TW548523B - Positive photosensitive composition - Google Patents

Abstract

A positive photosensitive composition comprises: (A) an acid generator capable of generating an acid upon irradiation with one of an actinic ray and a radiation; and (B) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and capable of decomposing by the action of an acid to increase the solubility in an alkali developer, wherein the acid generator (A) comprises at least two compounds of a sulfonium salt compound not having an aromatic ring, a triarylsulfonium salt compound, and a compound having a phenacylsulfonium salt structure.

Description

548523 A7 B7 V. Description of the invention (1) Field of the invention The present invention relates to a positive-type photosensitive composition, which can be used in the manufacturing process of semiconductors such as 1C, the manufacture of liquid crystal devices or circuit boards for thermal parallax, and other optical manufacturing. In the procedure, more particularly, it relates to a positive-type photosensitive composition which is favored for use when a far-ultraviolet light having a wavelength of 25 nm or less is used as an irradiation light source. BACKGROUND OF THE INVENTION Chemically amplified positive resist compositions are materials that can be patterned on substrates. That is, these compositions can use light such as far ultraviolet rays to generate light in the irradiated area and generate acids and use these acids as catalysts for reactions. This reaction causes a difference in the solubility of the developing solution between the area irradiated with actinic rays and the area not irradiated, and thus a pattern can be formed. When KrF excimer laser is used as the light source, the composition mainly contains a resin having a basic structure of poly (hydroxystyrene), where poly (hydroxyacetophenone) is in the 248 nm wavelength region used Absorptivity is not large ', so it is possible to ensure high sensitivity, high resolution, and high pattern formation compared to the case where a conventional fluorene quinone diazide / novolac resin is used. But 'when using a light source with a much shorter wavelength, such as an ArF excimer laser (193 nm), basically because the compound with an aromatic group has a large absorption in the wavelength range of 193 nm, it cannot even meet the chemical amplification resistance combination. The use of poly (meth) propionate is described in J. Vac. Sci. Technnl B9, 3357 (199 1). It can be used as a polymer with low absorption in the 193 nm wavelength region. However, this polymerization Materials are generally resistant to semiconductor manufacturing processes -4-This paper is suitable for national standards (CNS) A4 ('210 X 297 mm) 548523

The completed dry etching is inferior to the conventional phenolic resin having an aromatic group. A type 3 specific sulfonium salt (an anion having from 1 to 5 carbon atoms) and an aryl salt-salt mixed acid generator are disclosed in 2929 丨 7 (JP-A used in Hongi-Okana refers to "Unexamined announcement of this patent application "), Triarylsulfonium salt combination of perfluoroalkanesulfonic acid with 4 to 8 carbon atoms and 2-alkyladamantyl (meth) propionate The system is disclosed in jp_A_〇〇_ 275845 and a specific sulfonium salt of a perfluoroalkanesulfonic acid having from 4 to 8 carbon atoms (an anion having from 丨 to 8 carbon atoms) and a triphenylsulfonium salt or The mixed acid generator of iodine and thorium is disclosed in Ep_A-10441442. For the processing of finer pattern manufacturing, it is generally used to change the irradiation method or phase shift mask. Can be used for contact hole pattern in many examples.-When using zone j or lighting, t wants to obtain high resolution and wide defocus, exposure wide valley. "Wide defocus exposure tolerance" means shift due to focal length. Causes small line width variation. 0 When using a dot phase shift mask, Light emitting pattern resolution Shao points of the problems caused by side lobe, it is desirable to obtain the solution for this problem. In addition, the p-hydroxystyrene resin used for KrF excimer laser resist can interact with an acid generator, especially an ionic compound such as a phosphonium salt, and can improve the solubility of the acid generator, but it has an acyclic Hydrocarbon-based resins are very hydrophobic and do not easily interact with ionic compounds such as tweezers salts. As a result, the solubility of the acid generator becomes low, which causes a problem that particles are easily generated during the storage of the resist solution. -5-This paper size is in accordance with China National Private Standard (CNS) A4 specification (210 X 297 public capital) 548523 V. Description of the invention (3 Breaking changes and other issues. In addition, at any time ρΕ) + 4 + 9 range and heavy blue glance The passage of time causes the problem of poor footing stability (PED) inside or outside the irradiation device, and the pattern size changes. The stability of the PED (exposure delay) means that the

Can be placed inside or outside the irradiation device. When adding A to oxidized grease, the stability of the film in the child. There is a problem that the uniformity of the thin sheet is reduced. tjl summary = The first object of the present invention is to provide a positive-type photosensitive composition that can provide wide defocus exposure when used in the area of illumination. Latitude point phase shift masks are difficult to produce when forming a pattern. It is not easy to generate particles during storage. ^ f4 # In addition, as described above, the above-mentioned technology has the latitude of laminar exposure, hole-pitch dependence, exposure width, sensitivity caused by aging materials, rigidity, and low film caused by resin engraved with oxide. And other disadvantages, so I hope to further improve these problems. Therefore, another object of the present invention is to provide a positive-type photosensitive composition, which has excellent performance in mesh exposure latitude, hole pitch dependence, and exposure range, and prevents sensitivity changes caused by aging storage. In addition, the stability of the p ED and the uniformity of the film due to the oxide etching resin are improved. = To provide the above-mentioned and other objects of the present invention by providing orthopaedic scabbard-preventing composition with the following composition as a concrete example of the present invention '. ^ (1) A positive-type photosensitive composition, comprising: (A)-a kind of 548523 A7 B7 which can be generated when irradiated with one of actinic rays and radiation. V. The acid generator of the invention; (B) -A kind of resin: it has a monocyclic or polycyclic alicyclic structure; and can be decomposed under the action of acid to increase the solubility of the developer; (C) a basic compound; and (D)-an interfacial activity Agent 'which has at least one of a chlorine atom and a broken atom; wherein the acid generator (A) comprises at least one species selected from the group consisting of a sulfonium salt compound without an aromatic ring, a triarylsulfonium salt compound, and a benzyl methyl group A group of compounds composed of compounds with a phosphonium salt structure (first specific example). (2) The positive-type photosensitive composition as described in item (1), comprising (E) a solvent mixture, the mixture comprising: a solvent containing a base; and a solvent containing no base. (3) The positive-type photosensitive composition as described in the item (1), wherein the basic compound (C) contains at least one selected from the group consisting of an imidazole structure, a bi-bicyclic structure, a mineral hydroxide structure, and a carboxylic acid. Compounds of the acid salt structure and the aniline structure. (4) The positive-type photosensitive composition as described in the item (1), further comprising (F) a low molecular weight dissociation inhibiting compound having a molecular weight of 3,000 or less; and Groups that can be decomposed to increase solubility in an ocular developer by the action of an acid. (5) The positive-type photosensitive composition as described in the item (1), wherein the acid generator (A) comprises a triarylsulfonium salt compound and a compound having a benzamidinemethylsulfonium salt structure.

Binding

548523 AT B7 V. Description of the invention (5 (6) A positive photosensitive composition as described in item (1), wherein the acid generator (A) contains a sulfonium salt compound having no aromatic ring and a benzyl group A compound with a donkey methyl sharp salt structure. (7) The positive photosensitivity · composition as described in item (1), wherein the acid generator (A) contains a sulfonium salt compound having no aromatic ring and a diaryl compound (8) The positive-type photosensitive composition as described in item (1), wherein the resin (B) contains at least one repeating unit selected from the group consisting of the following units: part of the structure includes the following Repeating unit of alicyclic hydrocarbon represented by formula (pI), (PII), (pill), (pIV), (pV) or (pVI); and repeating unit represented by formula (Π-AB): Install R11

/ PI (pi) ^ 12 ~ C ~ Fli3 (ρΌ latch 14 k (pill) I15? --CH-Α16 (pIV)?% R21 -8-This paper & degree applies Chinese National Standard (CNS) A4 specifications (210 x 297 mm) 548523 A7

『22『 23 〇 C-CH ^ c ~ r24 (pV)

R2S 〇 II · \ 〆 -— ,,, ——C-〇-P \ (pVI) »/ where Rll represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or Two bases; Z stands for Carbon? —From the atomic group forming an alicyclic fluorenyl group, each of Ru, R! 3, Ri4, Ris & R16 independently represents a linear or branched alkyl group, or an alicyclic hydrocarbon group having from 1 to 4 carbon atoms. Provided that at least one of the ruler gate and rm represents an alicyclic hydrocarbon group, and that Ri5 and the ruler "one middle soil represent an alicyclic hydrocarbon group; R17, R 〖s, R 丨 9, ruler, and R] 1 each independently represent A hydrogen atom, a straight or branched sloping group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R17, r18, Ri9, R20, and R2i represents an alicyclic hydrocarbon group, and R! At least one of 9 and represents a linear or branched alkyl group, or alicyclic hydrocarbon group having from} to 4 carbon atoms; R22, Ru, Han24, and R25 each independently have from 1 to 4 carbon atoms A straight or branched alkyl group, or an alicyclic hydrocarbon group, provided that at least one of r22, r23, R24, and R25 represents an alicyclic hydrocarbon group, and R23 and R24 may be bonded to each other to form a ring; ~ (宁 -p — (II-AB) R ”· R12 '-9-This paper size applies to China National Standard (C NS) A4 (210 x 297 mm) 548523 A7 B7 V. Description of the invention (where {1 | ^ and R u Each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group which may have a substituent; Z represents an atomic group which must form an alicyclic structure with two carbon atoms (CC), which may have a substituent. 9) The positive-type photosensitive composition 'as described in item (8), wherein Z' in the formula (π_ΑΒ) represents an atomic group which must form a bridge-containing alicyclic structure together with two carbon atoms (CC) , Which may have a substituent. (1 0) The positive-type photosensitive composition as described in item (8), wherein the compound represented by the formula (III-AB) is represented by formula (III-AB) or (III-B) Means:

R

(H-A)

Where R! 3 ', R〆, R1SH0' each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR5, a group which can be decomposed under the action of an acid, -CPCO-XA ^ RV, An alkyl group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent; R5 represents an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent or a -Y group shown below; X represents an oxygen atom, sulfur Yuanyu, -NΗ-, -NHS02- or -NHS〇2NH_; Af stands for single bond or divalent linking group; -10-The national standard (CNS) specification (210X297 mm) of this paper applies to the standard (210X297 mm) 548523 A7

R ", Rm 丨, R 丨 5 丨, and r 丨,… bowls DH0H may have substituents each other. ^. VA burst_c〇-nh-r6, -co-nh-S〇2_R6 or 10,000 ; :: ί ', represents a radical which may have a substituent or a cyclic hydrocarbon radical which may have a substituent, -Y radical: ”%

Wherein R2 to R30 each independently represent a hydrogen atom or an alkyl group which may have a substituent, and a and b each represent 1 or 2. (11) A positive-type photosensitive composition comprising: (A) — a compound that can generate an acid when irradiated with one of actinic rays and radiation; (B 1) — a species that can be increased under the action of an acid Resin of solubility in alkaline developer 'wherein the resin has: a repeating unit of a group represented by the following formula (v-1), (ν-2), (ν-3) or (V-4); and A aliphatic cyclic hydrocarbon group:

(V-1) (V-2) -11-This paper size applies to Chinese National Standard (CNS) A4 (210; < 297 male front) 548523 A7 B7 V. Description of the invention

〇〇 Where Rib, R2b, R4b and Rsb each independently represent a hydrogen atom, an alkyl group which may have a substituent, and a ring which may have a substituent:!: An end group or an allyl group which may have a substituent, Rib, R2b, Two of R3b, R4b, and R5b can be bonded to form a ring, and the acid generator (A) contains at least two compounds selected from the group consisting of a triarylsulfonium salt compound, a compound having a benzamidinemethylsulfonium salt structure, and an aromatic compound. Group of compounds consisting of sulfonium salt compounds of the ring (second specific example). Jingling

Line (12) is a positive-type photosensitive composition as described in item (1 1), wherein the resin (B) contains at least one repeating unit selected from the group consisting of the following units: A partial structure includes the following formula (pi ), (Pll), (pill), (pIV), (pV) or (pVI) repeat units of alicyclic hydrocarbons; and repeat units of formula (II-AB):

R12 —c-r13 (p ⑴ R * I4 -12-This paper is suitable for China National Standard (CNS) A4 size (2) 〇 X 297 mm) 548523 5 A7 B7

『1S 〇 (pill) a ch, r16« 17 • C i

R2D (PIV) 21

R C-r24 (pV) ^ 25

(pv0: h represents methyl, ethyl'-n-propyl, group, or second butyl; 2 represents must be from the carbon source-two: isobutyl atom group; Rl2, r13, Rl4, Ri5 And Ri6 each is a linear or bifurcated group of a L-based sense atom, or an alicyclic ring = table = to 2 less than one = at least one of them represents an alicyclic hydrocarbon group, ... two of them represent an alicyclic hydrocarbon group; R | 7, R | 8, R | 9, R "R2 | ^, lice atom, linear or branched alkyl group with 丨 to 4 carbon atoms, or alicyclic hydrocarbon group, provided that Rl7, Ri8, Rl9, At least two of ⑼ and 爿 represent the ring base, and at least one of R! 9 and ruler 2 I has from 1 to -13---- This paper size is applicable to China National Standards (CNs) A4 specifications ( 210 X 297 mm) 548523 V. Description of the invention (11 linear or branched alkyl groups of 4 carbon atoms, or alicyclic hydrocarbon groups; in R · 24 and Rn each independently represent having from 丨 to 4 carbons Atomic linear or silk branching morpho groups, or alicyclic hydrocarbon groups, provided that R22, R23, R2 ^ R25 to 7 one represents an alicyclic hydrocarbon group, and R23 and R24 can be bonded to each other to form a ring; AB) of which 1111 and 1112 'are mutually exclusive A hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent; Z represents an atomic group which must form an alicyclic structure with two carbon atoms, which may have a substituent. (13) As described in (12 The positive photosensitive composition described in item), wherein Z1 in formula (II-AB) represents an atomic group which must form a bridge alicyclic structure together with two carbon atoms (CC), which may have a substituent (14) The positive-type photosensitive composition as described in the item (1 2), wherein the compound represented by the formula (II-AB) is represented by the formula (Π_Α) or (Π-Β): Binding_ ( Gong-A)

