1988)' PM Collins et al, J. Chem. Soc., Chem. Commun., 532 (1972), S Hay ase et al, Macromo1ecu1es, 18, 1799 (1985) 'E. Reichmanis et al, J. Electrochem. Soc., Sol id State Sc i. Techno 1., 130 (6), FM Houlihan et a 1, Ma cr omo 1 ec u1e s, 21, 2001 (1 988), European Patent No. 0290,750, same as 046,083, same as 1,56,5 3 5, same as 27 1,85 1, same as 0,388, 343, U.S. Patent Nos. 3,901,710, the same as 4,181,531, Japanese Patent Laid-Open No. 60-1985985, Japanese Patent Laid-Open No. 53-133022, etc. Photoinitiator, M.TUNOOKA et al, Polymer Preprints J apan, 35 (8) 'G. Berne r et a 1, J. Rad. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

Curing, 13 (4) 'WJMijs et al, Coating Technol, 55 (697), 45 (1983), Akzo.H. Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent No. 01 99,6 No. 72, No. 84,515, No. 044,115, No. 618,564, No. 0101,122, U.S. Patent No. 4,371,605, No. 4,431,774, JP-A 64-143, JP-A 2-245756, Typical sulfonic acid compounds such as aminosulfonic esters described in Japanese Patent Application Laid-Open No. 3-1 40 109 and the like generate sulfonic acids. Japanese Patent Laid-Open No. 3-1 03854, same as 4-103856, same as 4-21 0960, etc. Documented diazolone mills and diazobismill compounds. -11- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of Invention l (〇) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. Compounds that generate acidic bases or introduce compounds into the main or side chains of polymers can be used, for example, MEWoodhouse et a 1, J. Am. Chem. Soc., 1 04,5586 (1 982) 'SPPappas et al, J. Imaging Sci., 30 (5), 218 (1986) 'S. Kondo et al, Makromol. Chem., Rapid Commun., 9,625 (1988) ^ Y. Yamada et a 1, Makromo 1, Chem. , 1 52, 1 53, 1 63 (1 972) 'JVCrivello et a 1, J. Polymer Sc i., Po1yr r Chem. Ed., 1 7,3845 (1 979), U.S. Patent No. 3,849,1 37 German Patent No. 3914407, JP-A-Sho 63-26653, JP-A-Sho 55-1 64824, JP-A-Sho 62- 69263, JP-A-Sho 63-1 46038, JP-A-Sho 63-1 63452 Compounds described in JP-A-Sho 62-1 53853, JP-A-Sho 63-1 46029, and the like. Alternatively, NRPillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetrahedron Lett., (47) 4555 (1 97 1) 'DHRBarton et a 1, J. Chem. Soc ., (C)? 329 (1970), US Pat. No. 3,799,778, and European Patent No. 126,712 are compounds which generate acid by light. The following is a description of the compounds which are particularly effective among the above-mentioned compounds used to generate an acid by irradiation with active light or radiation. (1) A trihalomethyl substituted triazine derivative represented by the following general formula (PAG1) or an S-triazine derivative represented by the general formula (PAG2). τ > 202 Ν — Ν // \\ i201'C, (/ C, C (Y) 3 (PAG1) N ^ N (Y) 3C ^ N ^ C (Y): i (PAG2) 12- this paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back before filling in A7 V. Description of invention jG) (where R ί represents a substituted or unsubstituted aryl group The group R represents a substituted or unsubstituted aryl group, a storage group, a radical, C (Y) 3. Y represents a chlorine atom or a bromine atom. Specifically, for example, there are the following compounds, but the present invention Not subject to these restrictions. (Please read back &

A Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 · · · A7 B7 Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Explanation (C1 > / = \ — ^^ ~ CH =: CH-C ",: C-CC13 (PAG1-1) 0 h3c NN CH = CH —C ",: C-CC13 0 (PAG1-2) __ NN H3CO CH = CH-C ",_;, C-CBr3 (PAG1-3) 0 NN // \, (iOQHgO CH = CH-C, 〇 / C-CC13 • 0 0

CH = CH 〇 ~ cVc—cc 丨 (Please read the notes on the back before filling in this page) # (PAG1-4) (PAG 卜 5)

N-N

N-N (D- ch = ch c ", 〇: c -cci (PAGl-6) N-N CH = CH-C, C-CCI3 o 〇 (PAGl-7)

< y NN CH = CH-CV / C-CCI3 0 (PAG1-8) 14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Order -------- Γ -Line 561 · 316316, A7 B7 V. Description of the invention (ο CC13 Cl Λ V ^ N ^ CC13 (PAG2-1) N into N ei3c person ν '(PAG2-2) och3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Please read the notes on the back before filling in this page) ·! Ding] I ^^ 1 ϋ ϋ §1 ϋ ϋ ϋ I ί ϋ— 11 ί ^ 1 ^ ϋ ^^ 1 ϋ ϋ ϋ n ιβ ni ^ i ϋ— i ^ in ϋ 1_1 an i I _ N ~ N C13C ^ N ^ CC13 (PAG2-3)

(PAG2-5)

C13C ^ N ^ CC13 (PAG2-7)

(PAG2-4)

COCH, (PAG2-6) OCH3 CH = CHN People N Λ Λ C13C N CC13 (PAG2-8) • 15 · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 V. Invention Explanation <4)

CH = CH

Q

CH-CII ό

N N C13C ^ N ^ CC13 8 C13C Wci3 (PAG2-9) (PAG2-10) j (2) An iodonium salt represented by the following general formula (PAG3), or a salt of the general formula (PAG4). Ar1. ^ Rule 203) ΦΦΘ r2〇4_ ^ s®z0 Αι ^ / j ^ 205 (PAG3) (PAG4) (where 'Ar1 and Ar2 represent each independently substituted or unsubstituted aryl group, preferably Examples of substituents are alkyl, halogenated alkyl, naphthenic, Intellectual Property Bureau of the Intellectual Property Bureau, employee consumer cooperatives, printed groups, aryl, alkoxy, nitro, carboxy, alkoxycarbonyl, hydroxyl, thiol, and halogen. Atoms: R20 3, r2 04, and r22 05 each represent an independently substituted or unsubstituted academic group or aryl group. Preferred are aryl groups having 6 to 14 carbon atoms and alkane groups having 1 to 8 carbon atoms. And these substituted derivatives. Preferred substituents for aryl are alkoxy having 1 to 8 carbons, alkyl having 丨 to 8 carbons, nitro, carboxyl, hydroxyl, and halogen atoms. Alkyl group has alkoxy group with carbon number of 1 ~ 8, Qian-16-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 public love) &quot; 561316 A7 B7 i, invention description 6) Alkoxycarboxyl. Is an anion such as BF4 ·, ASF6 ·, PF6 ·, SbF6-, SiF〆, C104_, CF3S03 · and other perfluoroalkanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, naphthalene-1-sulfonic acid anions, etc. The polynuclear aromatic sulfonic acid anion, anthraquinone sulfonic acid anion, sulfonic acid group-containing dye and the like are condensed, but the present invention is not limited thereto. In addition, at least two of R2G3, R2 (m, R2G5, and Ar1 and Ar2 may each be a single bond or a substituent. The specific examples are compounds shown below, but the present invention is not limited by these. (Please Read the lack of notes on the back before filling

C12H25 Ο ·-? (PAG3-1)

S〇f SbFe Θ (l) AG3-2) (PAG3-3) (PAG3-4), 17- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316-A7 B7 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives V. Invention Description (40-® (PAG3-5)

CF3S03 Θ 〇 ~]

/ -〇ch3 pf6 (PAG3-6) Θ

^} ~ 〇CH3 SbF6G (PAG3-7) 〇2n (PAG3-8) N02 {I} -1 CF3S03 θ (PAG3-9) Θ —arc AsF, (PAG3-10) ®

Θ (Please read the notes on the back before filling this page) l · '· * 0 n I —ϋ i · — Βϋ · ϋ ϋ Γ, I i ^ i i ^ i ϋ l · f

C12H25 θ

Cl

r®

(PAG3-13)

Cl —18— This paper is sized for China National Standard (CNS) A4 (210 X 297 mm)

SO —— — — — — — — — — — — — — — — — — — 561316 A7 B7 V. Description of the invention (mouth, .〇 ~ '©

F3C-\\ ^ / ~ CF3 (PAG3-1Ί) CF3SO3 Θ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) n —. 1 n I nnn 一 OJI n · ϋ I ϋ ϋ n I nn ϋ n ϋ ϋ In mnni--1 ϋ I m ϋ— I i I-mn ·

lBu ~ 〇 ~ Θ (PAG3-17) Θ (PAG3-18)

(PAG3-19)

PF (Θ pf6 Θ lBu SbF.®

C12H25 lBu X

S〇f PF (Θ CF3SO3 Θ • 19- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 561316,. A7 B7 V. Description of invention (d) Consumer Cooperatives of Intellectual Property Bureau, Ministry of Economic Affairs Print

—20 (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316,. A7 B7 V. Description of the invention (β

(PAG3-25)

〇 (PAG3-26) ©

s〇3 (och3 θ (Please read the notes on the back before filling this page) l ·! · ____ Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (PAG3-27) Sip-· ϋ ϋ —ϋ in an ϋ I ϋ ϋ ϋ ϋ .ϋ ϋ ϋ ^ 1 ϋ n ϋ n ι ^ 1 ϋ n ϋ ^ 1 ϋ n · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 'A7 _B7 / Five Description of the invention (/) N-&lt; Q &gt;-i ^ &lt; Q)-^ CF3 (CF2) 3S〇30 (PAG3-28) N-&lt; Q &gt;-I ^ Q) --- CFaiCF ^ TSO® (PAG3-29) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 2 This paper size applies to China National Standard (CNS) A4 (210 X 297 (Mm) 561316,. A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (w ^ 12 ^ 25 αα (PAG4-1)-S @ (PAG4-2) -S® (PAG4-3)

© S〇3 h3c ch3 ♦ ch3 ΘS〇3

AsF · Θ (Please read the notes on the back before filling this page) Θ

SbF6 Θ (PAG4-4) • s® CF3SO30 (PAG4-5). 18 ^ 1? 5〇3 Θ (PAG4-6)

FF F-0LS〇3G (PAG4-7) FF • 23 · 一 ^ I ^ 1 ι · ϋ ι ϋ ϋ ϋ I ϋ · ϋ n ϋ · ϋ n i_l ϋ n ϋ ϋ ϋ ϋ n ϋ ϋ ϋ ^ 1 « ϋ n-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 &gt;, A7 B7 h3co ®

OC2H5 CF3S03v (PAG4-8) ~ Qr% y (PAG4-9) Θ

Cl) CF3SO3 2 Θ h〇 ^ 〇- Θ S-CH3 CH3 (PAG4-10) pf6g (Please read the precautions on the back before filling this page)

c 3 Θ-H s — c

3 H

SbF6G H3c (PAG4-11)

HO 〇 ~ s9 (PAG4-12)

SO Θ ------- Order --------! Line • 丨 Win Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

CF3SO3 • 24 · Θ This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention (4 (lOQHg HO ⑻QHg PF6 Θ (PAG4-14) H〇 ^ C ^ ~ Sf} BF4 ch3 (PAG4-15) Θ

H3c HO H3C pf6 Θ (Please read the notes on the back before filling this page). * 'L. # (PAG4-16)

AsF, Θ

(PAG4-17) Order ------- / Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

C8F17S03 Θ (PAG4-18) • 25 · This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 561316 A7 B7 V. Description of the invention (Η &quot;

0 II 〇 C-CH ^ -S—CH3 SbF60 CII, (PAG4-19) PF. Θ (PAG4-20) &lt; Q-C-CH2-S0

AsFi Θ (Please read the notes on the back before filling this page) (PAG4-21) &lt; ^^ C-CH ^ S0 Cl

AsF (Θ 6 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (PAG4-22) 0 (^ -S-ch2-s® (PAG4-23) co ^, — € Cl2H25o- (PAG4-24) .26 · 本Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) so 561316 A7 B7 V. Description of invention C-CH factory S—⑹ QHg (n) C4II9 (PAG4-25) pf60

CgH17S〇3 Θ (PAG4-26)

0 ~ s ~ 0 ~ sC

C12H25

Θ 03 s (Please read the notes on the back before filling this page) l.l ·, # (PAG4-27)

S 2CF3SO3 ch3 S 2H3C &quot; ^^^-S〇f CH3 (PAG4-29) Θ Order ------- ^! Line • 丨. Printed by h3c (PAG4-30) of Employees ’Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs (PAG4-31)

• 27- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention (O-f CH2C1ch3 (PAG4-32)

/ = \ f ^ _jHc-ch2-s®

(PAG4-33)

(PAG4-34) (Please read the notes on the back before filling out this page) 0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs · 28 · 一 ον · n ϋ · _ϋ ϋ n ^^ 1 I i I i ^ in I ^^ 1 n ϋ · ϋ n · 11 -ϋ I— II ϋ n I— n-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention 厶) h3c ch3

CFaCCF ^ TSO® h3c

ch3 A

CFaCCF ^ Sof C8H17-〇

The above-mentioned iron salts shown by CFaCCF ^ Sof general formulae (PAG3) and (PAG4) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are known, such as JWKanpaczyk et al, J.Am.Chem.Soc., 91, 145 (1969) 'AL Maycok et a 1, J. Org. Chem., 3 5, 2532, (1970), E. Geothes et al, Bull.Soc. Chem. Belg., 73, 546, (1 964), HM Leices ter. J. Am. Chem. Soc., 51, 3587 (1929) 'JVCrivello et al, J. Polym. Chem. Ed., 18, 2677 (1 9 80), U.S. Patent No. 2,807,648 It is synthesized by the methods described in 4,247,47 No. 3, JP 53-101, 331 and the like. (3) A difluorene derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6). -29- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 g t) 56! 3l6 5. Is the invention explained? 0

Ar3 ~ S02-S0 Wide At4 R206-so2-on (PAG5) (ΡΛΓ.6) Λ ο (wherein Ar3 and Ar4 each represent an independent substituted or unsubstituted square group, and R 2 ° 6 represents brilliance A substituted or unsubstituted alkyl group or aryl group, A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but the present invention is not limited thereto . (Please read the phonetic note on the back of the article first) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 561316 · A7 B7 V. Description of the invention ( β! 〇-S02-S02-^^ (PAG5-1) H3C S〇2- S〇2_CH3 (PAG5-2)

Cl ·

Cl H3CO 乂)-S02- S02-^^-(PAG5-3) H3C S02- S〇2-^^ (PAG5-4)

OCH 3 (Please read the notes on the back before filling this page)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs f3c s〇2-s〇2 ~ ^ y ~ cp3 (PAG5-5) S02—so2—

Cl (PAG5-6)

H ^ O

S〇2- S〇2 (PAG5-7) ca S02-SO; (PAG5-8) O 'j_0 ~ • 31 ·

Cl

Cl This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 561316 ·, 1 A7 B7 V. Description of the invention (w)

Cl οα

Cl S02-so: (PAG5-9), 〇 CH, so2— so2— OCH, (PAG5-10) — ^ ~ ^ ~ so2—S02 (PAG5-11)

OCH3 HOC. \ f ~~ \ j H / C S〇2 ~ S〇2 \ _J h3c n 一 ^ ’(PAG5-12) F F S02— S02— ^ S— F F F F (PAG5-13)

F F F

F (Please read the notes on the back before filling this page)

Order ------ U --- line I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

H) — (\ &gt; -S02-S02- (PAG5-14) I S02— S02 — (PAG5-15) &quot; .32 · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) 561316 &gt; A7 B7 V. Description of the invention (Μ 0

〇

Ν-0-S02 Ό ~ CH, Ο Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs / (〇 (PAG6-2)

.33 · och3 CF, OCH, (Please read the notes on the back before filling this page)

The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561316-Α7 • &quot; Β7 V. Description of the invention ("0 [Γ ^ Ν-0 ~ S02-C2H5 〇 (PAG6-7) 〇 C ； no ~ so2 ^ ο (PAG6-8) ο

Ο

-------------------- tl --------- ^ I (Please read the notes on the back before filling out this page) Intellectual Property Bureau, Ministry of Economic Affairs Printed by Employee Consumer Cooperative

.34- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention

N one 0 one S02 one CF3 (PAG6-13)

(Please read the notes on the back before filling this page) 0

F F N-O-SOo -H-f Printed by Consumer Consumption Cooperative of Intellectual Property Bureau, Ministry of Economy

0 F F (PAG6-15) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) A7 137

561316 V. Description of the invention ") ο

CH, read the notes on the back t items i page Ο

2 ir3 X? 17

F Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the amount of these compounds that generate acid by irradiation with active light or radiation is based on the total weight of the resist composition (except the coating solvent), usually 0.001 ~ 40 1% to 5% by weight, preferably 0.01 to 20% by weight, and more preferably 0.1 to 5% by weight. If the amount of the compound that is decomposed to generate acid by irradiation with active light or radiation is less than 0.001% by weight, the sensitivity is low, and if it is more than 40% by weight, the light absorption of the resist is too high, the appearance is poor, or the engineering (especially Is baking) the range is too narrow to be desirable. -36- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Inventive Note Please read the notes on the back before filling in 4 Next, it is stated that (B) has at least one It is selected from a repeating unit represented by the following general formula (la) and general formula (lb) and a repeating unit represented by the following general formula (II), and has a group (acid-decomposable group) decomposed by an acid action. ) (Hereinafter referred to as "the resin of the present invention"). In the general formula (la), R! And R2 each represent an independent hydrogen atom, cyano, hydroxyl, -COOH, -COOR5, -CO-NH-R6, -CO-NH-S02-R6, and may have Substituted alkyl, alkoxy, or cyclic hydrocarbon group, or the following -Y group; wherein 1 ^ 5 represents an optionally substituted alkyl group, cyclic hydrocarbon group, or the following -Y group; R6 represents optionally substituted Alkyl group or cyclic hydrocarbon group; in the above-Y group, R21 to R30 are each independent hydrogen atom or an alkyl group which may have a substituent, a and b represent 1 or 2; X represents an oxygen atom , A sulfur atom, -NH-, -NHS02, or -NHS02NH-; A represents a single bond or a divalent linking group. In formula (lb), Z2 represents · 0- or -N (R3) ·; wherein R3 represents a hydrogen atom, a hydroxyl group, or -0S02-R4; R4 represents an alkyl group, a halogenated alkyl group, a cycloalkyl group, or camphor Residues. The above-mentioned alkyl groups of h, R2, R4, R5, R6, R21 ~ R3Q printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are linear or branched alkyl groups having 1 to 10 carbon atoms. Linear or branched alkyl group having 1 to 6 carbon atoms, the most preferable ones are methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, 2-butyl, and 3-butyl. Examples of the cyclic hydrocarbon groups of K, R2, R5, and R6 include cyclopropyl, cyclopentyl, cyclohexyl, gold-steel fluorenyl, 2-methyl-2-gold-steel fluorenyl, protonyl, borneol, Isobornyl, tricyclodecyl, dicyclopentyl, orthorane-37- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 * A7 ______________ B7 V. Description of the invention ί6) Base epoxy, calanyl, isocalyl, octyl, tetracycline, and so on. (Please read the precautions of Back®, and then fill it out.) The alkoxy groups of h and R2 include, for example, methoxy, ethoxy, propoxy, and butoxy having 1 to 4 carbon atoms. Examples of the halogenated alkyl group of R4 include trifluoromethyl, nonafluorobutyl, pentafluorooctyl, and trichloromethyl. Examples of the cycloalkyl group for R4 include cyclopentyl, cyclohexyl, and cyclooctyl. f The other substituents of the alkyl group, cyclic hydrocarbon group, and alkoxy group include, for example, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, a fluorenyl group, a cyano group, and a fluorenyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. For example, the alkoxy group has 1-4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy. The fluorenyl group includes, for example, methylamino, ethino, and the like. Base etc. For example, the divalent linking group of A in the general formulae (I a) and (I b) is used singly or in combination of two or more kinds of subordination groups, substituted subordination groups, ether groups, thioether groups, carbonyl groups, ester groups, or Groups of amino groups, sulfophosphonium groups, urethane groups, and urea groups. Examples of the alkylene group and substituted alkylene group of A include a group represented by the following formula. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-[C (Ra) (Rb)] r- (where 'Ra and Rb are hydrogen atoms, academic groups, substituted academic groups, halogen atoms, hydroxyl groups, alkoxy groups, And the two may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl, and the more preferable one is selected from methyl, ethyl, propyl, Isopropyl. Substituents of substituted alkyls include, for example, hydroxy'halogen atom, alkoxy. Alkoxy such as -38- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 ·. A7 ------ B7__ 5. The description of the invention is necessary) There are 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, etc. Halogen atoms such as chlorine, bromine and fluorine atoms , Iodine atom, etc. R is an integer of 1-10. ) Specific examples of the repeating unit represented by the above general formula (la) include the following Π-1] to [1-65]. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives This paper is printed in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 561316 ^ A7 B7 -CH ^ 0 = f 1 = ° [ii] 0 = f T ° n-21 0 1 OH 0 OH c (ch3) 3 1 h3ch2c_c (ch3) 2-CH charge 〇 = r T ° [1-3] 0 = f Γ ° Μ s OH 0 OH c (ch3) 3