Ri > 16 • Rl6Rl3., R Ά · K14 -14-This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297, 548523 A7 ____B7 V. Description of the invention (12) where Rn ', R14, R! 5 'and R! 6' each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR5, a group decomposable under the action of an acid, -C (= 〇)- X-Af-Rn ', an alkyl group which may have a substituent or an alicyclic fe group which may have a substituent; R5 represents an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent, or -Y shown below X represents an oxygen atom, a sulfur atom, _ΝΗ-, -NHSCV or -NHS〇2NH-; A · represents a single bond or a divalent linking group; at least two of RW, Ri ', RW and R16' may be bonded to each other Bind to form a ring, η represents 0 or 1; R17 'represents -COOH, -C00R5, -CN, meridian, fluorenyloxy which may have a substituent, -C〇-NH-R6, _c〇-NH-S02 -R6 or -Y group shown below; R0 represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent, and -Y group:

Wherein R " to Iο 'each independently represent a hydrogen atom or an alkyl group which may have a substituent, and a and b each represent 1 or 2. (15) The positive-type photosensitive composition as described in the item (11), further comprising (C) a surfactant having at least one of a chlorine atom and a silicon atom. (16) A positive-type photosensitive composition as described in item (π), further comprising (D) a solvent mixture, the mixture comprising: at least one solvent selected from the following group A solvents; and at least one selected from the following: Solvents for Group B solvents and solvents selected from Group C solvents -15-This paper is suitable for National Standards (cNS) A4 (2 lG X 297) 548523 A7

V. Description of the invention (13) One: Group A: propylene glycol monoalkyl ether acrylic vinegar, β group: propylene glycol monoalkyl ether, alkyl lactate and alkyl alkoxy propionate. Group C: γ-butyrolactone , Ethylene carbonate and propylene carbonate. (1 7) The positive-type photosensitive composition as described in the item (1 1), further comprising (D) a solvent mixture; the mixture contains at least one alkyl lactate; and at least an ester solvent and an alkoxy Alkyl propionate. (18) The positive-type photosensitive composition as described in the item (17), wherein the solvent (D) further contains at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate. (19) The positive photosensitive composition as described in item (1 1), further comprising (D) a solvent mixture comprising: at least one solvent selected from the group D solvents below; and at least one selected from One of solvents of group E solvents and a solvent selected from group F solvents: Group D: heptone, Group E: propylene glycol monoalkyl ether, alkyl lactate and alkyl alkoxypropionate, group F: γ- Butyrolactone, ethylene carbonate and propylene carbonate. Detailed description of the invention (A) Acid peak generator The acid generator used in the present invention can generate an acid when irradiated by one of actinic rays and light rays, which is a mixture containing at least two compounds (equivalent to Compound (A) or an acid generator ") hereinafter, wherein the compound is selected from the group consisting of a triarylsulfonium salt compound (triarylsulfonium salt), a benzamidine

Hold

Line -16-

548523 A7 _______B7 V. Description of the invention (14) A group consisting of a compound of methyl phosphonium salt structure (benzidine methyl phosphonium salt) and a sparse salt compound (phosphonium salt) without an aromatic ring. A triarylsulfonium salt which can generate an acid when irradiated with actinic rays or radiation is a salt containing erbium as a cation. The aryl group of the triarylsulfonium cation is preferably a phenyl group and a fluorenyl group, and more preferably a phenyl group. The aryl groups of the three triarylsulfonium cations may be the same or different. Each aryl group may be substituted with an alkyl group (such as an alkyl group having from 1 to 15 carbon atoms), an alkoxy group (such as an alkoxy group having from 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group . Preferred substituents are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and a third butyl group and an alkoxy group having 1 to 4 carbon atoms For the best. Any one of three aryl groups may be substituted or all three aryl groups may be substituted. The substituent preferably replaces the para position of the aryl group. The anion of the triarylsulfonium salt is a sulfonic acid anion, preferably an alkanesulfonic acid anion substituted with a fluorine atom and a benzenesulfonic anion substituted with an electron withdrawing group, and more preferably an anion having 1 to 8 carbon atoms. The perfluoroalkanesulfonic acid anion 'is preferably a perfluorobutanesulfonic acid anion and a perfluorooctanesulfonic acid anion. The use of these compounds can improve the decomposition rate of acid-decomposable groups, increase sensitivity, and suppress the diffusion of the acid generated, resulting in improved resolution. The monoarylfluorene structure may take the form of a plurality of triarylfluorene structures bonded to other triarylfluorene structures through a linking group such as a group. Examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, a nitro'cyano group, an alkoxycarbonyl group, a fluorenyloxy group, and a fluorenyl group. Specific examples of triarylsulfonium salts that can be used in the present invention include the following compounds, but these examples should not be construed to limit the scope of the present invention. -17-The paper ruler / ΐ Common Chinese National Standard (CNS) A4 specification (21 () 297 publish y 548523 A7 B7 V. Description of the invention (15) (〇 > S + CF3SO3-3

S + CF3 {CF2): jSCV 3

(I-2)

S + CF3 (CF2) 7S〇3-3 (b.3)

CF3SO3- Μ

CF3 (CF2) 3S03- (I-5)

Or

CF3 (CF2) 3S〇3- (MO)

CF3 (CF2) 3S〇3- (1-11)

CF3 (CF2) 7S〇3- (1-12)

-18-This paper is suitable for Sichuan National Standard (CNS) A4 (mo X 297 mm) 548523 A7 B7

548523 A7

V. Description of the invention (A compound containing a phosphonium salt represented by the following formula (1 [) without an aromatic ring is a salt of phosphonium as a cation: R1b \ R2b ~ S ^

R3b / (ID where R'W and each independently represent an organic group without an aromatic ring. Here the aromatic ring also includes an aromatic ring containing a heteroatom. R, R2b, and R3b represent those without an aromatic ring The organic group is an organic group generally having from 1 to 30, preferably from 1 to 20 carbon atoms. R, R and R each preferably represent an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, Alkyl or ethenyl is preferably straight-chain, branched or cyclic 2-oxoalkyl or pitoxycarbonylmethyl ', most preferably straight-chain or branched 2-oxoalkyl. R, The alkynyl groups represented by R and R may be linear, branched or cyclic. The car parent group is a straight or branched alkynyl group having 1 to 10 carbon atoms (such as methyl, ethyl, propyl Radicals, butyl and pentyl) or cycloalkyl radicals (e.g. cyclopentyl, cyclohexyl, norbornyl) having from 3 to 10 carbon atoms. The 2-oxoalkyl radicals represented by R, R and R may be Straight-chain, branched or cyclic 'is preferably taken as an example of the alkyl group having 0 0 in the above position 2. The above Rlb, chi 21) and the alkoxy group in the alkoxycarbonylmethyl group represented by 11313 Alkyl groups having from 1 to 5 carbon atoms (such as methyl, (Ethyl, propyl, butyl and pentyl). rU, R2b and may be additionally substituted with a halogen atom, an alkoxy group (such as an alkoxy group having from 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. -20-

The size of this paper is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297). 548523 5. Description of the invention (π) R, R 2 b η 3 b ^ »^ ^ KT can be combined to form a ring Structure, while dagger lice atoms, sulfur atoms, ester bonds, amido bonds or carbonyls. Examples of groups formed by Rib, 〇 2 b virtual η 3 b., And two combinations include pit groups (such as butyl and pentyl).忮 From the viewpoint of photoreactivity, any one of Rlb and R3b preferably represents a group having a carbon-carbon double bond or a carbon-oxygen double bond. 2. The anion without 10,000 ranks is a sulfonic acid anion, preferably ^ ^ ljk gas atom-substituted alkanesulfonic acid anion and electron-withdrawing group substituted f & acid anion 'more preferably have from 1 to An 8-carbon perfluoroalkanesulfonate anion 'best is a perfluorobutanesulfonate anion and a perfluorooctanesulfonate anion. Use of these compounds can improve the decomposition rate of acid-decomposable groups, increase sensitivity, and inhibit the production of Acid diffusion, resulting in better resolution. Examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkoxy group, a fluorenyl group, and a fluorenyl group. Among the compounds represented by formula (π), at least one of Rib, ^ and RSb may be bonded to at least one of Rib, P, and P of the other compounds represented by formula (II) '. Specific examples of the sulfonium salt having no aromatic ring which can be used in the present invention include the following compounds, but these examples should not be construed as limiting the scope of the present invention. -21-Standard of this paper ❹1 Medium-sized house standard guide (CNS) Μ specifications (2ΐ () χ297 public funds) 548523 A7 B7 5 Invention description (19)

ο CF * 3 (CF2) 7S〇3- (II-3) O CF3 (OF2) sS〇3- (Π-5) CF3S ° 3- CF3 (CF2) 3S〇3- (IM) (H-2)

O CF3SO3- (H-4) 〇 CF3 (Cp2) 7S〇3- (Π-6)

CF3S03- CF s (CF 2) 3 ^ 03- 玎

(II-7) (II-8) line

C2 丄 CF3 (CF2) 7S〇3- (II-9) -22-This paper size applies to Chinese National Standards " (CNS) A4 Specification (210X 297) 548523 A7 B7 V. Description of the Invention (2)

CF3 (CF2) 3S03- (11-11) o CF3 (CF 2) 7 ^^ 3- (IM2)

2 CF3SO3-

2 CF3 (CF2) 3SOr (11-14)

〇 山 〇2 CF3 (OF2) 7 ^^ 3- (IMS) GJ0, said 〇p3 (CF * 2) 3 ^^ 3- (IM 7) d CF3CF2-aCF2CF2S03- (Π-19) CF3 (CF2) 3SOr (11-16) CH2CH2 (CF2) 5CF3 CF3 (CF2) 3S〇3 * (11-18)

O CF3CF2O-CF2CF2SO3- (II-20)

d-BlT

〇

CF3 (CF 2) 3 ^ 03- (11-21) CF3 (Cp2) 3S〇3- (II-22) -23-This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 548523 V. Description of the invention (21 Compound II with actinic rays or a salt-like salt structure; " The benzene-producing methyl group that can produce acid is a compound represented by the following formula (III) ...

Pic 〇

Rx

Rec ^ 5c R / c Λ X '(III) where Rlc, R2c, R, and D ^' 114. And R5e each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and each independently represent a hydrogen atom, an alkyl group, or an aryl group; RARy each represents an alkyl group, a 2-oxo group; Base, fluorenyl or ethylenyl. Any two of Rlc 'R2c' R3c, R4c, R5C, R6c and R7c and 1 ^ and Ry can be combined to form a cyclic structure, and the cyclic structure contains an atom, a fluorene atom, an ester bond or a amine bond . X · represents an anion of a sulfonic acid, a carboxylic acid, or a sulfonylimide. Ric ,, Rk, ruler and to 5. The alkyl group represented is linear and branched. If an alkyl group having 1 to 10 carbon atoms is taken as an example, it is preferably a straight chain or a chain having 1 to 5 gray atoms. Branched alkyl (such as methyl, ethyl, ethyl, straight and branched propyl, straight and branched butyl and straight and branched pentafur) and those having from 3 to 8 carbon atoms Cyclic alkyl (such as cyclopentyl and cyclohexyl) alkoxy groups represented by Ric, R2c, R3e, R4c, and R5e are linear, branched, and cyclic, such as having from 1 to 10 carbons The alkoxy group of the atom is an example. A good system has a straight chain and branched ~ 1 to 5 carbon atoms (such as methyl, ethoxy, straight chain and branched propoxy, straight chain and Branched butoxypropane or oxygen with straight oxygen 24-This paper's standard is applicable to China National Standard (CNS) Λ4 specification (210 X 297 male # > 548523

And linear and branched pentyloxy) and having from 3 to 8 oxy (such as cyclopentyloxy and cyclohexyloxy). , The original ... like 'force element is preferably if any one of Rlc, R2c, R3c, ^ and & represents a linear, branched or earthy alkyl group, or a linear, branched or cyclic alkoxy group, &, R2C, R3c, R4c and R5e preferably have a total of 2 to 15 carbon atoms, by which the solubility in the solvent can be improved and the generation of particles during storage can be suppressed. As the alkyl group represented by R? C, examples include the same alkyl groups as represented by ??. As a heart. With 1. The representative ^ group is, for example, an aryl group (such as a benzyl group) having 6 to 4 carbon atoms. Examples of the alkyl group represented by 1 and 1 ^ include and heart. ,, R4. And the same alkynyl group represented by ". As the 2 · oxyalkyl group represented by 1 and 1? ^, Examples include and I. ,,,

Rk, Min Shao and Ruler 5. Represents the same alkyl group with C = 0 at position 2. As the alkoxy group in the alkoxycarbonylmethyl group represented by R and Ry, C includes an alkoxy group having the same definition as Rlc, R2c, be, and Rk.

As a group formed by the combination of R ^ and Ry, examples include butyl and pentyl. The three-dimensional structure of the compound represented by formula (II) is fixed by forming a ring, and as a result, the photodecomposition property can be improved. When Ru, R2e, R; e, R4c, R5. For example, when Yimin is combined with any two of R? C to form a ring structure, any one of Rkj he, be, and RSc is combined with any of R0e and RTe to form a single bond or linker and form a ring. It is preferable, and an example in which a single bond or a linking group is combined with one of them to form a ring is particularly preferable. Examples of linkers include alkylene groups which may have a substituent, and alkenyl groups which may have a substituent ... 0-, 1, -C0-, -CONR- (where R represents a hydrogen atom, an alkyl group, or a fluorenyl group) And a group consisting of two of these groups, preferably having -25-

548523

The alkylene group which may have a substituent, an alkylene group which may have a substituent and an oxygen atom, and the alkylene group which may have a substituent and contain a sulfur atom. Examples of the substituent include an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), an aryl group (preferably = an aryl group having 6 to 10 carbon atoms such as a benzyl group), and a fluorenyl group ( Preferred is a fluorenyl group having 2 to 11 carbon atoms). The linking group is preferably a 5- to 7-membered ring such as methylene, ethylene, propyl, -CHyO- and -CHrS-, and a linking group such as ethylene, which can form 6 rings , -CHyO- and -CH ^ S- are particularly preferred. By forming a 6-membered ring, a plane of the carbonyl is nearly perpendicular to the σ bond of S-C, and the photodecomposition properties can be improved by using the rails. The compound represented by formula (III) may be a single bond or a compound. , Rk, Rk, Rk, ruler, and linker at any position in the ruler and 1 and Ry = or more compounds of the structure represented by formula (III). 1 X · preferably represents a sulfonic acid anion, preferably a sulfonic acid anion substituted with a fluorine atom at a position 1 and a benzenesulfonic anion substituted with an electron withdrawing group. Alkanes = The alkane moiety of an ion can be substituted with an alkoxy group (eg, a fluoroalkoxy group with from 1 to 8 carbon atoms (eg, from 〖to 8 carbon atoms). An example of electron withdrawing; ^ ^ atom, gas Atom, bromine atom, nitro group, aryl group, alkoxy group and fluorenyl group. Soil lice = good line X- represents the perfluorooctane sulfonate with very good quality perfluorooctane from 8 to 8 carbon atoms. Sulfuric acid anions, the best are perfluorobutane acid anions, and difluoro ▼ alkanesulfonic acid anions. These compounds can be used to change the cover: the decomposition rate of the group is increased and the sensitivity is increased. Improved. K-diffusion ': In the present invention, the compound examples of the benzyl methyl sparse salt structure are table materials τ, but these examples should not be construed as limiting the present invention Fanxin-26-

548523 A7 B7

548523 A7

This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

Binding

548523 A7 B7

548523 A7 B7

548523 A7 B7

548523 A7 B7

V. Description of the invention (30) Among the compounds of the present invention & " A, # ^ milk nails into knives (A), the defect is 丨) containing a mixture of triarylsulfonium salt and stupid methylsulfonium & methyl salt You ··, each ancient, this mouthpiece H) $ There are 锍 salts without aromatic rings and stupid methyl chloride salts 、, Kun compound, become 丨 丨 丨) the author Yiming A ιη) ϋ 有Diaryl sulfonium salt and without aromatic ring: a mixture of tiger salt. In the case where the mixture contains a triarylsulfonium salt and a benzamidinemethylsulfonium salt 丨), what is the right content? ij conditions: (1) Based on the total solids content of the composition, the content of triarylsulfonium salt is from 4 to 4 weight percent. It is preferably from 08 to 35 wt%, and more preferably from 1 to 3 wt%. / 〇. (2) Based on the total solids content of the composition, the content of benzamidine methyl phosphonium salt is ^ weight / 0 or more, preferably from 2 to i 2% by weight, more preferably from 3 to 8% by weight. (3) Based on the entire solid content of the compound, the total amount of the two acid generators added is 1.1% by weight or more, preferably from 5 to 12% by weight, and more preferably from 3 to 10% by weight. It is best to satisfy one or more of the conditions 丨) to 3), preferably two or more of the conditions 1) to 3), and the best is to satisfy the conditions 丨) to 3). When any condition cannot be satisfied, the amount of acid generated is insufficient and the sensitivity is liable to deteriorate. From the viewpoint of the k-leaf amplitude, the ratio (weight ratio) of triarylsulfonium salt to benzyl methylsulfonium salt is preferably from 20/8 to 80/20, more preferably from 25/75 From 75/25, the best line is from 30/70 to 70/30. In the example ii) where the mixture contains an acute salt without aromatic rings and a methyl benzamidine methylsulfonium salt, the following conditions are satisfied: (1) Based on the entire solid content of the composition, the content of the sulfonium salt without aromatic rings is 2% by weight or more, preferably from 2.5 to 15% by weight, more preferably from 3 to -33-This paper size is applicable to National Standards (CNS) Λ4 specifications (2) 0 X 297 mm 548523

1 2% by weight. (2) Based on the entire solid content of the composition, the content of benzamidine methyl phosphonium salt is 1 weight! % Or more 'is preferably from 2 to 12% by weight, and more preferably from 3 to 8% by weight. (3) Based on the total solid content of the group, the total amount of the two acid generators is 3 Weight f% or more, preferably from 4.5 to 20 weights. / 〇, more preferably from 6 to 15% by weight. It can satisfy one or more of the conditions 1) to 3), preferably it can satisfy two or more of the conditions 1) to 3), and the best can fully satisfy the conditions 丨) to 3). When any condition cannot be satisfied, the amount of acid generated is insufficient and the sensitivity is liable to deteriorate. In Example iU) where the mixture contains a triarylsulfonium salt and a sulfonium salt without an aromatic ring, the following conditions are preferably satisfied: (1) The content of the sulfonium salt without an aromatic ring is 2% by weight based on the entire solid content of the composition Or more preferably from 2.5 to 15% by weight, more preferably from 3 to 12% by weight. (2) Based on the entire solid content of the composition, the content of triarylsulfonium salt is from 0.1 to 4% by weight, preferably from 0.5 to 3.5% by weight, and more preferably from 1 to 3% by weight: (3 ) Based on the entire solid content of the composition, the total amount of the two acid generators added is 2.1% by weight or more, preferably from 25 to 20% by weight, more preferably from two to 15% by weight. «° Face I. Acids that can be used in combination with ingredients other than (A). Residues are generated in addition to the mixture of ingredient (A) and actinic rays and radiation. Compounds which occlude and generate acids can also be used in the present invention. ， 可 刀 The photoacid generator that can be used in combination with the component (A) of the present invention, ^ 里 ’若 -34-548523

V. Description of the invention (32 is expressed by the molar ratio of (ingredient (A)) / (other photoacid generator), 100/0 to 20/80, preferably 100/0 to 4〇 / 6. More preferably, it means from 100/0 to 50/50. The photoinitiator for photocationic polymerization, photoinitiator for photoradical polymerization, photodecoloring agent for dyes, Photofading agents, compounds known as microresistors, or similar compounds and mixtures of these compounds upon irradiation with actinic rays and radiation are examples of such photoacid generators that can be used in combination. Samarium salts such as diazonium, ammonium, scale, iodonium, osmium, selenium, and selenium salts, organic halogen compounds, organometallic / organohalides, ortho-nitrobenzyl-type protective groups As such compounds, acid generators, compounds which can be photolyzed to produce sulfonic acids, and dihydrazone compounds represented by imine sulfonate esters are used. In addition, those having these bases or compounds which can generate an acid when exposed to actinic radiation or radiation Compounds can be used in the present invention, in which these groups or compounds Is introduced into the polymer main chain or side chain, such as these US Patent No. 3,849,137, German Patent No. 3,914,407, Jin-A-63-26653, Jin-A-55-164824, JP-A-62-69263, JP -A-63-146038, JP-A-63-1 63452, JP-A-62,153 853, and JP-A-63-146029. And 'as in US Patent No. 3,779,778 and European Patent No. 126712 The compounds described as being capable of generating an acid by light can also be used in the present invention. Among the above compounds which can be used in combination with the component (A) and can be decomposed upon irradiation with actinic rays or radiation, these can be particularly effectively used in the present invention The compounds are described below. This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 male fluorescent) 548523 A7 _____ B7 V. Description of the invention (33) (1) Dream represented by the following formula (PAG 1) Sigma derivatives and S-Sangen derivatives represented by the following formula (PAG 2), which are substituted by trihalomethyl: PPA (PAG1) R20〆, 0.8C (Y) 3

(PAG2) where R2G1 represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted fluorenyl group; r2G2 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, Substituted or unsubstituted fluorenyl 'or -C (Y)]; γ represents a chlorine atom or a bromine atom. Specific examples thereof include the following compounds, however, these compounds should not be construed as limiting the scope of the present invention.

Ν—Ν // \\ CH = CH-C C_CCI3, 〇〆 (PAG1-1) ch3O ~ Ν_Ν // η CH = CH-C C-CCI3 '〇〆 (PAG1-2) -36-

This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 548523 A7 ---------- B7 V. Description of the invention (34) "

(PAG2 -1) C1

(2) The iodonium salt represented by the following formula (P AG3) or the thallium salt represented by the following formula (pAG4):

(PAG3)

Pack (PAG4) order

Line R203 R204> S + z r205 In the formula (PAG3), Ar1 and Ar2 each represent a substituted or unsubstituted aryl group. Examples of preferred substituents include alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, carboxy, alkoxycarbonyl, hydroxyl, hydrogenthio, and halogen atoms. In formula (PAG4), R2G3 and R2G5 each represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, provided that at least one of them represents a substituted or unsubstituted alkyl group and at least One representative is substituted or not -37-

This paper size applies to China National Standard (CNS) A4 (210 X 297 public dream) 548523 A7 B7

Substituted aryl. For example, the aryl group may have a group of 6 to "carbon atoms" as an example, and the alkyl group may have a group of from 8 to 8 carbon atoms as an example. The substituent of a square aryl group preferably has 丨 to 8 Carbon atom alkoxy group, alkyl group having 1 to 8 carbon atoms, nitro, carboxyl, hydroxyl or halogen atom, and the substituent of the alkyl group is preferably an alkoxy group having! To 8 carbon atoms, > Or alkoxycarbonyl. 1 ~ In the formulae (PAG3) and (PAM), ζ · represents a balanced anion, perfluoro, alkanoate anions such as BF4-, AsF6 ·, PF6 ·, SbFV, SiFV Such as CKV and CFJCV, pentafluorobenzene sulfonate anion, polynuclear ^ group sulfonate anion such as 荇-丨 _ sulfonate anion, anthraquinone sulfonate anion: = dyes containing sulfonate group, but this The invention is not limited by them. Κ 〆 In addition, any two m of R203, r204, and r205 may be individually bonded to each other through a single bond or a substituent.

Specific examples thereof include the following compounds, but the present invention is not limited thereto.

C12H25 (PAG3 ~ l)

SbFQ9 (PAG3-2) CF3SO? (PA63-3) __-38-This paper is suitable for the standard / fl towel _ home standard (CNS) A4 specifications (21Q > < 297 public director) 548523 A7 B7 V. Description of the invention (36 )

〇CH3 0〇3S (PAG3-4)

CbN

(PAG3-9) S〇3 binding f -39-This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 548523 A7 B7

548523 A7 B7

Pretend

548523 A7 B7 5 Description of the invention (39)

ch3 (PAG4 «9) pf8 Θ

(PAG4-10)

SbF6x Θ C4H9

(PAG4H)) H3CO H3CO (PAG4-12) CF3SO3

Line -42-This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 548523 A7 B7

548523 A7 B7 V. Description of the invention (41 The phosphonium salts represented by formulae (PAG3) and (PAG4) are well-known compounds, and can be used in accordance with, for example, U.S. Patent No. 2,807,648, No. 4,247,473, or Jp_ A-5 3 -10 Synthesized by the method disclosed in 1 3 3 1. (3) The second derivative represented by the following formula (PAG5) or the imine sulfonate derivative represented by the following formula (PAG6): Αχ3-S〇2-S 〇2—Αχ4 R206

(PAG5) (PAG6) where Ar3 and Ar4 each represent a substituted or unsubstituted aryl group; R2G6 represents, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; A represents a substituted or unsubstituted aryl group Unsubstituted alkylene, substituted or unsubstituted fluorenyl, or substituted or unsubstituted aryl. Specific examples thereof include the following compounds, but the present invention is not limited thereto. 548523 A7 B7 5 Description of the invention (42) C1

Cl (PAG5 -1) H3C ^^^ S〇2-S02-^^-CH3 (PAG5-2) H3C〇-^^-S02-S〇2 ^^^ CH3 (PAG5-3):-^^ ^ S02-S〇2 * (PAG5-4) h3c-

Cl F3CH0 ^ S〇2-CF3 (PAG5-5)

S〇2-S〇2 -9

Cl h5c2〇

(PAG5-6) S02 a (PAG5-7)

Cl

s〇2-so2 < ^ · (PAG5-8)

Cl 45-This paper is fully compliant with China National Standard (CNS) A4 (Magic () x 297 mm) 548523 A7 B7

548523 A7 B7

548523 A7

The meaning of this paper applies the Chinese National Standard (CMS) A4 specification (210 x 297 mm) 548523 A7 B7 V. Description of the invention (46)

(PAG6-13) (4) A diazodisulfone derivative represented by the following formula (PAG7) (PAG7) (PAG7) wherein R represents a straight-chain, branched or cyclic alkyl group, or a substituted aryl group. Specific examples thereof are shown below, but the present invention is not limited thereto. -49-This paper size is applicable to China National Standard (C NS) A4 specification (210 X 297 public and redundant) 548523 Λ7 Β7 V. Description of the invention (47)

(PAG7-3)