〇 I H3C-CH 〇rH〇P-5] OCH2CH3 CH2 och3 ° = fr ° Μ 0 OH 1 H3C-CH OCH2CH2CH2CH3 〇 == fr ° p-8] &quot; ^ CH-CH ΓΓ0 [1-7] 0 OH 1 0 OH H3C-CH Λ OCH2CH (CH3) 2 卞 ^ CH-CH 冲 0 = f Γ0 [1-9] 0 OH ^ CH-CH ^ 0 = (] = 0 • 0 NH 1 1 h3coh2c—c ( ch3) 2 c (ch3) 3? 〇2 [M〇] CH, .40 · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling in this Page) ·· --- Order ------- ίέ—φ ---------------------- 561316 Α7 Β7 V. Description of the invention (V7)卞 ^ CH-CH 冲 γ ^ ο π-ιΐ] Ο ΝΗ C (CH3) 3 s ° 2

Π-12] Ο

^ CH-CH ^ 0 = f 0 'pO NH | [1-13] 0 = f 0 r ° NH | 1 C (CH3) 3 S02 1 t | H3C — CH S〇2 NH 1 CH〇ch3 OCH2CH3 卞 ^ CH-CH 冲 ° = f Ί = ο [1-15] 0 = fr ° 0 〇, 0 0, C (CH3) 3 ch2ch2oh C (CH3) 3 CH; [1-14] ^ CH-CH ^ 0 = ^ γ = 0 Π-17] 〇 0, 0 (CH3) 3 CH2CH2OCH2CH2COOH

CH2CH2COOH Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 0 = (γ = 0. [1-18] 〇. 0Ν &amp; ch2ch2conhso2ch3

^ CH-CH ^ 〇 = (1 = 0 [1-19] 〇 iΝ i (CH3) 3 N ™ C〇〇H

0 = Ί Τ ° [1-20] 〇 ΗN &gt; C (CH3) 3 NCH2CH2〇H -41- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the back Please fill in this page again) I ϋ ϋ 1_1 ϋ nn 一 _ 口 V · I n ϋ n II ϋ I ϋ n ϋ ϋ ϋ ϋ Β —Β ϋ n ϋ ϋ ϋ ϋ I nn I n-561316. A7 B7 5 Description of the invention (40) 〇 = f &gt; = 〇 [丨 -21]? 〇, ch2ch2cn 0 =] ^ = 0 [1-22]? 〇, C (CH3) 3 cH2CH2COOCH3 \, CH-CH J 0 = f [1-24] 0 0. 〇 (Please read the notes on the back before filling out this page) I ------- Order · -------- I · Consumption by the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative prints c (ch3) 3 o = f γ〇? 〇 &amp; ch3) 3 ch2ch2coo [1-23]

c (ch3) 3 \, CH-CH / 〇 = f &gt; = 〇 [1-25] 0 0, .0 c (ch3) 3 h3c

o h3c .CH-CH / 0 = Ί IT0 [1-27] 〇 o, c (ch3) 3

/ CH-CH 7 0 I 1 = ° [1-29]

v .CH-CH J 0 I ^ T0 [1-26] 0 0, 々Ο H3C *-? H Co OCH2CH3

[1-28] [1-30]

[1-32] COOH This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 561316,. A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling in (This page)

V. Description of the invention

V charge v CH-CH 1 〇 = ([1-33] OH 〇CH3t charge V ^ CH-CH J n 〇frl 0 = ^ ten = 0 [b 35] OH OCH2CH2CN

&quot; ^ CH-CH 0 = T Y &quot; 0 [1-34] OH OCHpCH ^ OH Seven CH-CH red rl 0 = ^ γ = ο [卜 36] OH OCH2CH2COOH &quot; K Red CH-CH 1 〇 = TY ° OH O,

CT 〇 [1-37] Seven CH-ChT ^ OH 0,

ch3 ch3 [1-38] Chong, CH-CH J 〇Π &quot; Γ0 [1-39] NH 〇, S02 I CH3

o ^ 〇 cT 〇t Impact v CH-CH 1 0 = (^ = 0 [1-40] OCH3

cT 〇

0 1 NC-H2CH2C

OH o,

0 ^ 0

&quot; K Chong \ / CH-CH y [1-41] 0 = ([M2] och3 och2ch2cn [M3] v / CH-CH 1 o = f &gt; = 〇 0H 0

[1-44] • 43 · This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 561316, *-A7-B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the (Please fill in this page again)

5. Description of the invention (β

[Μ5] 〇〇 OH 〇

0 = (y = 〇 [1-47] OH OH? V ^ CH-CH 1 0 = 1 [1-49] O 〇C (CH3) 3 C (CH3) 3 V ^ CH-CH 1 〇 = f Y 〇 [1-51]? 〇 \ C (CH3) 3 iH2 och3 0 = f Y ° [1-53] O 〇, C (CH3) 3 V ^ CH-CH 1 ° = f 〇hc-ch3 och2ch3

V ^ CH-CH; 0 = f OH Y = 0 [M8] nhso2ch3 V ^ CH-CH 1 0 = 1 [1-50] 0 S 1 IC (CH3) 3 C (CH3) 3 凇 CH-CH 彳 0 = f 〇Γ [1-52] c (ch3) 3 ch-ch3 OCH2CH3 V ^ CH-CH 10 = f 〇 &quot; Γ ° [1-54] 〇 [1-55] XCH-CH3 I OCH2CH3 CH2 I och3 ch2 I och3 -44- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) \ 561316 A7 _B7 V. Description of the invention (〇)

: CH-CH 7〇 = &lt; r ° 0

CH2OCH3 [1-58]

CH-CH Λ Γ〇 [1-59] ch-ch3 och2ch3; CH-CH f〇 = &lt; r ° 0

IS 0 c (ch3) 3 [1-60]; CH-CH 7〇 = &lt; r ° HN 0 [1-61]

C (CH3) 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

c (ch3) 3 [1-62] [1-64]

[1-63] C (CH3) 3

Γ _ CH2OCH3 • 45 ·-^ 1 ϋ ϋ Mi · — —% '^ i «ϋ« ϋ m atmmm I «I i ^ i ϋ ϋ · ϋ ϋ · ϋ JV · ϋ · ϋ ϋ I i ^ i I n ft— mmi ϋ ϋ I ϋ ϋ nn nn ϋ ϋ ϋ n ϋ n —i I Language (please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 561316 Α7 B7 V. Description of the invention (44) Specific examples of the repeating unit shown by the above general formula (lb) are as follows [I ~ [I '-7], but the present invention is not subject to such specific forces Restricted. -1] CH— [Γ-1] ο ο

(Please read the notes on the back before filling this page) ·· Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ------ * --- Line 丨 ------ -46 This paper size applies to China National Standard (CNS) A4 Specification (210 X 297 mm) 561316 A7 B7 V. Description of Invention (4Γ)

I-I5 Fine 3η rL (Please read the precautions on the back before filling this page) CH-

0 &lt; C, N / C ^ 0

u6-5τι r-L 0 — S〇2—CF3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

The size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 561316 A7 --- B7 V. Description of the invention 4) (Please read the notes on the back Φ before filling in the page) In the above general formula (II ), RM and R12 each represent an independent hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent; Z is a group which contains two carbon atoms (CC) and is a lipid which may have a substituent Atomic group of ring structure. Examples of the halogen atom in the Rn and R12 include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. f The alkyl groups of the above RM and R12 are linear or branched alkyl groups having 1 to 10 carbon atoms, and more preferably, linear or branched alkyl groups having 1 to 6 carbon atoms. These are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl. Examples of the substituent of the alkyl group of Rh and R12 include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, a fluorenyl group, a cyano group, and a fluorenyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, and butoxy. Examples of the fluorenyl group include methyl fluorenyl and ethino. Base etc. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the above-mentioned atomic group forming an alicyclic structure forming Z is an atomic group of a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin. An atomic group having a bridged alicyclic structure as a repeating unit of the formula alicyclic hydrocarbon is preferred. The structure of the alicyclic hydrocarbon formed is, for example, the structure shown below. -48- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention (0 □ &gt; 〇〇 &gt; ① co (1) (2) (3) ( 4) (5) 〇 &gt; 〇〇〇〇