Ο Ο (PAG7-4) of o (p

〇MS = o Applicable to Chinese National Standards (CNS) A4 specifications (2) 0 X 297 male and female 548523 A7 B7

Binding

Line 548523 V. Description of the invention (49 Any resin having a monocyclic or polycyclic alicyclic ring to increase the solubility of the developer;; == acid-decomposable resin used in the next specific example; A formula (vl), fV 9, 7 in the second specific example of the present invention (B1) is a kind having a garden represented by (2), (V-3) or (V-4) > Tongue σ Group of cyclic hydrocarbon groups and can be used as an acid in the resin and the resin. Under the action of μ ~ Solubility in additive developer m- In the first specific example, resins with the basic formula represented by the above formula (), (2), (V-3) or (V-4) are also preferred. Repeating units. The formulae (V 丨), (V.2), (V-3), and (V-4) are described below. In the formulae (V-1), (ν-2), (ν-3), and (V-4), Rlb and Rn each represent a hydrogen atom, a cycloalkyl group which may have an alkyl group which may have a substituent, or may have a substituent Alkenyl, and any two of Rib and Rsb can be bonded to form a ring. In the formulae (V-1), (ν-2), (V-3) and (V-4), the alkyl group represented by Rlb and hb is a linear or branched alkyl group R2b, R4b May have substituents R2b, R3b, R4b, groups R2b, R3b, R ^ b which may have a substituted linear or branched alkyl group, preferably a straight or branched chain with 1 to i2 carbon atoms Alkyl is preferably a linear or branched alkyl group having from 1 to 10 carbon atoms, more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, Dibutyl, third butyl, pentyl, hexyl: heptyl, octyl, nonyl and decyl. -52 This paper is again suitable for China National Standard (CNS) A4 (210 X 297 mm) 548523 A7

, Rb, Rw,! The cycloalkyl group represented by ^ and U / f is preferably a cyclohexyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

The alkenyl groups represented by Rib, Rn, Rh, Chi 46 and Ru are preferably amidino groups having 2 to 6 carbon atoms, such as vinyl, propenyl, butenyl, and hexamethylene.

Rings formed by any two of Rib, R2b, R3b, R4b, and R5b can be 3- to 8-membered rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, and cyclobutane ring example. In the formulae (v-1), (V-2), (ν · 3), and (V-4), Rib, R2b, R3b, R4b, and Ru may be bonded to any carbon atom constituting a cyclic structure. The preferred substituents of the above-mentioned tiger group, cyclohexyl group and alkenyl group may have a halogen atom of from 4 to 4 carbon atoms, a halogen atom (such as gas, chlorine, bromine, and K), and from 2 to 5 carbons. As an example, an amidino group, a donkeyoxy group having 2 to 5 carbon atoms, a cyano group, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group having 2 to 5 carbon atoms, and a nitro group are exemplified. The repeating unit having a group represented by the above formula (Vl), (V-2), (V-3) or (V-4) includes the repeating unit represented by the above formula (Π-A) or (II-B) , Wherein at least one of Ri3, Ri4 ', R15' and Ri6 'has a group represented by formula (Vl), (V-2), (V-3) or (V-4) (such as -C〇〇 R5 in R5 represents a group represented by formula (V-1), (v-2), (V-3) or (V-4), and a repeating unit represented by the following formula (AI).

^ bO-one tCH2—〇 ten ° ~ ^ (AI) 〇

I a .—— b2 -53-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7 V. Description of the invention (51) where Rb0 represents a hydrogen atom, a halogen atom, or has A substituted or unsubstituted alkyl group from 1 to 4 carbon atoms. Rb. The preferred substituents of the alkyl group shown include the same substitutions as the preferred examples of preferred substituents of the above formula (V)), (ν · 2), (v, 3) or (ν · 4) ^ base. The function atom represented by 包括 includes a fluorine atom, a chlorine atom, a desert atom, or a chi atom. Rb0 preferably represents a hydrogen atom. The base diagram A 'represents a single bond, an ether group, an ester group, a carbonyl group, and an alkenyl group. The group b2 in the table represents any formula (v-1), (v_2), (v_3) or (v_4). The intermediate linker includes, for example, the following groups.

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 548523 A7 — ___B7 V. Description of the invention (52) In the above formula, Rab and Rbb may be the same or different, each of which represents a hydrogen atom, and a yuan base , Substituted alkyl, halogen atom, hydroxyl, or alkoxy. The alkyl group is preferably a low carbon number alkyl group such as methyl, ethyl, propyl, isopropyl or butyl ', and is preferably methyl, ethyl, propyl or isopropyl. Examples of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group having from 1 to 4 carbon atoms. Examples of pitoxy include alkoxy having from 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy. Examples of the self atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. rl represents an integer from 丨 to 10, preferably an integer from 丨 to 4, and m represents an integer from 丨 to 3, and preferably 1 or 2. Specific examples of the repeating unit represented by the formula (AI) are shown below, but these compounds should not be construed as limiting the scope of the present invention. -55-548523 A7 B7 V. Description of the invention (53) CH3 CH3 ~ ^ ch2-c—j- 0

ch3 * ch2-c—} c—o (lb-3) 〇

ch3

(lb-4)

Wood paper scale applies Chinese National Standard (CNS) A4 size dagger> 1 gt x 297 male) 548523 A7 B7 V. Description of the invention (54) ch3 CH2- C-) CH ^ ~ ^ CH2-c · c— h3c ( lb-9)

H-^ CH2— 〇 H I .CH ^ —c ·

ch3 ch2-c—} r / C—〇0 H3c h3c (lb-12) CH3 ~ ^ CH2 ~ C—y ~ 〇 / 一 0 > Τ) \ 〇h3c- ^ V >, 〇H3c CIb-13) (lb -14)

This paper size applies to China National Standard (CNS) A4 (! 210 x 297 mm)

548523 A7 B7

548523 A7 B7 V Description of the invention (56) CH:-(ch2-c · ^ // C 1〇

, (CH2) 2-〇, // ° CH, C — (CH2) 2-C \ 〇◦ (lb-24) CH 'CH2-C' oc-o (CH2) 2-0,, // c- (ch2) 2-c, // o (lb-25)

HX CH, ch2-c- c-o (ch2) 2-〇. \ // (lb-26) C — (CH2) 2—C,

-59-This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 548523 A7 B7 5

Description of the invention (57) ch3 I CH, ~ (ch2-ς —- C · // c-o 〇 // // c-o H3C (U 0 · (lb-27) 〇 0

ch3 • ch〇-c-4 CH1 · I, ch2-c-c-o 0 // 4, Η43 0_ h3c (lb-29) 〇

ch3 CH〇-C ~ \ H CH2—c- c-o // C one 0 o //

0 o // c—c CH, h3c CHr o-

H, C (lb-32) ch3 ch2-c-4 / A one ◦, // (CH2) 2-C,-(ch2-c '0 CH3 (lb-33)

o -60

This paper size applies Chinese National Standard (CNS) A4 specification (210 x 297 mm) 548523 A7 B7 Five invention descriptions (58) ch3 ^ ch2 ~ c —] " ― CH】 • CHo-C-ί 〇C 一 0 // 〇

〇 ^ a 0, (CH2) 2-C ^ (lb-36)

CH3-(ch2-c Η (~ (CH2-., Ten -fCH, Ο

Ο C 一 〇 〇

CH: ch9-c— C— 〇 (CH2) 2-〇, // P-(CH2) 2-c, // 〇 (lb-40) -61-CH,

This paper size applies the Chinese National Standard (CNS) A4 specification (21〇x 297 mm) 548523 A7 B7 Five invention description (59) ch3-(ch2-c ^-) — co. 〇 (CH2) 2—ο, \ // 〇 (lb-41) //, C— (CH2) 2—

ch3— ^ CH2-c xi c one, o k (CH2) 2-0, P c— (ch2) 2— // 〇 (lb-42)

CH3- ^ ch2-c -j- c-0, 〇

o H-^ ch2 ~ c- (/ C'〇x (ch2) 2-o, c— (ch2) 2—c, \ // o (lb-44) -62-This paper size applies to Chinese national standards ( CNS) A4 size (210 x 297 mm)

H, C

548523 Five A7 B7, description of the invention (60) In the resin (B) and resin (B 1) of the present invention, it is preferable to include at least one group selected from the following repeating units: part of the structure includes formula (pi), ( PΠ) (pill), (pIV), (pV), or (pVI) repeating units of alicyclic hydrocarbons; repeating units shown by formula (Π-AB): white, and / F i (Pi) ^ 12 ~ C-R13 (pit) r14 οI -CH-r16 (pm)

r21 (piv) ^ 22 ^ 23 -C—CH—c—R24 R25 (pV) -63-The standard of this paper is applicable to Chinese National Standard (CMS) Λ4 specification (210 x 297 mm) A7 B7

548523 V. Description of the invention (where R11 represents methyl, ethyl, n-propyl, isopropyl, n-titanyl or second butyl; Z represents a group that must be a butyl atom with a carbon atom ... R1 "-, each representing : = To radical 4: straight or branched alkyl of carbon atom, or alicyclic hydrocarbon group, conditions,

At least one of Rn and Rm, or Han Yi or! ^ Stands for alicyclic hydrocarbon group: 1 = R1S, R [9, Rm and Rh each represents a hydrogen atom, a straight or branched alkyl group having 7 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that ^ 7 , ≪ at least one of ho and Rn represents an alicyclic hydrocarbon group, and R! 9 or a straight or branched alkyl group having k 1 to 4 carbon atoms, or an alicyclic hydrocarbon, earth, 2 or 2, R23, Hu, and R25 each represent a linear or branched fire radical, or an alicyclic warp radical having 1 carbon atom, provided that at least one of r22, r23, r24, and Rh represents an alicyclic hydrocarbon group, and R23 and R24 can be bonded to each other to form a ring;

Binding

line

I I

-64-

This paper size applies to China National Standard (CNS) A4 specifications (2) 0x 297 mm) 548523 A7

RU and Λ Rl2 in the two each represent hydrogen atom, cyano group, halogen atom or may have a substituent (the recognition group 'z' contains two bonded carbon atoms (cc) and represents an atom required to form an alicyclic structure A group which may have a substituent. The compound not represented by the formula (II AB) is preferably represented by the formula ⑴ · A) or ⑴ · B):

(Gongong-Α)

Among them, Ru ', RW, and Rumy each represent an argon atom, a halogen atom, a cyano group, -COOH, -COOR5, a group which can be decomposed under the action of an acid, {卜 〇) _ X-A' -Rn ', an alkyl group which may have a substituent, or an alicyclic hydrocarbon group which may have a substituent; R5 represents an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent, or X-Y in Table 7F; Oxygen atom, sulfur atom, _NH-, or -NHS02NH-; A 'represents a single bond or a divalent linking group ;, R | ^, ruler and! At least two of ^ 6 'may be bonded to each other to form a ring; η represents 0 or 1; R17' represents -COOH, -C00R5, _CN, a hydroxyl group, an alkoxy group which may have a substituent, -C〇-NH-R0 , -C〇-NH-SCVR0 or _γ-based -65-the standard Chinese paper standard (CNS) Α4 (210 X 297 mm) 548523

Wherein R21 ′ to RW each represent a hydrogen atom or an alkyl group which may have a substituent, and a and b each represent 1 or 2. In the formulae (Pΐ), (Pΐΐ), (ρΙΠ), (piv), (pV), and (pVI), the alkyl group represented by Ri2 to r25 is a substituted or unsubstituted group having 1 to 4 carbon atoms , Substituted, linear or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl and third butyl as examples. Examples of the substituent of the substituted alkyl group include a fluorenyloxy group having 1 to 4 carbon atoms, a halogen atom (e.g., fluorine, chlorine, bromine, and aryl), a fluorenyl group, a fluorenyl group, a cyano group, a hydroxyl group, a carboxyl group, and an alkane group. Oxycarbonyl and nitro. The alicyclic hydrocarbon group represented by R !! to R25 and the alicyclic fluorenyl group formed by Z and a carbon atom may be monocyclic or polycyclic. In particular, it may have a monocyclic, bicyclic, tricyclic or tetracyclic structure and 5 or more carbon atoms, preferably from 6 to 30 carbon atoms, and particularly preferably from 7 to 25 carbon atoms. example. These alicyclic hydrocarbon groups may have a substituent. Examples of the structure of the alicyclic part of the alicyclic hydrocarbon group are shown below. -66------ This paper size applies to Chinese national standard ⑴ ^ A4 (210 X 297 male I) 548523

This paper is suitable for the National Standard (CNS) A4 specification (210/297 mm) 548523

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523

May be adamantyl, pro-adamantyl, fetane residue, tricyclodecyl, four% undecyl, norbornyl, cedarol, cyclohexyl, cycloheptyl, cyclooctyl ^ The cycloundecyl group is used as a preferred example of the above-mentioned alicyclic moiety in the present invention. Among them, adamantyl group, I 垸 residue, noryl group, cedarol group,% hexyl, cycloheptyl, cyclooctyl, Decyl and cyclododecyl are preferred. Examples of the substituents of some of the aliphatic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a low carbon number alkyl group such as methyl, ethyl, propyl, isopropyl and butyl, and more preferably methyl, ethyl, propyl and isopropyl. Examples of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. The alkoxy group is an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. The structures represented by the formulae (pI), (pII), (pln), (pIV), (pV), and (pVI) in the resin (B) and the resin (Bi) can be used to protect alkaline soluble groups. A variety of well-known basic soluble groups in this technical field can be taken as a conventional example of this experimental soluble group. Teli 1] fluorene can be exemplified by a few acid groups, a transverse acid group, a g group, and a thiol group, and preferably a few acid group and a carboxylic acid group. Resin (B) and Resin (B1) The soluble soluble groups which are protected by the structures represented by formulae (pI), (pII), (piII), (pIV), (p V) and (p VI) include the following The group represented by the formula (p v11), (pVIII), (pix), (pX), or (ρχι) ... -69-The paper rule > degree applies Chinese National Standard NS) Α4 size (210 x 297) Absolutely) 548523 A7 B7 V. Description of the invention (67)

(pVII) (pVIII) i?? --C-〇-CH-r16 R17 Rie5? -C 010-C ^ 20 I R21 〇 ^ 22 R23 〇li I '' II-C --〇-C --CH--C —R24 I R25 (pix) (pX) (pXI) -70-This paper size applies to China National Standard (CNS) A4 (210 X 297 public 548523 A7 B7) V. Description of the invention (68) Formula (pVII), (pVIII ), (PIX), (pX), and (pXI), the definitions of Rn to R25, and Z are the same as those described above. In resin (B) and resin (B1), there are warp formulas (pi), (pll), The repeating unit of the basic soluble group protected by the structure represented by (pill), (pIV), (pV) or (pVI) is preferably represented by the following formula (pA):

R

〇 wherein R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted, linear or branched alkyl group having from 1 to 4 carbon atoms. Multiple R · s may be the same or different. A represents two or more groups selected from the group consisting of a single bond, a fluorenyl group, a substituted alkenyl group, an ether group, a thioether group, a carbonyl group, an ester group, a fluorenyl group, a sulfonyl group, a urethane group, and a fluorenyl group Composition.