(6) (7) ⑻ ⑼

(10) (11)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) 561316 A7

I n i_ ^ i I nw ^^ 1 I in y. IV · ϋ * ^^ 1 ^^ 1 I ϋ ^ 1 ϋ I / ^ w ^ l ^ 1 u ^ 9 Words (Please read the notes on the back first (Fill in this page again) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention 厶) The preferred bridged alicyclic hydrocarbon architecture is in the above structure (5 &gt;, (6), (7), (9), (10), (13), (14), (15), (23), Please read the precautions on the back and then page (28) ), (36), (37), (42), (47). In the above-mentioned alicyclic hydrocarbon structure, there may be a substituent. The substituent is, for example, the general formula (II-A) or (II) R13 to R16 in -B). In the repeating unit having the above-mentioned bridged alicyclic hydroxyl group, the repeating unit represented by the above general formula (II-A) or (II-B) is more preferable. In general formula (II-A) or (II-B), R13 to R16 are each independently hydrogen atom, halogen atom, cyano group, -COOH, -COOR5 (R5 represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. Or the same -γ group as the general formula (I)), A solution group, -C (= 0) -XA-R17, or a substituent or a cyclic hydrocarbon group. Η represents 0 or 1. X represents oxygen, sulfur, -N 原子-, -NHS02 Or -NHS02NH-. R17 means -COOH, -COOR5, -CN, hydroxyl, alkoxy which may have a substituent, -C〇-NH-R6, &lt; (Synonymous with the above) or the -Y group of the general formula (la) above. A is a single bond or a divalent linking group. The acid-decomposable group printed on the resin of the present invention by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy also includes The above-(:-(= 0)-乂 -AR〆-C (= 0) -XA-R2 also includes the substituent of Z in the general formula (II). The structure of the acid-decomposable group is shown as = (Wherein, R. Examples include tertiary alkyl groups such as 3-butyl and 3-fluorenyl groups, isobornyl, 1-ethoxyethyl, 1-butoxyethyl, and 1-isobutoxy Alkylethyl, 1-epoxyethyl, etc. Alkoxyethyl, 1-Methoxymethyl, Buethoxymethyl, etc. Ethyloxymethyl, 3-Methyl radical, Tetrahydroran Base, IV-51- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) &quot; 561316 A7 137 V. Invention (If it is clear) (Please read the precautions on the back 1 before filling in the hydrogen furanyl group, trialkyl alkyl ester group, 3-carbonyl cyclohexyl ester group, 2-methyl-2-adamantyl group, methylhydroxylactone Residues, 2- (7-butyronitrileoxycarbonyl) -2-propyl, etc., eh! (Synonymous with X.) The halogen atoms of h 3 to R 16 include, for example, a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. The above-mentioned alkyl groups of R13 to R16 are linear or branched courtyards with 1 to 10 carbon atoms. The more preferred, linear or branched courtyards with 1 to 6 carbon atoms are most preferred. These are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl. Examples of the cyclic hydrocarbon group of R13 to R16 include a cyclic alkyl group, a bridged hydrocarbon, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an arsenoline group, a 2-methyl-2-adamantyl group, and a protopazine Alkyl, norbornyl, isobornyl, tricyclodecyl, dicyclopentyl, orthoalkylepoxy, calanyl, isocalyl, octyl, tetracyclododecyl and the like. At least two of R13 to R16 are bonded to form a ring, for example, a ring having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, the alkoxy group of R17 mentioned above has 1-4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy. Examples of the substituent of the alkyl group, cyclic hydrocarbon group, and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, a fluorenyl group, a cyano group, and a fluorenyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy. Examples of the fluorenyl group include formamyl, ethenyl, and the like, and the alkoxy group includes acetoxy. Wait. -52- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 561316 A7 B7 V. Description of the invention 6) The divalent linking base of A above is, for example, the A of the above general formula (I a) The divalent linking group is the same and can be independently selected from a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, amidino group, a sulfonamido group, and a carbamate group. , Urea groups, or a combination of two or more kinds. The alkylene group and substituted alkylene group of A are, for example, the same as the divalent linking group of A of the general formula (I a). The group decomposed by the acid action in the resin of the present invention may contain at least one repeating unit represented by the general formula (la), a repeating unit represented by the general formula (lb), and a repeating unit represented by the general formula (II). The unit and the superposition unit of the superposition unit of the following copolymerization component. The various substituents of R13 to R16 of the general formula (II-A) or general formula (Π-B) are atomic groups of the alicyclic structure formed in the general formula (11) or bridged alicyclic groups. Formed by the substituents of the atomic group Z constructed by the formula. Specific examples of the repeating unit represented by the general formula (II-A) or general formula (Π-B) are as follows (II-1) to (11-66), but the specific examples of the present invention are not limited. . (Please read the note of Φ? Matters before filling in the page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs • 53- This paper size applies to China National Standard (CNS) A4l ^ (210 x 297 public love) 6 1X 3 lx 6 5 A7 B7 77 Description of the invention (

〇 〇 [II-1]

[II-21

[II-3] 0 0

H CH2OCH2CH3 [II-4] ^ == 00 0H CH (CH3) OCH2CH3 (Please read the precautions on the back before filling this page) ··

[II-5] 0 0H CH (CH3) OCH2CH (CH3) 2

[II-6]

[II-7] 0

[II-8] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

〇〇 '

[II-10]

ο 、 CH2OCH2CH3

0 0, ο, CH (CH3) OCH2CH3 • 54_ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ϋ ϋ n a 0, V l ^ ia ^ i I 1 ϋ I ϋ ϋ ϋ ϋ 11 ϋ nnnnn ϋ I— —.1 nnnn &lt; I561316 · A7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economy B7 V. Description of the invention (Η

[11-11] [II-13] 0 0

0 0 hoh2ch2c c (ch3) 3

[II-14] 0 0 hoh2ch2c ch2och2ch3 h3ch2coh2ch2c ch2och2ch3

[II-15]

[11-16] 0 0 0 0 hooch2ch2coh2ch2c ch2och2ch3

[11-17] NHO HOOCH2C C (CH3) 3

NHO hoh2ch2c c (ch3) 3

[11-20] H3C-o2s—HN-oc -h2ch2c c (ch3) 3 h3co2s ch2och2ch3 -55 «This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) ------ Kllr ——------- Order ------- (Please read the notes on the back before filling out this page) 561316, A7 B7 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

[11-21]

[II-22]

Ο Ο I 〇 [11-23]

HO

C (CH3) 3

〇 〇 I CH2OGH2CH3

Ο [11-24]

Ο Ο C (CH3) 3

0 gas / &gt; = 〇 [11-273 / ^^ 0 0 ^ ° [11-28] That is ~ Z L2〇CH2CH3 it / iH (CH3) 〇CH2CH (CH3) 2

.56 · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------- Order --------- Line—AWI (Please (Please read the notes on the back before filling this page) 561316 '' A7 B7 V. Description of the invention (π

0 [II-31]

0 [11-32] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) -Γ-. -I «&gt; ϋ I— n &gt; 1 ^ 1 I in ϋ 1 ^ · · Ϋ · ϋ · · ϋ ϋ— I— Hi i§ I in · ϋ 1_1 ^^ 1 an ^ i &gt; ϋ ϋ ϋ nn ϋ 1 i ^ im ϋ υ 〇I Η

[II-33]

0 [II-34] 0

0 0

00 [II-37] CH2CH2CN

[II-38] CH2CH2OCH2CH3

[II-39]

CH2C00H

[II-40] = 0 〇HNI CH (CH3) C00H • 57 · This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention (β

[II-41J 0 0

Lll 42J 0 0

[II-43] 0 0 H CH2〇CH2CH3

[II-44] 0 0 (Please read the notes on the back before filling this page)

[11-45]

ΝΗ〇 C ^ -0〆 C (CH3) 3 0 0H CH (CH3) 〇CH2CH (CH3) 2 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

[II-47]

0 0 I

[II-48]

ο ο 0 == ^ CH2OCH2CH3 〇-

CH2OCH2CH3 • 58 · This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 ^ ___. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economy Invention Description (r?)

0 0 [II-49]

[11-50]

[II-53] 0 0

[11-52] hoh2ch2c c (ch3) 3

hoh2ch2c ch2och2ch3 h3ch2coh2ch2c ch2och2ch3

[II-55] 0 0 hooch2c ch2och2ch3

0 0 NCH2CH2C CH (CH3) OCH2CH3 [11-56] (Please read the notes on the back before filling this page) Order ------ l ·! Line! -59- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) k I -------------------- 561316 A7 B7 V. Invention Explanation (j)

HOOC (H3C) HC CH (CH3) OCH2CH3 H3C02SHN0CH2C C (CH3) 3 Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs

—6 0 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) 561316 A7 B7 V. Description of the invention (π

[II-66], 0 0

[II-67] 0 0 I (Please read the precautions on the back before filling this page) 0 CH (CH3) OCH2CH (CH3) 2

ch2och2ch3

[11-68]

[II-69] 0 0 I car 〇〇 I CH2〇CH3 CH (CH3) 〇CH2CH3 Order -------! Line! Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

H00C

r— I! I I I This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 Α7 Β7 V. Description of invention u. )

0 0 IΗ

L11-72J Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

• 62— This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) t rJ a · ^ — ϋ n —— ϋ ϋ Lf ϋ I — ^ 1 ϋ ϋ ϋ ^ 1 ϋ j ^ I ϋ ϋ ^ 1 ^ 1 ϋ (Please read the notes on the back before filling out this page) l ----! k --------------------- 561316 A7 B7 V. Description of the invention (y)

[I Pl 79]

OHN

[II-80]

CHXOOH so2ch3

0C (CH3) 3

ο I

[II-83] (Please read the notes on the back before filling this page) CH2OCH3 CH2OCH2CH3

[11-84] 0

[11-86] 0 CH (CH3) OCH2CH3 CH (CH3) OCH2CH (CH3) 2 u Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-87]

—63 ·

I · _1 ϋ I ϋ II · ϋ I ϋ ϋ ϋ n ϋ ϋ ϋ ϋ ϋ ^ 1 ^ 1 ^ 1 ϋ n ϋ ^ 1 ^ 1 ^ 1 · ϋ I This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) 561316 A7 B7 V. Description of the invention (k

[II-97]

[11-98] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 Ich2ch2cn

[11-101]

[11-100]

------- ^ I -------------- Order _______ 1 __- (Please read the notes on the back before filling out this page) -〇 [11-102] 〇-CH2CH2OCH2CH3 〇, ch2_ -64- r- — — — — — — — — — — — — — — — — ————————————————————————————————————————————————————————— This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention (w

0 [11-103]

HN

[II-104]

HN ^ 〇 \ CH (CH3) COOH ^^^,

CHXOOH

[11-106]

[11-108] [II-L10] HN

HN

[II-109], CH (CH3) C00-^^ &gt; = 〇

HN

[II-111] ------ r *-L-1111 --- I --- Order ------- r--I (Please read the notes on the back before filling this page) ,

CH2COOCH2CH2CN,

CH2COOCH2CH2OH Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

HN, [II-112], CH2COOCH2CH2OCH2CH3 • 65 · This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 ', Α7 Β7 V. Description of Invention (M) Employees ’Intellectual Property Bureau, Ministry of Economic Affairs Consumption Printed by a cooperative

CH (CH3) OCH2CH3 CH (CH3) 0CH2CH (C:

[II-120] ο

Γΐτ 11Γ) 1 CH2OCH2CH3

[II-121] ο

[II-124] Ο ο [II-118] (Please read the precautions on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Invention Explanation (κ)

ΓΙΤ-1251

OH

II l;! (U

COOH

S02CH3

(Please read the notes on the back before filling out this page) # Order ------ l ·! Line! Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

[11-133] 0

[11-134] CH2CH2OCH2CH3 0 ch2cooh • 67 · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention (A)

[1I-135J

(Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs n n ϋ ϋ ϋ ϋ ϋ 1 0, · ϋ «ϋ ϋ H ι_1 ϋ I ϋ ϋ · 1_1 ϋ ϋ ^ 1 ϋ I ^ 1 ^ 1 ^ 1 ^ 1 ^ 1 ^ 1 · 0 II ch2ch2och2ch2oh ch2cooh

[II-141] HNCH (CH3) COO «

[II-143]

CH (CH3) COOH

0 0 ch2coo &lt; T ° 0

[II-144]

HN ICH2COOCH2CH2CN

HNCH (CH3) COOCH2CH2OH -68 · This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention (π)

HN I — — — — — — — —fill · · — — — — — — — — — «— — — — — l · — — I · (Please read the notes on the back before filling this page) Wisdom of the Ministry of Economy Printed by the Consumer Affairs Cooperative of the Property Bureau Γττ

ΓΤΤ-HOI

HN I CH2COOCH2CH2OH

[11-147] CH2COOCH2CH2OCH2CH3 [11-149] [11-148]

CN

Cl

[II-149] H3C CN

[II-150] HO

[II-151] conh9 [II-152] h3c conh2 [11-153] [11-154] C0NHC (CH3) 2CH2S03H 〇coch3

[II-155]

[11-156]

[II-157]

[11-160] -69- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Cl

CONH 2 561316 A7 B7 V. Description of the invention ")

[II-162] CONHC (CIl3) 2ai2SU3H [11-165]

[11-163] OCOCIl ·

[11-166] The resin of the present invention contains one of several types of repeating units represented by general formula (la) and / or general formula (lb), and general formula (11) (including general formula ( II-A) and the repeating unit shown by the general formula (Π-B) to adjust the dry etching resistance or the standard developing solution suitability, the substrate adhesion, the external shape of the barrier, and the resolution of the general requirements of the barrier, In the case of heat resistance, sensitivity, etc., the copolymer may contain the repeating units of various monomers. Preferred copolymer components include, for example, the repeating units represented by the following general formulae (IV ·) and (V ').

0 ZO 〇 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

ζ 〇 (wherein Z represents -NΗ-, -N (R5.)-, -N (-〇S02R5 ())-, and R represents the same (substituted) alkyl group and (substituted) cyclic hydrocarbon group as described above. ) Specific examples of the repeating unit represented by the general formulae (IV 1) and (V ′) include, for example, the following (IV'-9) to (IV'-16), (V'-9) to (V -16), but the present invention is not limited by these specific examples. -70- 50 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 Α7 Β7 5. Description of the invention (β)

〇so2ch3

[IV, -15] 0

oso2-cf2 (cf2) 6cf3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Ο Ο, 0

Η

[V, -11] 〇so2ch3 -------, 1 ---- Γ ----------- Order ------- M--Green Read the notes on the reverse side and fill out this page) P— — — — — — — · 71 · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of invention {〇)

[V,-oso2cf3

[V, -14] oso2ch2ch2ch2ch3 oso;