Ra represents a group represented by the formula (pi), (pll), (pill), (pIV), (pV), or (pVI). Specific examples of the monomer corresponding to the repeating unit represented by the formula (p A) are shown below. -71-This paper is fully compliant with China National Standard (CNS) Λ4 specifications (2) 0, < 297 public goods)

Binding

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548523 A7 B7

548523 Α7 Β7 V Description of the invention (π

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523 A7B7 V. Description of the invention (72)

-75-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 548523 A7 B7

548523 A7 B7 V. Description of the invention (74)

-77-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 548523 Fifth invention description (75) In the above formula (II-AB), Ru and R〆 each represent a hydrogen atom, a cyano group Alkyl groups may or may have an alkyl group having a substituent. It contains two bonded carbon atoms (C-C) and represents an atomic group required to form an alicyclic structure, which may have a substituent. ^^ With! The halogen atom represented by ^ 2 includes a chlorine atom, a desert atom, a gas atom, or a broken atom. The alkyl group represented by R, 2 ', Rn' to RW is the most straight or branched alkyl group having 1 to 1 carbon atoms, preferably having ^ to 6 carbon atoms Or branched alkyl, more preferably methyl, ethyl, propyl, propyl, n-butyl, isobutyl, second butyl, or third butyl. Examples of the other substituents of the above-mentioned alkyl group include a light group, a prime atom, a fluorene group, a oxo group, a donkey group, an amino group, and an amino group. Examples of the function atom include a gas atom, a bromine atom, a fluorine atom, and an iodine atom. The alkoxy groups include alkoxy groups having from 1 to 4 carbon atoms, such as methoxy, ethoxy, amyl and butoxy. Examples of fluorenyl include formamyl and acetamyl, and alkoxy includes acetamyloxy. a The atomic group represented by soil I to form an alicyclic structure is an atomic group used to shape resins to repeat units of alicyclic hydrocarbons, the origin of bridged alicyclic structures = radicals, especially to form bridged aliphatic The alicyclic bridge-containing atomic group of the cyclic hydrocarbon repeating unit is preferable, and it may have a substituent. Examples of the skeleton of the alicyclic hydrocarbon to be formed include the following structures. Dimensions This paper is sized for China National Standards (CNS) A4 (2i〇 -78-x 297 ^ 57 548523 A7 B7

548523 A7 B7

548523 A7 __ B7 V. Description of the invention (78) In the above structure, the preferred bridged alicyclic hydrocarbon skeletons are (5), (6), (7), (9), (10), (13), (( 14), (15), (23), (28), (36), (37), (42), and (47). The alicyclic hydrocarbon skeleton may have a substituent, such as R13, R15f, and R16 in the formulae (II-A) and (II-B), and examples of the substituent may be used. Among repeating units having an alicyclic hydrocarbon, repeating units represented by formula (Π-A) or (II-B) are preferred. In the formula (Π-A) or (Π-Β), Ri3 ,, Ri4 ,, Ri5 ', and R16, each of which represents a hydrogen atom, a # prime atom, a cyano group, -COOH, -COOR5, may be under the action of an acid Decomposed groups, alkyl groups which may have a substituent or alicyclic hydrocarbon groups which may have a substituent, r5 represents an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent, or -γ group; X represents Oxygen atom, sulfur atom, -NH-, -NHS〇2- or -NHSO2NH-; A 'represents a single bond or a divalent linking group; at least two of Rn', R! 4 ', R15, and R! 6 Can be bonded to each other to form a ring; η represents 0 or i; Rl / represents -COOh, -COOR5, -CN, hydroxyl, alkoxy group which may have a substituent ... c〇_NH- R6, -C0-NH-S02-R6 or -Y group 'R6 represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent. In the above-Y group, 'min ^' to 'each represent a hydrogen atom or a fluorenyl group which may have a substituent, and a and b each represent 1 or 2. In the resin according to the present invention, the acid-decomposable group may be contained in _c (= 〇) · X-A'-R, 7 'or substituted by a substituent of formula (Ι 〖-ΑΒ) * Z. Of it. The acid-decomposable group is represented by -C (= 〇) _Xi-R0, where R0 represents a tertiary alkyl group such as a third butyl group or a third pentyl group; a 1-ethoxy group such as i- Ethoxy-81-CNS A4 Specification 548523 A7 ------------- B7 V. Description of the Invention Υ79) a ~ '------ ethyl, Butoxyethyl, 1-isobutoxyethyl, or cyclohexylethyl; alkoxymethyl, such as N methoxymethyl or ethoxymethyl; 3 • pendant oxyalkyl, tetrahydrofresh Tetrahydrocranyl, dialkylsilyl ester, 3-oxocyclohexyl ester, 2-methyl-2-adamantyl or mevalonate residues. The definition of \ is the same as X above. Examples of the halogen atom represented by R! 3, Ru ', ruler ... and! ^ 6' include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. The alkyl group represented by R5'6, R13f, R14f, R15 'and Ri6' is preferably a straight or branched alkyl group having 1 to 10 carbon atoms, and preferably has ^ to 6 carbons. Atoms are straight or branched alkyl, more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl or third butyl. The ring nicotyl represented by R5, R6, Ri3 ', Ri4 ·, R15', and R16 'is a cyclic alkyl group or an alicyclic hydrocarbon-containing hydrocarbon. In particular, it can be cyclopropyl, cyclopentyl, cyclohexyl, adamantyl , 2-methyl-2-adamantyl, norbornyl, norbornyl, isobornyl, tricyclodecyl, dicyclopentenyl, norbornane epoxy, quatyl, isocryl, new lid As an example. , Rm ’, ruler ^ and! The ring formed by at least two bonds in ^ 6 ′ may have a ring of 5 to 12 carbon atoms, such as cyclopentene, cyclohexyl, cycloheptyl, and peroxin. The alkoxy group represented may have an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, as an example. Other substituents of pit group, cyclic smoke group and pit milk group can be exemplified by side group, halide atom, carboxyalkoxy group, fluorenyl group, cyano group, fluorenyl group, alkyl group and cyclic hydrocarbon group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an atom of (80) atom. Examples of the alkoxy group include alkoxy groups having from 1 to 4 broken atoms, such as methoxy, ethoxy, propoxy, and butoxy. Examples of fluorenyl include formamyl and ethenyl, and fluorenyl includes ethenyl. Examples of the alkyl group and the cyclic hydrocarbon group include those described above. Can be alone or two or more selected from the group consisting of alkenyl, substituted alkenyl, ether, thioether, carbonyl, ester, amido, sulfa, carbamate, and amidino As an example, as A, the bivalent linking group represented by. A. The fluorenyl group and substituted alkenyl group are a type of the group represented by the following formula: * [C (Ra) (Rb)] r- where Ra and Rb may be the same or different, and each represents a hydrogen atom, an alkane Radical, substituted: radical, halogen atom, hydroxyl or alkoxy. The alkyl group is preferably a lower carbon number alkyl group such as methyl, ethyl, propyl, isopropyl or butyl ', and is preferably methyl, ethyl, propyl or isopropyl. Examples of the substituent of the substituted alkyl group include an alkyl group, a halogen atom, and an alkoxy group. An alkoxy group is an alkoxy group having from 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Examples of self atom include gas atom, bromine atom, fluorine atom and Qi Yuanyu. r represents an integer from 1 to 10. In the resin according to the present invention, the group that can be decomposed by the action of an acid may be encapsulated in at least one repeating unit, wherein the repeating unit is selected from the group consisting of partial structures including formulas (pi), (pll), (pill), The repeating unit of the alicyclic fluorene represented by (pIV), (pV), or (pVI), the repeating unit represented by formula (II-AB), and the repeating unit containing the copolymer component described later. $ The substituents of Rl3 ,, Rl4 ,, r | 5, and Ri6 in various formulae (II-A) or (113) are -83-

This paper size is applicable to Chinese National Standard (CNS) A4 specifications f) 548523 A7 B7 V. Description of the invention (81) In the formula ([I-AB), an atomic group that can form an alicyclic structure or can form a bridging alicyclic ring Substituent for the atomic group Z of the structure. Specific examples of the repeating unit represented by the formula (VII-A) or (Π-Β) include the following four compounds [II-1] to [11-175], however, these compounds should not be construed as limiting the present invention range. -84-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 548523 A7 B7 V. Description of Invention (82)

[II-3] 0 0 I I

H CH (CH3) OCH2CH3 H CH20CH2CH3

0 0 I I CII-5] H CH (CU3) OCE2CH (CH3) 2

ch2och2ch3

CH (CH3) OCH2CH3 -85-This paper size applies to China National Standard (CNS) A4 (210 X 297 cm) 548523 A7 B7

548523 A7 B7 5 Description of the invention (84)

[I 卜 21] Ο Ο

[11-22], 0 0 ch2och2ch3

[11-24]

HO

ο [11-25] HQ

Ο Ο C (CH3) 3

C (CH3) 3

ο ο c (ch3) 3 m ο ο C (CH3) 3 cor '-87-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) binding

Line 548523 A7 B7 V description of the invention (85)

[II-31]

-88-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7

548523 A7 B7

548523 A7 B7

548523 A7 B7

548523 A7 B7

548523 A7 B7

548523 A7 B7 V Description of the invention (92)

[II-98] 0 I ch2ch2cn

• CH2CH2OCH2 [11-101]

-95-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7

548523 A7 B7

548523 A7 B7

548523 A7 B7

548523 A7 B7

548523 A7 B7

548523 A7 B7 g & invention description

[11-173] co ~ ch2-〇-ch2ch2 ~ o-ch2ch3 〇 [11-174] [11-175] COO-0 The acid-decomposable resins (B) and (B1) according to the present invention may include a compound having the following formula ( IV) The repeating unit of the lactone structure represented: (IV) "la ten H2-〒 ten COO-Wi-Lc

Wherein Ru represents a hydrogen atom or a methyl group; represents a group or a rain or a combination of groups selected from the group consisting of a single bond, a natural group, an ether group, a sulfur bond group, a carbonyl group, and an ester group; Ra [, Rb t , Rc !, Rd i and i each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; m and n each represent an integer from 0 to 3, 102-548523 A7 B7 V. Description of the invention (100 ) And m + η is from 2 to 6. Examples of the alkyl group having 1 to 4 carbon atoms represented by, Rbl, Rdl, and Rel include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl, and Tributyl. The fluorenyl group represented by \ ¥! In formula (IV) is a group represented by the following formula:-[C (Rf) (Rg)] rl- where Rf and Rg may be the same or different, and each represents a hydrogen atom, Sulfonyl, substituted alkyl, halogen atom, hydroxyl or alkoxy. Alkyl is most preferably a low-carbon fluorenyl, such as methyl, ethyl, propyl, isopropyl or butyl, preferably methyl, ethyl, propyl or isopropyl. Examples of the substituted alkyl group include a vinyl group, a halogen atom, and an alkoxy group. An alkoxy group is an alkoxy group having from 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an Angstrom atom. q represents an integer from 1 to 10. Other substituents of the aforementioned alkyl groups include carboxyl, fluorenyloxy, cyano, alkyl, substituted pit, halogen atom, hydroxyl, alkoxy, substituted alkoxy, acetamido, alkoxycarbonyl, and fluorene base. Provincial bases are low carbon number peryl, such as methyl, ethyl, propyl, isopropyl, butyl, propyl, cyclobutyl or cyclopentyl. Examples of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the substituted alkoxy group include a k-oxy group. Pitoxy is a tiger oxygen group having from 1 to 4 hard atoms, such as methoxy, ethoxy, propoxy or butoxy. An example of ethoxy is ethyl alcohol. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and a chi atom. Specific examples of the monomers corresponding to the repeating structural unit represented by the formula (IV) are shown below τπ, but these compounds should not be construed to limit the scope of the present invention. -103-

548523 A7 B7 V. Description of the invention (101) Η Η CH〇 一 C —

ch2—C

H C = 0 (IV-2)

Η

• CH factory 〒 c = o I (IV-5).