0S02-CF2 (CF2) 6CF3 (Please read the note about exhaustion of SJ first, and then print the resin of the present invention with the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, within the range that can effectively obtain the effect of the present invention. The single body is copolymerized as a repeating unit constituting the resin, but is not limited by the following single body. This can finely adjust the properties required for the above resin, especially (1) the solution of the coating solvent Properties, (2) film-forming properties (glass transition temperature), (3) alkali developability, (4) film edges (hydrophobicity, alkali-soluble group selection), (5) adhesion to substrates in unexposed areas, ( 6) Dry etching resistance The comonomers include, for example, acrylates, methacrylates, methacrylates, methacrylates, allyl compounds, vinyl ethers, vinyl esters, etc. A compound selected from addition-polymerizable unsaturated bonds, etc. Specifically, for example, acrylic esters are, for example, alkyl acrylate (alkyl-72-)-This paper is in accordance with China National Standard (CNS) A4 (210 X 297) (Mm) 561316 A7 V. Description of Invention ΐ) ( Please read the notes on the back ® first, and then fill in the carbon number with 1 ~ 10 is preferred. Ester (such as methyl acrylate, ethyl acrylate, lactone, pentyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate) Octyl acrylate, 3-octyl acrylate, ethyl chloroacrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxylactone acrylate, 5-hydroxybenzyl acrylate, trihydroxy monoacrylate Methylpropane ester, pentaerythritol monoacrylate, benzyl propionate, methoxybenzyl acrylate, methyl acrylate, tetrahydromethyl acrylate); for example, methacrylates include alkyl methacrylate (alkyl The carbon number is preferably from 1 to 10) (such as methyl methacrylate, ethyl methacrylate, methacrylic lactone, isolactone methacrylate, ethyl methacrylate, hexyl methacrylate, Cyclohexyl methacrylate, benzyl methacrylate, benzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, methacrylic acid 5-hydroxybenzyl methyl ester and methacrylic acid 3-Hydroxylactone, Trimethylolpropane monomethacrylate, Pentaerythritol monomethacrylate, Ethyl methacrylate, Tetrahydromethyl methacrylate, etc. ); Acrylamides such as acrylamide, N-alkyl acrylamide (alkyl is 1-10 carbon, such as methyl, ethyl, propyl, butyl, 3-butyl, heptane Octyl, octyl, cyclohexyl, hydroxyethyl, etc.), N, N-dialkylacrylamide (alkyl is 1 to 10 carbons, such as methyl, ethyl, butyl, isobutyl, ethyl Hexyl, cyclohexyl, etc.), N-hydroxyethyl-N-methacrylamide, N-2-vinylfluorenylethyl-N-ethylacrylamide, etc .; methacrylamines such as There are methacrylamide, N-alkyl methacrylamide (alkyl groups are 1 to 10 carbons, such as methyl, ethyl, 3-butyl-73- This paper size applies to Chinese national standards ( CNS) A4 specification (210 X 297 Gt) 561316 A7 B7 V. Description of the invention &lt; 2) (Please read the note on pregnancy and then fill in ^^ pages), ethylhexyl, hydroxyethyl, cyclohexyl, etc. , N, N-dialkylmethacrylamide (alkyl is ethyl, propyl, butyl, etc.), N-hydroxyethyl-N-methylmethacrylamine, etc .; allyl compounds such as There are lactones (e.g., lactone acetate, caprolactone, caprolactone, laurolactone, palmitolide, lactone stearate, lactone benzoate, Acetyl acetolactone, lactone lactone, etc.), allyloxy ethanol, etc .; Vinyl ethers include, for example, alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, and ethylhexyl ethylene). Ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chlorinated ethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether , Hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylamino ethyl vinyl ether, diethyl amino ethyl vinyl ether, butyl amino ethyl vinyl ether, benzyl vinyl ether, Hydrogenated vinyl ethers, etc .; Vinyl esters printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as vinyl butyrate, vinyl isobutyrate, and ethyl trimethylacetate Esters, diethyl vinyl acetate, vinyl caprate, vinyl caproate, vinyl chloride chloride, vinyl dichloride, vinyl methoxyacetate, vinyl butoxylate, ethylacetate Vinyl esters, vinyl lactate, vinyl / 3-phenylbutyrate, vinyl cyclohexyl carboxylate, etc .; dialkyl itaconates (such as dimethyl itaconate, diethyl itaconate, itaconic acid) Acid dibutyl ester, etc.); acrylic acid, methacrylic acid, citric acid, itaconic acid, acrylic acid, methacrylic acid, etc. In the resin of the present invention, the general formula (la) and / or the general formula (lb) are ___ -74- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 meals) 561316 A7 B7 V. Invention Explanation ί 3) Please read the precautions on the back before filling in the pages: The content of the repeating unit and the repeating unit shown in the general formula (11) (including the general formula (Π-A), general formula (II-B)) The resistance, dry etching resistance, sensitivity, iodine crack prevention of the pattern, substrate adhesion, external shape of the resistor, and the resolution and heat resistance of necessary elements of the resistor are appropriately set. In general, the content of the repeating unit represented by the general formula (la) and / or the general formula (Ifb) of the resin of the present invention and the repeating unit represented by the general formula (11) are each contained in all the repeating units of the resin. 25 mol% or more, preferably 30 mol% or more, and more preferably 35 mol% or more. '' In addition, in the resin of the present invention, the content of the repeating unit (general formula (IV ') or general formula (V1)) derived from the above-mentioned preferred comonomers depends on the desired barrier properties. It is appropriately set, but generally speaking, for the total mole number of the repeating unit represented by the general formula (la) and / or the general formula (lb) and the repeating unit represented by the general formula (II) It is preferably 99 mol% or less, more preferably 90 mol% or less, and most preferably 80 mol% or less. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition, the content of the resin in the above-mentioned repeating unit, which is based on the monomer of the copolymerized component, is also appropriately set according to the desired barrier properties. The total number of moles of the repeating unit represented by formula (la) and / or general formula (Ib) and the repeating unit represented by general formula (11) is preferably 99 mole% or less. The more preferred is 90 mol% or less, the best is 80 mol% or less. If the amount of the coating unit based on the monomer of the copolymerization component is more than 99 mol%, the effect of the present invention cannot be obtained sufficiently, so it is not desirable. In addition, the resin (B) contains two kinds of acid components -75----: two- &lt; υ 1 B A) \ 561316 A7 B7_ in all the repeating units. A resin having a difference in content of the repeating unit of 5 to 30 mol% is preferred. (Please read the precautions on the back first and then fill in) When the content difference between all the repeating units of the acid-decomposable repeating units containing at least two resins is less than 5 mol%, or greater than 30 mol%, the barrier The storage stability and sensitivity of the composition tend to deteriorate, so it is not desirable. In addition, when the resin (B) contains three or more kinds, the difference between the resin having the most content of the repeating unit containing the acid-decomposable group and the least amount of the repeating unit is 5 to 30 mol%. The difference is preferably 6 to 25 mole%, and more preferably 7 to 20 mole%. Further, the base decomposed by the acid action in the resin of the present invention includes a repeating unit represented by the general formula (la) and / or a general formula (lb), a repeating unit represented by the general formula (π), and Any of the repeating units based on the monomer of the polymerization component may be used. The content of the repeating unit containing a base that is decomposed by the action of acid is 10 to 80 旲% for all the repeating units of the resin. It is better to use 12 ~ 75 mole%, and more preferably 15 ~ 70 mole%. 〇 The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the resin with the most acid-decomposable groups. The resin contains acid-decomposable groups. The content range of the repeating unit is preferably 12 to 90 mole%, more preferably 15 to 85 mole%, and most preferably 18 to 80 mole%. In addition, for the resin having the least acid-decomposable group content, the content of the repeating unit containing the acid-decomposable group in the resin is preferably 5 to 70 mole%, more preferably 8 to 65 mole%, and the most preferable. It is 10 to 60 mol%. The resin of the present invention can make the unit of the repeating unit shown in the general formula (II) and -76- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 561316 A7 B7 V. Description of the invention 6 ) (Please read the note of back silicon first "and then fill in the ^ | page: maleic anhydride, copolymerize the monomer of the copolymerization component when using the copolymerization component, and copolymerize in the presence of a polymerization catalyst to make the obtained The repeating unit of the maleic anhydride of the copolymer is cyclically esterified with alcohols under basic or acidic conditions, or hydrolyzed, and the carboxylic acid moiety formed after it is synthesized by the desired substitution method. The weight f average molecular weight of the resin of the present invention is calculated by polystyrene conversion of the GPC method and is preferably 1,000 to 200,000. If the weight average molecular weight is less than 1,000, heat resistance or dry etching resistance is deteriorated. If it is more than 200,000, it will cause poor results due to poor developability and extremely high viscosity. This results in undesirable results. The positive-type photoresist composition for far-ultraviolet exposure of the present invention Group of all resins of the present invention The compounding amount of the whole substance is preferably 40 to 99.99% by weight, and more preferably 50 to 99.97% by weight of the total solid-blocking solid components. (A) The photo-acid generator or (B) the solid component of the resin, etc. The solid content of 0.3 to 25% in the above-mentioned solvent is better to dissolve, more preferably 5 to 22%, and the best 7 to 20%. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed this invention. It is preferable that the positive-type photoresist composition for ultraviolet exposure contains a fluorine-based and / or silicon-based surfactant. The fluorine-based and / or surfactant-based agent is at least one fluorine-based surfactant, a silicon-based surfactant, And a surfactant containing both a fluorine atom and a silicon atom. The positive-type photoresist composition for far-ultraviolet exposure according to the present invention contains the above-mentioned acid-decomposable resin and the above-mentioned surfactant, and uses 250 nm or less, especially 220 nm or less. Sensitivity, resolution, and -77- when this light source is exposed, this paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention 6) Substrate adhesion and dry etching resistance Excellent and rarely visible Resistive body pattern with the residue of disadvantages. (Please read Hiroyuki's note before filling in the ^ | ^ pages) Commercially available surfactants that can be used are, for example, Gefton Department (transliteration (EF 3 0 1, EF303 (made by Shin Akita Kasei Co., Ltd.), Floraton (transliteration) FC430, 431 (made by Sumitomo Shrimiya (share)), Mekafak (transliterated) F171, F173, F176, F189, F08 (made by Dainippon Ink (share)), Saf Long (transliteration) S-382, SC101, 102, 103, 104, 105, 106 (made by Asahi Glass Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. Polysiloxane polymer KP-341 ( Shin-Etsu Chemical Industry Co., Ltd. can also be used as a silicon-based surfactant. The compounding amount of the surfactant is based on the solid content of the composition of the present invention, and is usually 0.001% to 2% by weight, preferably the 0.01% by weight to 1% by weight. These surfactants can be used singly or in combination of two or more. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the above specific examples of other surfactants such as polyethylene oxide lauryl ether. , Polyethylene oxide stearyl ether, polyethylene oxide cetyl ether, polyepoxide Polyethylene oxide alkyl ethers such as alkanoic acid ethers, polyethylene oxide octyl phenol ethers, polyethylene oxide nonyl phenol ethers, and other polyethylene oxide alkyl aromatic ethers, polyepoxides Ethane · polypropylene oxide block copolymers, sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol Trioleate, sorbitol tristearate, etc. Sorbitol monobromolate, polyethylene oxide sorbitol monostearate, polyethylene oxide sorbitol fatty acid esters, poly Ethylene oxide sorbitol monolaurate, polyethylene oxide sorbitol tri-oil-78- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love) 561316 A7 B7 V. Invention Description ο) Nonionic surfactants such as polyethylene oxide sorbitol fatty acid esters such as acid esters, polyethylene oxide sorbitol tristearate, etc. The compounding amount of these surfactants is 100 The solid content in the composition of the present invention is usually 2 parts by weight or less, and preferably 丨 parts by weight. Agent may be added separately, can also be added in several group-containing compound having stronger basicity than phenol organic basic compound is preferably used in the present invention is to them, nitrogen-containing basic compound is preferred.

R 25 1

R 2 5 0—N—R 252 (wherein R25., R2 ”and R252 may be the same or different carbon atoms, alkyl groups having 1 to 6 carbon atoms, amino alkyl groups having 1 to 6 carbon atoms, and carbon number Hydroxyl group 1 ~ 6 or substituted or unsubstituted aryl group with 6 to 20 carbon atoms, and R 2 5 2 can be bonded to each other to form a ring) (B) Please read the note on the back% = C—N = C — Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs = C_N_ (Ο (D) R254 R255 R ^ -i — HC-R256 *** (E) (of which R253, R 2 5 4, R255, and R256 May be the same or different alkyl groups with carbon number i ~ 6.) In addition, the preferred compound is two or more different in one molecule. -79- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 137 561316 V. Description of the invention (8) (Please read the note below ¾? Matters and then fill in the nitrogen atom of the chemical environment with nitrogen-containing basic compounds, and more preferably contains substituted or unsubstituted Two compounds of the ring structure of an amine group and a nitrogen atom are compounds having a k-based amine group. Preferred examples include a substituted or unsubstituted vein, a substituted or unsubstituted amine group Pyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted Substituted pyrazines, substituted or unsubstituted pyrimidines, substituted or unsubstituted purines, substituted or unsubstituted imidazolines, substituted or unsubstituted pyrazolines, substituted or unsubstituted Substituted piperidine, substituted or unsubstituted morpholine, substituted or unsubstituted aminomorpholine, etc. Preferred substituents are amino, aminoalkyl, alkylamino, aminoaryl , Arylamino, alkyl, alkoxy, fluorenyl, fluorenyl, aryl, aryloxy, nitro, hydroxy, cyano. The Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives printed better compounds such as Vein, 1,1-dimethyl vein, i, 丨, 3,3-tetramethyl vein, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylamino Pyridoxine, 4-dimethylaminopyridine, 2-diethylaminopyridine: 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino Methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrole, Pyridine, N- (2-limylethyl) pyridine, N- (2-aminoethyl) methyl, 4-amino-2,2,6,6-tetramethylpiperidine, 4- Pyranylpiperidine, 2-iminopyridine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-methylamine, 5-amino-3-methyl -1-p-tri-tftu sitting, whispering, 2- (aminomethyl) -5-methylazine, tl · midine, 2,4-diaminomouth D, 4,6-di Jingjiche -80- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention &lt; 9) ) Pyridine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazobicyclo [4 · 3 · 0 ] Non-5-one, 1,8-diazobicyclo [5.4.0] undec-7-one, 2,4,5-triphenylimidazole, N-methylmorpholine 'N-ethyl Morpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholine ethylthiourea (CHMETU) Level 3 morpholine derivative, JP 1 1 - hindered amine Publication No. 52575 described (e.g. the publication [0005] those described), but is not limited by these. More specific examples are, for example, 5-diazobicyclo [4. 3 · 0] non-5-one, 1, 8-diazobicyclo [5,4,0] undec-7-one, 1 , 4-Diazo ring [2.2.2] Octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrrole, pyrazole, imidazole , Pyridazines, pyrimidines, CHMETU and other tertiary morpholines, bis (1,2,2,6,6-pentamethyl-4-pyrimidinyl) decanoates and other hindered amines. By using these, it is possible to have excellent density correlation. Among them, 1,5-diazobicyclo [4,3,0] non-5-one, 1,8-diazobicyclo [5,4,0] undec-7-one, 1, 4-Diazocyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,2,6,6-pentamethyl-4- Pyrimidinyl) decanoate is preferred. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs These nitrogen-containing alkaline compounds can be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound used is usually 0.00 1 to 10% by weight, preferably 0.0 1 to 5% by weight, based on the solid content of the entire composition of the photosensitive resin composition. If it is less than 0.001% by weight, the above-mentioned addition effect of the nitrogen-containing basic compound cannot be obtained. If it is more than 10% by weight, the sensitivity tends to decrease or the developability of the non-exposed portion tends to deteriorate. -81 &quot; This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 A7 B7 V. Description of the invention (such as) (Please read the note on the back of the case and then fill in JmsBC: In the positive form of the invention The photoresist composition may further contain an acid-decomposable solvent blocking compound, a dye, a plasticizer, a sensitizer, and a compound that promotes solubility in a developing solution, etc., as necessary. The positive-type resist composition of the present invention The above components are dissolved in a solvent and coated on a carrier. The solvent used here is ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, r-butyrolactone, methyl ethyl Ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, Ethyl acetate, methyl lactate, ethyl lactate, ethyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, pyruvate lactone, N, N-dimethyl Formamidine, dimethylimine, N-methylpyrrolidone, tetrahydrofuran, etc. are preferred, and these can be used alone Or mixed use. Among the above-mentioned preferred solvents are 2-heptanone, r-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. , Methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, tetrahydrofuran. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the present invention. The body composition is coated on a substrate to form a thin film. The film thickness of the coating film is preferably 0.2 to 1.2 / m. In the present invention, a commercially available inorganic or organic antireflection film can be used as required. The anti-reflection film can be made of an inorganic film type of titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon dioxide, or an organic film type made of a light absorbing agent and a polymer material. The former must be formed of a film Vacuum evaporation equipment, CVD equipment, sputtering equipment, etc. Organic anti-reflection film such as -82- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 561316 ^ A7 B7 V. Description of the invention ) The reason described in Special Fair 7-696 1 No. 1 Condensate of aniline derivative and formaldehyde-modified melamine resin, alkali-soluble resin, light absorber, or reactant of maleic anhydride copolymer and diamine light absorber described in US Patent No. 5,294,680, JP 6- 1 1 863 No. 1 containing a resin binder and a methylolmelamine-based thermal cross-linking agent, as disclosed in Japanese Patent Application Laid-Open No. 6-1 1 8656, which has a carboxylic acid group, an epoxy group, and light absorption in the same molecule. Acrylic resin-based anti-reflection film based on hydroxymethylmelamine and benzophenone-based light absorbing agent described in Japanese Patent Application Laid-Open No. 8-87115, and polyethylene described in Japanese Patent Application Laid-Open No. 8-1 79509 Those who add a low-molecular light absorbing agent to the diol resin. In addition, as the organic anti-reflection film, DUV30 series or DUV-40 series manufactured by Newark Keynes Co., Ltd., and AC-2 and AC-3 manufactured by Western Lightning Co., Ltd. can also be used. The above-mentioned body-blocking fluid is placed on a substrate (such as a silicon / silicon dioxide coating) used in manufacturing a precision integrated circuit element (as required, on a substrate provided with the above-mentioned antireflection film) by a spinner, a roller, etc. After being coated by an appropriate coating method, it is exposed through a Steady reticle, baked, and a good resist pattern is produced by development. Here, the exposure light is preferably light having a wavelength of 150 nm to 250 nm. Specifically, there are, for example, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, electron beams, and the like. The imaging solution can use inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium water, primary amines such as ethylamine and n-propylamine, diethylamine, di-n-propylamine, etc Secondary amines, tertiary amines such as diethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and tetramethylammonium hydroxide-8 3-This paper applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) Please read back note I Fill in the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Consumer Cooperative Printed 561316

5. Description of the invention G), quaternary ammonium salts such as tetraethylammonium hydroxide, cyclic amines such as pyrrole and piperidine, and other alkaline aqueous solutions. [Examples] The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. Synthesis Example (1) Synthesis of Resin (1-A) A tetracyclododecene derivative (1-) obtained by reacting an acrylate of 3-carbonyl-1,1-dimethylbutanol with cyclopentadiene 1) A mixture with a tetracyclododecene derivative (1-2) obtained by reacting acrylonitrile and cyclopentadiene with a molar ratio of maleic anhydride of 4/1/1/5 is added to a separation flask, under nitrogen Heated at a gas flow of 8 ° C. At a stable reaction temperature, 2.5 mol% free radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 12 hours, the reaction mixture was diluted with tetrahydrofuran to After 2 times, put a mixed solution of hexane / isopropanol = 1/1 to crystallize the white powder. The crystallized powder is taken out by filtration and dried. The target resin (1-A) is obtained. CH3

I

COO — C 1 CH Factory C — CH3 I II CH, 〇 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (M)

(1-2) Determination of the resin obtained by UA) When using GPC's molecular weight analysis, 'Yi-84- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 561316 A7 ____B7 _ V. Invention Note 纟 3) The styrene conversion is 10400 (weight average). In addition, the ratio of the (1 -1) and (1-2) units to the maleic anhydride repeating unit in the resin (1) by the NMR spectrum is (1-1) / (1-2) / maleic anhydride = 38/1 2 / 50. Therefore, the ratio of acid-decomposable repeating units is 38%. Resins (1-B) to (12-C) were synthesized in the same manner as in Synthesis Example (1-A). In the structures of the synthetic resins U-A) to (12-C), each of the A to C systems is a resin having the same repeating unit and a different content ratio. The structures in the following resins (1) to (12) are described below. (Please read the note on the back of the page first, and then fill in ^ = printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy -85- V. Description of the invention (red

ch3 I c〇〇 一 c-ch2-c-ch3 I II CHn 〇

CN ⑴

ch3 I coo—c—ch3 ch3

P00 ^ ch3

〇J ⑵ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 〇〜〇

〇 -Q6— This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ⑶ ^ --- line. 561316 A7 B7 V. Description of the invention (κ)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-07- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ϋ ϋ ϋ · ϋ ϋ ϋ ^ 1 Βϋ emmt l · / 1_1 ϋ I 1 1 ϋ ^^ 1 n ϋ — —ϋ One sip, I ^^ 1 1_§ · ϋ I ^^ 1 1_1 I ϋ. (Please read the precautions on the back before filling this page) 561316 A7 B7 V. Description of the invention (office

, 〇OOCH2C〇〇C (CH3) 3, CO〇H cooch2ch2oh

⑼

O ^ O ^ O

, c〇oc (ch3) 3 cooh

COO ^ I ^ i ^ OH (10) 〇 乂 〇 乂 〇 (Please read the notes on the back before filling this page)