CH,

ch3I —ch2—c— I

c = o I (IV-6) O

—Ch2—c—-| —ch2—c— c = 〇c = c 1 (IV-7) i 〇〇1 1 H3C—C — ch3 A) h3c—c—c Λ ο 0 ch3 H 1 —ch2— c—-—CH2—c — c: = 0 1 (IV -10) c = c 1 〇0 1 H3C-C — CH3 q 1 jj c〇〇-p \ 〇 (IV-8) CH, (IV- Chuan-104-〇

H

I -CHo — C —

I c = 〇 I (IV-9) 0 1

H3C-C — CH3 Q coo · ch3

• CHo_C

I c = 〇 I (IV-12) 〇 Fire Ό ^ 〇 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523 A7

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7

548523 A7

In the specific example of the formula (IV), (IV-17) to (ΐν · 36) are preferred from the viewpoint of the significant improvement. In addition, the structure represented by the formula (IV) of the ester structure is preferable in terms of the ability to improve the roughness of the edges. There is C 'hearing bismuth: According to the present invention, the acid decomposable resin contains the complex unit represented by the following formula (VI).

(VI)

Pack B 6: -〇-c 一 or --c ^ O--

II II 〇 〇 Among them, 8 and 6 represent a group or two or more selected from the group consisting of a single bond, an allyl group, and a cycloalkyl group.

, Ether group, thioether group, carbonyl group and ester group. la represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or a halogen atom. The allyl group represented by a < 5 in the formula (VI) is a group represented by the following formula:-[C (Rnf) (Rng)] r- wherein each may be the same as or different from Rng, and each represents a hydrogen atom, an alkane Radical, substituted alkyl, halogen atom, hydroxyl or alkoxy. The alkyl group is preferably a low-carbon alkyl group such as methyl, ethyl, propyl, isopropyl or butyl, and more preferably methyl, ethyl, propyl or isopropyl. Examples of the substituent of the substituted alkyl group include a radical, a halogen atom, and an alkoxy group. Alkoxy is a kind of alkoxy with 1 to 4 carbons-107-this paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 548523 A7 B7 V. Description of the invention Alkyl alkoxy, such as methoxy, Ethoxy, propoxy or butoxy. Examples of halogen atoms include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. "Represents an integer from 1 to 10. The cyclofluorenyl group represented by 'VIII-6 in formula (VI) is a cycloalkenyl group having from 3 to 10 carbon atoms, such as cyclopentenyl, cyclohexenyl, or cyclooctylfluorenyl. The Z-containing alicyclic ring may have a substituent. Examples of the substituent include, for example, a halogen atom, a pitoxy group (preferably having 1 to 4 carbon atoms), a fluorenyloxycarbonyl group (preferably having 1 to 5 carbon atoms), a fluorenyl group (such as formamyl and Benzamyl), ammonium (such as propionyloxy and benzamyloxy), alkyl (preferably having 1 to 4 carbon atoms), carboxyl, hydroxyl, and alkylsulfonylaminesulfonyl (Eg -CONHS〇2CH3). The alkyl group as a substituent may be further substituted with, for example, a hydroxyl group, a halogen atom, or a fluorene * oxy group (preferably having 1 to 4 carbon atoms). In the formula (VI), the oxygen atom of the ester group bound to Αό may be bonded to any carbon atom which can constitute a bridge-containing alicyclic structure containing Z6. Specific examples of the repeating unit represented by formula (IV) are shown below, but these compounds should not be construed as limiting the scope of the present invention. -108-

This paper size applies to China National Standard (CNS) A4 (210 X 297 male yellow) 548523 A7 B7

548523 A7 B7

548523

r2 <

R < 4c Rac 3c The acid-decomposable resin according to the present invention may further include a repeating unit having a group represented by the following formula (v⑴: (VII) wherein Rk, R3, and Rk each represent a hydrogen atom or several groups, provided that At least one of I, Min and R4c represents a hydroxyl group. ° The group represented by the formula (νπ) is preferably a dihydroxy product or a monohydroxy product is preferably a dihydroxy product. The formula (II-A) or (II-B The repeating unit represented by) or the repeating unit represented by the following formula (νπ) is taken as an example, and as a repeating unit having a group represented by the following formula (VII) ' , Ri4 ,, Rh, and a group represented by the formula (νπ) (such as 1 in -C00R5 is a formula (v_ 1), (V-2), (V-3), or (V- 4) the group represented).

Zing CH2-〒 十

(AID order

c = 〇 I 〇 R

f ^ 3c k where Ru. represents a hydrogen atom or a methyl group; Rk, ruler, and R4. Each represents a hydrogen atom via a radical, provided that at least one of Rk, ruler, and R4c represents a hydroxyl group. Represented by the formula (All) Specific examples of repeating units are shown below, but these compounds should not be construed to limit the scope of the present invention. -111-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 548523 A7 B7 5 Description of the invention (109) —CH2 — CH —

(1)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7

(VIII) V. Description of the invention (1 彳 〇) The acid-decomposable resin according to the present invention may contain a repeating unit having a group represented by the following formula (νπί) ... —CH-CH — Renren where Z2 represents-. -Or-)), wherein r41 represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or -OSO ^ R42 ·, and Re represents an alkyl group, an alkyl group, a cycloalkyl group, or a camphor residue. In the formula (VIII), z2 represents -0- or -N (R41)-, wherein R4l represents a hydrogen atom, a #empty group, a aryl group, a haloyl group, or -〇S〇2_R42, and a ruler 42 represents an alkyl group, a halogen Alkyl, cycloalkyl or camphor residues. ^ The alkyl group represented by R42 is preferably a linear or branched alkyl group having from 1 to 10 carbon atoms, and is preferably a linear or branched chain member having from 1 to 6 carbon atoms The group 'is more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl or third butyl. The haloalkyl represented by hi and Re is trifluoromethyl, nonafluorobutyl, pentafluorooctyl, or trifluoromethyl. KG stands for cycloalkyl as cyclopentyl, cyclohexyl or cyclooctyl. The alkyl group and haloalkyl group represented by li and R42 and the cycloalkenyl group and camphor residue represented by R42 may each have a substituent. Examples of the substituent include, for example, a light group, a carboxyl group, a cyano group, a halogen atom (such as gas, bromine, fluorine and iodine), an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms, such as methyl Ethoxy, ethoxy, propoxy and butoxy groups), fluorenyl groups (preferably fluorenyl groups with 2 to 5 carbon atoms 113-this paper size applies to Chinese National Standard (CNS) A4 specifications (210 X (297 mm)

Binding

548523

, Such as formamyl and ethenyl), fluorenyl (preferably fluorenyl having 2 to 5 carbon atoms, such as ethenyl), and aryl (preferably having 6 to 14) An aryl group of a carbon atom, such as phenyl). Specific examples of the repeating unit having a group represented by the formula (Am) include the following compounds II,-? To [r-7], but these compounds should not be construed to limit the scope of the present invention. CH— (ρκ) 〇 < C, — ο ο [Γ-1]

-114-

548523 Α7 Β7 V. Description of the invention (112)

O ^ C, · [Γ-6]

N 0—S〇s-cf3 [I, -7]

In order to adjust the resistance to dry etching, the adhesion to the standard developing solution, the adhesion to the substrate, the profile of the resist, and the characteristics required for general resists, such as heavy weight, heat resistance, and sensitivity, the acid can decompose the resin component (B ) And (B1) ^ In addition to the above repeating structural units, various repeating structural units may be included. It is possible to correspond to the repeating structural unit of the monomer shown below as an example. As this complex structural unit ', it is not limited to this. Due to the inclusion of these monomers, it becomes possible to finely adjust the desired characteristics of the acid-decomposable resin into (B) and (B 1), especially the following characteristics. (1) Solubility in coating solvent, (2) Film-forming property (glass transition point), -115-This paper size is applicable to China National Standard (CNS) A4 specification (2ΐ ^ Γ ^ 7mm) 548523 A7

(3) alkaline development ability, (decrease in film thickness (hydrophilic / hydrophobic, choice of alkaline soluble groups), (5) adhesion to unexposed areas of the substrate, and (6) dry etching resistance Such a monomer may have an addition polymerizable unsaturated bond as an example. The compound is selected from, for example, acrylates, methacrylates, trimethoprim, methacrylamide, and propyl. Compounds, ethyl ethers, and vinyl esters. In particular, the following monomers can be taken as examples. A translucent esters (preferably alkyl acrylates, in which the alkane has a carbon atom from 1 to 〇01) : Methyl Acrylate, Ethyl Acrylate, Propyl Propionate, Amyl Acrylate, Cyclohexyl Acrylate, Ethyl Hexyl Acrylate, Octyl Acrylate, Second Octyl Acrylate, Chloroethyl Propionate, 2 -Chloroethyl acrylate, 2,2-Dimethytantacrylopropylpropionate, 5-Hydroxypentyl acrylate, Trimethylolpropane monopropionate, Isopentyl alcohol monoacrylate, Benzyl acrylate, methoxybenzyl propionate, g-propionate, g-propionate, and g-propionate. Esters (preferably alkyl methacrylates, where the alkyl group has up to 10 carbon atoms): methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate g purpose, valeryl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate Esters, 2-hydroxyethyl methylpropionate, hydroxymono-butyl methylpropionate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3, hydroxypropylmethyl Acrylic acid ester, trimethylmethacrylic acid monomethyl acrylate, 116-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Η

548523 A7 I ____B7 V. Description of the invention (1U) Isopentaerythritol monomethylpropionate, furan methyl methacrylate, and tetrahydromethylpropionate vinegar. Acrylic acid: Acrylic acid, N-alkylpropylamine (with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, third butyl, heptyl Octyl, octyl, cyclohexyl, and ethyl-free groups can be used as pit groups), N, N-di-aeroyl propylene · amines (alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, Butyl, isobutyl, ethylhexyl and% hexyl can be used as pit groups), N-Ethylethyl-N-methylpropionase amine, and N-2 -Ethylamine ethyl-N-ethylpropionylpropionate Stuffed amine. _Methylpropanylamine: fluorenylpropanamine, N-alkylmethylpropanamine (alkyl groups with 1 to 10 carbon atoms, such as methyl, ethyl, third butyl , Ethylhexyl, hydroxyethyl and cyclohexyl can be used as alkyl), N, N-dialkylmethylpropionamine (such as ethyl, propyl and butyl can be used as alkyl), and N-hydroxyethyl -N-methylmethylpropanamide. ~ Dilute propyl compounds: Allyl esters (such as allyl acetate, allyl hexanoate, allyl octanoate, propyl laurate, propyl propyl ester, stearic acid (Propyl acetate, allyl benzoate, allyl acetate and allyl acetate) and allyloxyethanol. Ethyl bond: Alkyl ethyl ether (such as hexyl ethyl ether, octyl vinyl ether, decyl ethyl ~ dilute ether, ethyl hexyl ethyl ether, methoxy ethyl ethyl ether, ethyl Oxyethyl vinyl ether, ethyl acetoacetic acid, 1-methyl · 2,2-dimethylpropylacetamido_ _-117-This paper size applies to China National Standard (CNS) Α4 specification (210X297 (Public double) 548523 A7 B7 ___ V. Description of the invention (115) Ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylamine ethyl vinyl ether, two Ethylamine ethyl vinyl ether, butylamine ethyl vinyl ether, benzyl vinyl ether and tetrahydrofuryl ethyl fluorenyl ether) ° 1 alkenyl ester · vinyl butyrate, vinyl isobutyrate, trimethyl Vinyl acetate, ethyl diethyl acetate, ethyl valerate, vinyl hexanoate, vinyl chloroacetate, digas vinyl acetate, methoxy vinyl acetate, butoxy vinyl acetate, ethyl acetate旨 The purpose of vinyl acetate, vinyl lactate, vinyl-β-phenylbutyrate and cyclohexylmetanoic acid. Itaconic acid dife based purpose: dimethyl itaconate, diethyl itaconate and dibutyl itaconate. Dialkyl fumarate or succinate: Dibutyl fumarate. Others • Crotonic acid, itaconic acid, maleic anhydride, maleimide, propanil, methylpropanyl and malaysian. In addition to the above-mentioned compounds, addition-polymerizable unsaturated compounds that can be copolymerized with monomers corresponding to the various repeating structural units described above can be used. In the acid decomposable resin, the molar ratio of each repeating structural unit content can be arbitrarily set to adjust the dry etching resistance of the resist, the suitability to a standard developing solution, the adhesion to the substrate, the profile of the resist, and general resist Desired characteristics such as resolution, heat resistance and sensitivity. Preferred specific examples of the acid-decomposable resin component (B) of the present invention can be exemplified by the following compounds. -118-This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X 297 male ¢ 7 548523 A7 B7) V. Description of the invention (116) (1) Contains some structures with formula (pi), (p (I) Component (B) (side chain type) of the repeating unit of the alicyclic hydrocarbon represented by (pill), (pIV), (pV), or (pVI). (2) Containing the repeating unit represented by formula (II-AB) Component (B) (main chain type). In item (2), the following compounds are also taken as examples. (3) Contains a repeating unit represented by formula (II-AB), a maleic anhydride derivative, and (methyl) ) The component (B) (mixed type) of the g structure of propionate. Part of the structure of the acid-decomposable resin component (B) includes formula (ρί), (pII), (pill), (pi V), (pV The content of the repeating unit of the alicyclic hydrocarbon represented by) or (pVI) preferably accounts for 30 to 70 mole% of the entire repeating structural unit, preferably from 35 to 65 mole%, and more preferably from 4 to 60 mole%. 0 to 60 mole%. The content of the repeating unit represented by formula (II-AB) in the acid-decomposable resin component (B) preferably accounts for 10 to 60 mole% of the entire repeating structural unit, preferably from 1 5 to 5 5 mol%, more preferably from 20 to 5 Mole%. The content of the repeating structural unit containing other copolymerizable component monomers in the acid decomposable resin component (B) can also be arbitrarily set according to the characteristics of the target resist, but it is generally selected as part of the structure to include The total molar number of the repeating unit of the alicyclic hydrocarbon represented by the formula (pi), (pH), (ρΠΙ), (pIV), (pV), or (PVI) and the repeating unit represented by the formula (ιι-αΒ) is 99 Molar% or less, preferably 90 Molar 0/0 or less, and more preferably 80 Molar% or less. When the composition of the present invention is used for ArF exposure, in view of the penetration of ArF light, 'The resin preferably does not contain an aromatic group. Preferred specific examples of the acid-decomposable resin component (B 丨) of the present invention can be exemplified by the following compounds. (1) Including resins having the formula (Vl), (V-2 ), (V-3) or (V-4) the repeat of the group -119-This paper is suitable for the national standard (CNS) of the country of breeding (CNS) eight 4 rules _ grid (210〆297 public goods) ----- ----- 548523 A7 B7