COOC (CH3) 3 cooh

ch3 (11) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

, co〇c (ch3) 3 cooh coo

h3c, / CH3

(12) Table 1 shows the molar ratios and weight average molecular weights of the respective repeating units of the resins (1-B) to (12-C). -88 · This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561316 A7 Β7 V. Description of invention (type) Table 1 Printed resin maleic anhydride maleic Acid boat acid-decomposable claw is the ratio of bit Mw 1 2 3 1-B 26 14 50 26% 10,700 1-C 35 15 50 35% 10,500 2-A 40 10 50 40% 9,700 2-B 25 15 50 25 % 9,200 2-C 33 17 50 33%? 9,500 3-Λ 38 12 50 38% 8,400 3-B 24 26 50 24% 8,100 8,300_ 3-C 30 20 50 30% 4-A 42 8 50 42% 8,400 4 -B 30 20 50 30% 8,100 4-C 36 24 50 36% SJ00 5-Λ 43 7 50 43% 9,500 5-B 31 19 50 31% 9,300 5-C 37 13 50 37% 9,700 6-Λ 36 14 50 36% 7,800 6-B 23 27 50 23% 7,300 6-C 32 18 50 32% 7,700 7-A 45 5 50 45% 8,900 7-B 34 16 50 34% 8,400 7-C 40 10 50 40% 8,700 8 · Λ 46 4 50 46% 9,200 8-B 36 14 50 36% 8,600 8-C 41 9 50 41% 8,800 9-Α 38 7 5 50 38% 10,3009-B 26 10 14 50 26% 9,600 9 -C 30 9 11 50 30% 9,900 10-Α 38 6 6 50 38% 10,900 10-B 26 12 12 50 26% 10,600 10-C 34 8 8 50 34% 10,700 11-Λ 36 6 8 50 36% 9,700 11-Β 24 12 14 50 24% 9,100 11-C 32 8 10 50 32% 9,500 12C 39 5 6 50 39% 9,700 12B 28 11 11 50 28% 9, 100 12C 34 8 8 50 34% 9,400 V-601; 2,2'-even M double (2-ψM | Αί acid boat) -89- This paper size applies to Chinese national standards (CNS> A4 specifications (210 X 297 (Mm) (Please read the notes on the back before filling this page) ------^ --------- lacquer-^ ------------- ---------- 561316 A7 B7 V. Description of the invention 纟 8) Examples 1 to 1 2. Comparative examples 1 to 1 2 1.4 g of the resin shown in Table 2 synthesized by the above synthesis example ( (Full amount), (please read the urgent notes on the back, and then fill in the ^ page) and 0.18g photoacid generator (PAG4-36), 10mg organic basic compound (amine), surfactant (addition amount to composition The total solid content of the product is 1% by weight.) It is compounded as shown in Table 2, and each is dissolved in propylene glycol monoethyl ether acetate at a ratio of 14% by weight of the solid content, and then filtered with a 0.1 #m micro-filtration. The filter was filtered to prepare the positive photoresist composition of Examples 1 to 12. The surfactant is W-1: Mekafak (Transliteration) F176 (manufactured by Dainippon Ink Co., Ltd.) (fluorine) W-2: Mekafak R08 (manufactured by Dainippon Ink Co., Ltd.) (Department of fluorine and polysiloxane) W-3: Polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Industry Co., Ltd.) W-4: Polyethylene oxide nonylphenyl ether amine is 1: 1,5-diazobicyclo [4.3.0] -5-nonene2: Department of Economics, which represents bis (1,2,2,6,6-pentamethyl-4-pyridyl) decanoate Printed by the Intellectual Property Bureau's Consumer Cooperatives 3: It indicates tri-n-butylamine (evaluation test) The obtained positive photoresist composition solution was coated on a silicon wafer with a spin coater at 140 ° C Dry for 90 seconds, make a positive photoresist film of about 0.5 // m, and expose it with an ArF excimer laser (193ηπ〇. The heat treatment after exposure is performed at 140 ° C for 90 seconds to 2.38 Developed with a tetramethylammonium hydroxide aqueous solution and washed with distilled water to obtain the shape of the resist. -90- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 561316 Intellectual Property Bureau of the Ministry of Economic Affairs Employee Consumer Cooperative ___ five B7 system, the invention described G) For these, barrier body composition assessment of the storage stability of the composition. [Sensitivity] (Initial value of relative sensitivity) The minimum exposure of the pattern resolution of 0.1 5 // m can be set as the sensitivity ', and the sensitivity of No. 1 is taken as 1, and the sensitivity is expressed by the relative exposure. [Preservation stability of barrier composition] (Sensitivity change rate) The above-mentioned barrier fluid was stored at 40 ° C for 15 hours, and after being stored at 4 ° C for 15 days, the sensitivity was evaluated, and self-preservation was performed. The previous sensitivity change rate is measured by the following formula. In addition, the above sensitivity is defined by the exposure amount that reproduces the pattern of 0.1. // m of the scarf. {(Exposure amount before saving)-(exposure amount after saving) } / (Exposure before storage) x 100 (initial particle size and increase number of particles) Make the number of particles directly measured after the above-mentioned liquid-blocking body fluid is prepared as the initial phase, and measure the initial phase and make the body fluid concentration at 3 (The number of particles stored after 1 month under TC, and the number of particles increased before and after the above-mentioned time-saving storage. The above evaluation results are shown in Table 2. This paper size applies to China National Standard (CNS) A4 (210 X 297) (Mm) 561316 A7 B7 V. Explanation of the invention ...) Table 2 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Co., Ltd. The composition ratio of the resin in the example is aim%) The difference in acid decomposition rate (mole%) Amine surfactant sensitivity Change in mm (%) grains * Initial _ nr increase 1 1-Α / 1- = 75/25 12 1 1 1.0 &lt; 5% &lt; 5 &lt; 5 2 2-Λ / 2-Β = 53/47 15 ΐ 2 1.0 &lt; 5% &lt; 5 &lt; 5 3 3-Α / 3 -Β = 43/57 14 3 4 1.3 5% 10 10 4 4-Α / 4-Β = 50/50 12 1 3 1.0 &lt; 5% &lt; 5 &lt; 5 5 5-Α / 5-Β = 50 / 50 12 3 1 1.1 &lt; 5% 5 5 6 6-Α / 6-Β = 69/31 13 1 2 1.0 &lt; 5% &lt; 5 &lt; 5 7 7-Α / 7-Β = 55/45 11 2 3 1.0 &lt; 5% &lt; 5 &lt; 5 8 8-Λ / 8-Β = 50/50 10 1 1 1.0 &lt; 5% &lt; 5 &lt; 5 9 9-Α / 9-Β = 33 / 67 12 2 2 1.0 &lt; 5% &lt; 5 &lt; 5 10 10-Λ / 10-13 = 67/33 12 1 3 0.9 &lt; 5% &lt; 5 &lt; 5 Π 11-Α / 11-Β = 67/33 12 2 1 0.9 &lt; 5% &lt; 5 &lt; 5 12 12-Α / 12-Β = 55/45 11 1 2 0.9 &lt; 5% &lt; 5 &lt; 5 Comparative Example 1 1-C 0 1} 1.6 30% 100 500 2 2-C 0 2 2 1.6 30% 100 500 3 3-C 0 3 4 2.2 50% 500 1200 4 4-C 0] 3 1.6 30% 100 550 5 5-C 0 3 1 1.8 40% 300 1000 6 6-C 0 1 2 1.6 30% 100 600 7 7-C 0 2 3 1.6 30% 100 500 8 8-C 0 1 1 1.6 30% 100 500 9 9-C 0 2 2 1.6 30% 100 500 10 10-C 0 1 3 1.5 30% 100 450 11 11-C 0 2 1 1.5 30% 100 450 12 12-C 0 1 2 1.5 30% 100 400 -92- KI — · Order --- --- Γ · Green ...---------------------- (please first Read the notes on the reverse side and fill in this page again.) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 561316 &lt; A7 ____B7__ V. Description of the invention. The positive photoresist composition for the far-ultraviolet exposure of the resin (Examples 1 to 12) mixed with resins having different units and acid-decomposable groups in different proportions and only one resin (Comparative Examples 1 to 1) 12), it has satisfactory sensitivity and storage stability. In other words, the resins shown in Comparative Examples 1 to 12 contain the content of the repeating unit containing an acid-decomposable group, and the resins mixed with the two resins of Examples 1 to 12 contain a covering of the acid-decomposable group. The average content of the units is approximately the same, and the two resins have excellent sensitivity and storage stability when mixed. The positive-type photoresist composition for far-ultraviolet exposure according to the present invention is suitable for photolithography using far-ultraviolet rays starting from ArF excimer laser exposure. [Inventive effect] The positive-type photoresist composition for far-ultraviolet exposure of the present invention is particularly suitable for light in the far-ultraviolet wavelength range in the range of 170 nm to 220 nm, and has excellent storage stability. (Please read the note of r? Matters? ^ E-sc

Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

561316 6.Scope of patent application- No. 89122075 "Positive photoresist for far-ultraviolet exposure 6. Application scope of patent: ---- J ^ 1 · A positive photoresist composition for far-ultraviolet exposure, comprising: (A) 0 · 0 1 ~ 20% by weight of a compound that generates an acid by irradiation with active light or radiation, (B) 40 ~ 99.99% by weight has at least one repeating unit selected from the following general formula (la) and general formula (lb) A resin having a repeating unit represented by the following general formula (II) and having a group (acid-decomposable group) decomposed by the action of an acid, which contains at least two kinds of resins containing an acid-decomposable group in all the repeating units. Repeated resins with different single content (mol%), Rn 〇12 (In the formula (la), Rr and R2 are each independently a hydrogen atom, a cyano group, a hydroxy group, -COOH, -COOR5, -CO-NH-R6, -C0-NH-S02-R6, 561316 6. The scope of the patent application can be substituted by 1Q alkyl, -4 alkoxy or c3-i5 cyclic nicotyl, or the following -Y group; x represents an oxygen atom, a sulfur atom, _NH_, -NHSOr or -NHS 〇2NH-; wherein Rs represents an optionally substituted L — 1Q alkyl group, a c3 —15 cyclic hydroxyl group, or the following -Y group; I represents an i group that may be substituted. Alkyl or c3-15 cyclic hydrocarbon group; A is a single bond or a divalent linking group; -Y is Among them R21 ~ R3. Each represents independently a hydrogen atom or a substituted Cuo alkyl group, and a, b represents 1 or 2; in the formula (lb), Z2 represents -0- or -N (R3)-; wherein R3 represents hydrogen Atom, hydroxyl group or -0S〇2-R4; L represents c Q alkyl, Cl_1Q haloalkyl, C3-15 cycloalkyl or camphor residue; 'Rii' in formula (II); ^ 2 represents each Independent hydrogen atom, cyano group, halogen atom, or ci-1 which may be substituted. Alkyl; Z contains 2 carbon atoms (C-C) ′ to form a substituent 561316 VI. Aliphatic structured atomic group within the scope of patent application; the above "substitutable" means that it can be substituted with ci_4 oxygen, hydroxyl, carboxyl, COOR5, cyano or halogen atom; where resin (B ) Is a resin containing two kinds of repeating unit having an acid-decomposable group in all of the repeating units, and the difference in the content of the repeating unit is 5 to 30 mol%. 2 · The positive photoresist composition for far-ultraviolet exposure as described in item 1 of the patent application, wherein Z in the general formula (Π) is a bond containing 2 carbon atoms (CC) and may have a substituent It has a bridged alicyclic structure. 3. A positive photoresist composition for far-ultraviolet exposure as described in item 1 of the patent application, wherein the general formula (11) is the following general formula (Π-A) or general formula (Π-B) '. In the formulae (II-A) and (Π-B), Rn ~ are each independently a hydrogen atom, a halogen atom, a cyano group, -COOH, and -COOIML are synonymous with the above), a group decomposed by an acid action, -C (20) -XA-Ri7, or a C1--10 alkoxy group or a C3-15 cyclic hydrocarbon group which may have a substituent; and Ri3 ~ Ru are bonded to form at least 2 rings; η represents 0 or 1; this Here, X and A are the same as the above 561316 6. The scope of the patent application; R17 is -COOH, -COOR5, -CN, cyano, CV4 alkoxy which may have a substituent, -C0-nh-r6, -C〇_nh-so2-r6 (r5 and ruler 6 are each synonymous with the above) or the -Y group described above. 4. The positive-type photoresist composition for far-ultraviolet exposure according to any one of items 1 to 3 of the patent application chart, which contains a nitrogen-containing basic compound. 5. The positive photoresist composition for far-ultraviolet exposure according to item 4 of the patent application, wherein the nitrogen-containing basic compound is at least one selected from 1,5-diazobicyclo [4 · 3 · 0] -5 -nonene, 1,8-diazobicyclo [5 · 4 · 0] -7-undecene, 1,4-diazobicyclo [2.2.2] coreane, 4-dimethyl Aminoaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrrole, imidazole, pyridazine, pyrimidine, tertiary morpholine, and hindered amines with hindered piperidine structure compound of. -4-