V. Description of the invention (117 Units and part of the structure contain a repeating unit of an alicyclic hydrocarbon represented by the formula (ρ 〖), (ρΠ), (ρΠί), (pIV), (pV) or (pVI) (B 丨) (Side-chain type). (2) Including repeating units having a group represented by formula (V-1), (ν-2), (V-3), or (V-4) and formula (II-AB) The component (Bι) (main chain type) of the repeating unit represented. In (2), the following compounds are also taken as examples. (3) Containing the repeating unit represented by formula (II-AB), derived from maleic anhydride Substance and component (Bl) (mixed type) having a repeating unit of a group represented by formula (Vl), (V-2), (V-3) or (V-4). Acid decomposable resin component (B1) The content of the repeating unit having a group represented by the formula (ν · υ, (ν-2), (ν-3), or (V-4) preferably accounts for the entire repeating structural unit < 2 to 50 mole%, It is preferably from 5 to 40 mole%, and more preferably from 10 to mole%. Some structures in the acid-decomposable resin component (B1) include formulae (pi), (pll), (pin), ( piv), (pV) or (pVI) K shows that the content of repeating units of alicyclic hydrocarbons is the most: 30% of the total repeating structural units 70 mol%, preferably from & to 65 mol%, more preferably from 40 to 60 mol%. The content of the repeating unit represented by formula (II-AB) in the decomposition resin component (B1) is the most It accounts for 10 to 60 mole% of the entire repeating structural unit, preferably from 15 to 55 mole%, and more preferably from 20 to 50 mole%. The acid decomposable resin component (B 丨) contains The content of the repeating structural unit of other copolymerizable component monomers can also be arbitrarily set according to the characteristics of the target inhibitor, but its content is generally best to have the formula (v-1), (v_2), ^ 3) 戋 (^ 4 The repeating unit and partial structure of the group shown by) includes the repeating unit of alicyclic ring shown by formula (ρ1), (ρπ), (ρΠΙ), (piv) (PV) or (PVI) and formula AB) -120-t Paper wattage applies to Chinese national standard M specifications (21 () χ Norwegian mm) ----- 548523 A7 ____ Β7 V. Description of the invention (118) 99 mol% of the total mol number of repeating units Or less, preferably 90 mole% or less, and more preferably 80 mole% or less. The decomposable resin components (B) and (β 1) for use in the present invention can be synthesized according to a general method such as radical polymerization. In the general synthesis method, the monomer seeds are sent to the reaction tank in batches or during the reaction and are dissolved in the solvent as needed, such as ethers such as tetrahydrofuran, 1,4 · oxane or diisopropyl Ketones such as methyl ethyl ketone or methyl isobutyl ketone, ester solvents such as ethyl acetate, and solvents for dissolving the composition of the present invention, such as propylene glycol monomethyl ether acetate, described later, under nitrogen or argon as required Heating under an inert gas atmosphere, and polymerization is initiated using a commercially available free-radical polymerization initiator (such as an azo-based initiator or a peroxide). If necessary, the initiator is added separately or in batches. After the reaction is terminated, the polymer is placed in a solvent and the target polymer is recovered by means of powder recovery or solid recovery. The reaction concentration is 20% by weight or more, preferably 30% by weight or more, and more preferably 40% by weight or more. The reaction temperature is from 10 to 150 ° C, preferably from 30 to 120t, and more preferably from 50 to 100 ° C. The weight average molecular weight of the resin according to the present invention, as measured by the GPC method and calculated in terms of polystyrene terms, is preferably from 1,000 to 200,000. When the average weight ratio is less than 1,000, heat resistance and dry etching resistance are disadvantageously deteriorated. However, when it exceeds 200,000, the developing ability is deteriorated and the viscosity becomes very high, which reduces the film-forming property. In the positive photosensitive composition according to the present invention, the proportion of all acid-decomposable resins in the entire composition is preferably from 40 to 99.99% by weight, preferably from 50 to 99.97% by weight, based on the solids of the entire resist. The content is the benchmark. -121-This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210M97 mm) 548523 A7 B7 V. Description of the invention (119) (C) Examination of life > f The positive-type photosensitive composition contains (C) a test compound. The positive-type photosensitive composition of the second embodiment of the present invention preferably contains (C) an experimental compound to reduce roundness caused by aging during exposure to heating. Preferred test compounds may have compounds represented by the formula (A), (B), (C), (D) or (E) as examples: R251 R250-N-R252 (A) of which R25G, R251 and R252 Each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an alkyl group having 6 to 20 carbon atoms A substituted or unsubstituted aryl group, and R251 and R252 may be combined with each other to form a ring. = N-

—N == C

= C—N— R253

(B) (C) (D) (E) -122-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 male I) 548523 A7 B7 V. Description of invention (120) of which R253, R254, R255 And R256 each represent an alkyl group having 1 to 6 carbon atoms. Preferred specific examples of this test compound include substituted or unsubstituted guanidines, substituted or unsubstituted amines, substituted or unsubstituted amine alkylpyridines, substituted or unsubstituted Amino 17-pyrrolidine, substituted or unsubstituted 4a, substituted or unsubstituted p-bite, substituted or unsubstituted 17-ratio, substituted or unsubstituted polyanhydride, Substituted or unsubstituted purines, substituted or unsubstituted Mijun 17 forests, substituted or unsubstituted 17 pipit 17 forests, substituted or unsubstituted hexahydro? Than P, Well, substituted or unsubstituted amino Morpho 17 Lin, substituted or unsubstituted amino Morpholine, mono-, di- or tri-alkylamine, substituted or unsubstituted Aniline, substituted or unsubstituted hexahydropyridine and mono-, di-ethanolamine. Preferred substituents include amine, amine alkyl, alkylamino, amine aryl, aryl amine, pit, -pitoxy, alkoxy, donkey 1, square, square, nitro, Light and cyano. Specific examples of preferred test compounds include vein, 1,1-monoguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4- Aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine , 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylp 3-aminopyridine 17 alkane, hexahydro 17 ratio, N- (2-aminoethyl) hexahydropyridine well 17, N- (2-amineethyl) hexahydro 17 ratio, cardiac amino-2 , 2,6,6-tetramethylhexahydropyridine, 4-hexahydropyridylhexahydropyridine, 2-iminohexahydropyridine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-Amino-5-methylpyrazole, 5-Amino-3- 123-This paper size applies to China National Standard (CNS) A4 (210 X 2 grilled public funds) 548523

V. Description of the invention (121) Methyl-1 -p-tolylpyrazole, pyridine, 2- (aminemethyl) -5-methylpyridine, shouting, 2,4-diaminopyrimidemia , 4,6-dichloropyrimidium, 2-leaf 17-leaf, 3-leaf 17-leaf, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5- Two-mouthed bicyclo [4.3.0] non-5-woman, 1,8_diazine bicyclic [5.4.0] undec-7-fluorene, 2,4,5-; phenylimidazole, tris (n-butyl) ) Amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylhexahydropyridine, 2,6-diisopropylaniline and N-cyclohexyl-N ^ morpholinoethyl Sulfur, but the present invention is not limited to this. Other preferred compounds include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or Unsubstituted hexahydropyridine " Well, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, substituted or unsubstituted hexahydropyridine, and others A compound having an imidazole structure, a bi-bicyclic structure, a mineral hydroxide structure, a phosphonium carboxylate structure, and an aniline structure. Examples of compounds having an imidazole structure include 2,4,5 · triphenylimidazole and benzimidazole. Compounds with a diazine bicyclic structure can be 1,4-diazinebicyclo [2.2.2] octane, 1,5-diazinebicyclo [4.3.0] non-5-ene, and 1,8-diazinebicyclo [5.4 .0] ΊCarbon-7- 晞 is an example. Compounds with a hydrazone hydroxide structure can be diaryl hydroxide, benzamidine methyl hydrazone hydroxide, hydrazone hydroxide with 2- pendant alkynyl groups, especially triphenylphosphonium hydroxide Compounds, tris (tertiary butylphenyl) triarylsulfonium hydroxide, bis (tertiary butylphenyl) breaker hydroxide, benzamidinemethyl 4-phenoxide and 2-oxopropyl An example is thiophene hydroxide. Compounds with wrong hydroxide structure, anionic moieties that can be replaced by an acid salt such as acetate, adamantane small carboxylates, and perfluoroalkyl groups

Hold

• 124-

548523 A7

The acid salt can be used as a compound having an acid structure. Examples of the structure < compound. With aniline, knot. However, these examples of isopropylaniline and N, N-4ylaniline are not to be construed as limiting the scope of the present invention. These test compounds ((C) T have been used alone or as a mixture of two or more of them. The basic compounds are ^^ " ', and Gary are generally from 0.001 to 10, from 0 · 0 to 5% by weight, as long as the solid winter amount of Bi Youjia i light resin composition is based on it. When this content is less than 0.001% by weight, no addition can be obtained;

On the other hand, if it exceeds 10% by weight, the sensitivity is lowered and the developability in the unexposed area is liable to deteriorate. "(P__L_ contains at least one of the interfacial activity of fluorine, the positive photosensitive composition of the first embodiment of the present invention & one or two or more of a gas-containing and / or silicon-containing surfactant ( Fluorine-containing surfactants and silicon-containing surfactants, surfactants containing both fluorine atoms and silicon atoms). The positive-type photosensitive composition of the second embodiment of the present invention preferably contains component (D).

When the positive photosensitive composition of the present invention contains a surfactant component (D), when irradiated with a light source of 250 nm or less', especially 220 nm or less, sensitivity, resolution, adhesion, and Excellent resist pattern with no development flaws. JP-A-62-36663 x JP-A-6 1-226746 λ JP-A-6 1-226745 'JP-A- 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, Jin-eight-9-54432, Jin-eight-9-5988, and U.S. Patent Nos. 5,405,720, I-Nos. 5,360,692, 5,529,88 1, 5,296,330, and 5,436,098 No.5,576,143, No.5,294,5 1 No.1, and No.5,824,45 No.1 -125-This paper is applicable to China National Standard (CNS) A4 (210 X 297 male I) 548523 A7 ________B7 5 2. Description of the invention (123) The unexposed surfactant can be used as the surfactant component (D). In addition, the following commercially available surfactants can also be used. Examples of commercially available surfactants that can be used in the present invention include fluorine-containing surfactants and silicon-containing surfactants, such as Eftop EF301 and EF303 (manufactured by Shin-Akita Chemical Co., Ltd.), Fiolad FC43. And FC43 1 (manufactured by Sumitomo 3M Co., Ltd.), Megafac FI 7 I, F173, F176, F189 and R08 (manufactured by Dainippon Ink & Chemical Co., Ltd.), Sarfron S-382, SC101, SC102, SC103, SC104 , SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.) and Troy Sol S-3 66 (manufactured by Troy Chemical Industry Co., Ltd.). The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a crushed surfactant. The proportion of the surfactant (D) is preferably from 0.0001 to 2% by weight, more preferably from 0.001 to 1% by weight, based on the entire positive photosensitive composition (excluding solvent). . (E) Organic reagent The photosensitive composition according to the present invention is generally dissolved in a predetermined organic solvent. Examples of solvents that can be used in the present invention include dichloroethane, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, 2-methoxyethyl acetate, ethylene glycol monoethyl bond acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate Purpose, methyl methoxypropionate g purpose, ethylene mono-ethoxypropionate g purpose, methyl pyruvate purpose S, ethyl pyruvate purpose S, acrylic g purpose acid propyl purpose, N, N-dimethyl Formamidine, dimethylmethylene, N-methylpyrrolidone and tetra-126-This paper is in accordance with China National Standard (CNS) A4 (210 x 297 mm)

Hold

k 548523 A7 _________ B7_ 5. Description of the invention (124) The wind squeaked. In the first embodiment of the present invention, it is preferable to use a mixed solvent containing a hydroxyl group-containing solvent and a hydroxyl group-free solvent in the structure, thereby reducing the generation of particles during storage of the resist solution. Examples of solvents containing hydroxyl groups include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl chain, propylene glycol monoethyl ether, and ethyl lactate. Among these solvents, propylene glycol Monomethyl ether and ethyl lactate are particularly preferred. : Examples of non-hydroxyl-containing solvents include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, ν, N-dimethylformamide and dimethyl sulfoxide. Among these solvents, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, Cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, and 2-heptanone are most preferred. The mixing ratio (weight) of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group is generally from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60 / 40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by weight or more of a non-hydroxyl-containing solvent is particularly preferred. The photosensitive composition according to the second embodiment of the present invention preferably contains a mixed solvent as the component (E). Such mixed solvents may contain at least one propylene glycol monoalkyl ether acrylate (group A solvent), at least one propylene glycol monoalkyl ether, alkyl lactate, and alkoxypropionic acid alkyl ester (group B solvent) and / or γ-Butane-An example of a mixed solvent of the purpose, propylene carbonate and propylene carbonate (group C solvent). In other words, a combination of a group A solvent and a group B solvent, and a group A solvent -127-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (21ί) × 297 mm) 548523 A7 _ B7 V. Description of the invention (125 ) And Group C; the composition of cereals and A; the composition of cereals, Group B, and Group C solvents as component (E). When a combination of a group A solvent and a group B solvent is used, the sensitivity to the resolution of the contact hole is excellent and the formation of particles in the resist solution at the initial stage can be improved. By using a combination of a group A solvent and a group C solvent, particles in the resist solution are increased over time and a change in sensitivity is revealed, so that a resist having excellent aging stability can be obtained. Preferred examples of propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, and propylene glycol monoethyl ether propionate. . Preferable examples of the glyceryl monoalkyl ether include propylene glycol monomethyl ether and glycerol monoethyl ether. Preferred examples of the alkyl lactate include methyl lactate and ethyl lactate. Preferred examples of feoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and methyl ethoxypropionate ester. A private: The weight ratio (a / B) of agent i to group B solvent is preferably from 90/10 to 15/85 ', more preferably from 85/15 to 20/80', and more preferably from 80/2 〇 to 25/75. The weight ratio (A / C) of the group A solvent to the group C solvent is preferably from 99 9 / 〇1 to 75/25, preferably from 99/1 to 80/20, and more preferably from 97/3 to 85 / 15. When the three solvents are combined, the proportion of the Group C solvent used in all solvents is preferably from 0.1 to 25% by weight, preferably from 1 to 20% by weight, and more preferably from 3 to 17% by weight. The solid content of the resist composition containing the above components is dissolved in the above-mentioned mixed liquid, wherein the concentration of the solid content is preferably from 3 to 25% by weight, and preferably from 5 to 22% by weight , More preferably from 7 to 20% by weight. -128-^ Paper scale is applicable to Chinese National Standard (CNS) A4 specification (210X297 public funding) 548523 V. Description of the invention (126) The mixed solvent containing propylene glycol monoalkyl ether acrylate in the present invention is better. The system is shown below. Propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and ethyl lactate, propylene glycol monomethyl ether acetate and 3-ethoxyethyl propionate, propylene glycol monomethyl ether Acetate and γ-butyrolactone, propylene glycol monomethyl ether acetate and ethylene carbonate, propylene glycol monomethyl ether acetate and propylene carbonate, propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether and γ -Butyrolactone, propanol monomethyl ether acetate, ethyl lactate and γ-butyrolactone, propylene glycol monomethyl ether acetate, 3-ethoxyethylpropionate and γ-butyrolactone, Glycol monomethyl ether acetate, propylene glycol monomethyl ether and ethylene glycol, propylene glycol monomethyl ether acetate, ethyl lactate and ethyl carbonate, propylene glycol monomethyl ether acetate, 3-ethoxylate Ethyl ethyl propionate and ethylene carbonate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and propylene carbonate, propylene glycol monomethyl ether acetate, ethyl lactate and propylene carbonate, and propylene glycol Monomethyl ether acetate, 3-ethoxyethyl propionate and propylene carbonate. Among the above combinations, particularly preferred combinations are: propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and I-butyrolactone, propylene glycol monomethyl ether acetate, ethyl lactate and y-butyrolactone, and propylene glycol monomethyl Ethyl acetate, 3-ethoxyethylpropionic acid vinegar and γ-butane-129-This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm)

Binding 548523 A7 B7 ___ V. Description of the Invention (127)-Esters, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and ethylene carbonate, propylene glycol monomethyl ether acetate, ethyl lactate and ethylene glycol Esters, propylene glycol monomethyl ether acetate, 3-ethoxyethyl propionate and ethylene carbonate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and propylene carbonate, propylene glycol monomethyl ether Acetate, ethyl lactate and propylene carbonate, and propylene glycol monomethyl ether acetate, 3-ethoxyethylpropionate and propylene carbonate. As the ingredient of the present invention, a mixed solvent containing at least one kind of lactic acid :): a solvent (solvent (1)) and at least one of an solvent and an alkyl alkoxypropionate (solvent (2)) E). By adding the solvent (2) to the solvent (1), the sensitivity to the resolution of the contact hole is excellent and the particle formation in the resist solution at the initial stage can be improved. ; Methyl lactate and ethyl lactate can be used as examples of alkyl lactate. Examples of the ester solvent include butyl acetate, amyl acetate, hexyl acetate, and butyl propionate, and butyl acetate is preferably used. Examples of alkyl alkoxypropionates include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and methyl 3-ethoxypropionate . The ratio of the solvent (1) to the solvent (2) [(1) / (2)] is preferably from 90/10 to 1 5/85, preferably from 85/15 to 20/80, and more preferably from 80/20 to 25/75. In the present invention, the 'mixed solvent (E) preferably further contains at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate (solvent (3)). By adding one of the solvents (3), it is revealed that the particles in the resist solution increase with time and the sensitivity changes' so that a resist having excellent aging stability can be obtained. -130-The national standard (CNS) of this paper is suitable for fiscal countries. Λ4 specifications (21G X 297 mm) — 548523 A7 ____B7 V. Description of the invention (128) The amount of solvent (3) used is the best ratio of all solvents It is from 0.1 to 25% by weight, preferably from 1 to 20% by weight, and more preferably from 3 to 15% by weight. The solid content of the resist composition containing each of the above components is dissolved in the above-mentioned mixed solvent, wherein the concentration of the solid content is preferably from 3 to 25% by weight, 'preferably from 5 to 22% by weight, and more preferably From 7 to 20 weights. / 〇. The preferred combination of the mixed solvent containing the alkyl lactate in the present invention is shown below. Ethyl Lactate and Ethyl Acetate: Ethyl Lactate, Butyl Acetate and γ-Butyrolactone, Ethyl Lactate, Butyl Acetate and Ethyl Carbonate, Ethyl Lactate, Butyl Acetate and Ethyl Carbonate, Lactic Acid Ethyl acetate, ethyl 3-ethoxyacrylate and γ-butyrolactone, ethyl lactate, ethyl 3-ethoxyacrylate and ethyl carbonate, and ethyl lactate, ethyl 3-ethoxyacrylate and Sodium propylene carbonate. Among the above combinations, particularly preferred combinations are: ethyl lactate, butyl acetate and γ-butyrolactone, ethyl lactate, butyl acetate and ethylene carbonate, ethyl lactate, butyl acetate and propylene carbonate, lactic acid Ethyl acetate, ethyl 3-ethoxyacrylate and γ-butyrolactone 'ethyl lactate, ethyl 3-ethoxyacrylate and ethylene glycol carbonate', ethyl lactate, ethyl 3-ethoxyacrylate With propylene carbonate. In addition, at least one heptone (group D solvent), at least one propylene glycol monoalkyl ether, alkyl lactate, and alkoxypropionate tiger group vinegar (group E solvent) and / or γ-may be used. Mixture of butyrolactone, ethylene carbonate and propylene carbonate (F-grouping agent) -131-This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public expense) 548523 A7 B7 V. Description of the invention ( A solvent 129 is used as the component (E) of the present invention. In other words, a combination of a group D solvent and a group E solvent, a combination of a group D solvent and a group F solvent, and a group (E) solvent, a group E solvent, and a f group solvent can be used. The composition is used as the component (E). When a composition of a group D solvent and a group E solvent is used, the sensitivity to the resolution of the contact hole is excellent and the formation of particles in the resist solution at the initial stage can be improved. With the group D solvent The use of a composition with a group F solvent increases the particles in the resist solution over time and shows a change in sensitivity, so that a resist having excellent aging stability can be obtained. Examples of heptone include 2-heptanone, 3 -Heptanone and 4-heptanone, preferably 2-heptanone. Good examples include propylene glycol monomethyl ether and propylene glycol monoethyl ether. Preferable examples of alkyl lactate include methyl lactate and ethyl lactate. Preferable examples of oxypropionic acid, j: endyl g include 3 -Ethyl ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate and methyl 3-ethoxypropionate. Weight ratio of Group D solvents to Group E solvents ( D / E) is preferably from 90/10 to 15/85, preferably from 85/15 to 20/80, more preferably from 80/20 to 25/75. Weight ratio of Group D solvents to Group F solvents (D / F) is most preferably from 99.9 / 0.1 to 7 5/25, preferably from 99/1 to 80/20, and more preferably from 97/3 to 85/15. When these three solvents are combined, The proportion of the use amount of the F-group solvent to the total amount of all solvents is preferably from 0.1 to 25% by weight, more preferably from 1 to 20% by weight, and more preferably from 3 to 17% by weight. The solid content of the above-mentioned resist composition of each component is dissolved in the above-mentioned mixed solvent 'wherein the concentration of the solid content is preferably from 3 to 2 5 weight -132-This paper size is applicable to China National Standard (CNS) A4 specifications ( 210X297 mm) 548523 A7 B7 V. Invention It is (130)%, preferably from 5 to 22% by weight, more preferably from 7 to 20% by weight. The preferred combination of the mixed solvent containing heptone in the present invention is shown below. 2-heptanone With propylene glycol mono-T-ether, 2-heptanone and ethyl lactate, 2-heptanone and 3-ethoxyethylpropionate, 2-heptanone and γ-butyrolactone, 2-heptanone and carbonic acid Ethyl ester, 2-heptanone and propylene carbonate, 2-heptanone, propylene glycol monomethyl ether and γ-butyrolactone, 2-heptanone, ethyl lactate and γ-butyrolactone, 2-heptanone, 3 -ethoxyethylpropionate and γ-butyrolactone, 2-heptanone, propylene glycol monomethyl ether and ethylene carbonate, 2-heptanone, ethyl lactate and ethyl carbonate, 2-heptane Ketone, 3-ethoxyethylpropionate and ethylidene carbonate, 2-heptanone, propylene glycol monomethyl ether and propylene carbonate, 2-heptanone, ethyl lactate and propylene carbonate, and 2 -Heptanone, 3-ethoxyethylpropionate and propylene carbonate. Among the above combinations, particularly preferred combinations are: 2-heptanone, propylene glycol monomethyl ether and γ-butyrolactone, 2-heptanone, ethyl lactate and γ-butyrolactone, 2-heptanone, 3-ethoxylate Ethyl ethyl propionate and γ-butyrolactone, 2 · heptanone, propylene glycol monomethyl ether and ethylene carbonate, 2-heptanone, ethyl lactate and ethyl carbonate, 2-heptanone, 3- Ethoxyethylpropionate and ethylidene carbonate, -133-This paper size applies to China National Standard (CNS) A4 specification (1210X297 mm) 548523 A7 — ________ B7 ^ ________ — V. Description of the invention (131) 2- Heptone, propylene glycol monomethyl ether and propylene carbonate, 2-heptanone, ethyl lactate and propylene carbonate, and 2-heptanone, 3-ethoxyethylpropionic acid wine. Other unnecessary solvents may be added to these mixed solvents of the present invention as long as they do not hinder the effect of the present invention. Generally speaking, every! Each of the mixed solvents is added in an amount of 0.00 parts by weight, and the additional solvent is added in an amount of 30 parts by weight or less. In addition to the solvents described for the necessary solvents of the above mixed solvents, the other solvents may be dichloroethylene, cyclohexanone, cyclopentanone, methyl ethyl ketone, toluene, Ν, Ν-dimethylformamide, dimethyl As examples, fluorene, N-methylpyrrolidone, and tetrahydro 17-furan. (F) Acid-decomposable dissociation inhibiting compound The positive-type photosensitive composition of the present invention preferably contains (F), a low-molecular-weight decomposition-dissociation inhibiting compound having a molecular weight of 3,000 or less, which has a function under the action of an acid Groups that increase the solubility of alkaline developers (also equivalent to "acid-decomposable dissociation inhibiting compounds," below). In order to achieve no reduction in light transmittance of 220 nm or less, it is best to use An alicyclic or aliphatic compound such as a bile acid derivative containing an acid-decomposable group as an acid-decomposable dissociation inhibiting compound (F) described in SPIE Gazette, Vol. 2724, page 355 (1996). Can be used with the above-mentioned acid-decomposable resin The same acid decomposable group and alicyclic structure are taken as an example. Based on the solid content of the entire positive photosensitive composition, the addition amount of the acid decomposable dissociation inhibiting compound (F) is preferably from 3 to 50% by weight. It is preferably from 5 to 40% by weight. Specific examples of the acid-decomposable dissociation-inhibiting compound (F) are shown below, but the present invention is not limited thereto. -134-This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 PCT) 548523 A7 B7

548523 A7 _________B7 V. Description of the Invention (133) (GL alkaline pen can be used in this helmet. The photosensitive composition may contain (G) —a kind of alkaline developer that is insoluble in water but soluble in acid-decomposable groups. Resin can be used to improve the sensitivity. / Knife amount of novolac resin of about 10,000 to 20,000 and polyhydroxystyrene with a molecular weight of about 3,000 to 50,000 Resins, but because they have a great absorption of light of 250 μm or less, it is best to use them after partial hydrogenation or in an amount of 30% by weight or less of the entire resin amount. Carboxyl groups can also be used as Resins with basic soluble groups. For the purpose of improving the resistance to dry etching, resins containing carboxyl groups should contain single or multiple aliphatic groups. In particular, they may have an alicyclic hydrocarbon structure but do not show acid decomposition. Examples are copolymers of methacrylic acid and (meth) acrylic acid, and (meth) propionate resins containing alicyclic hydrocarbons at the terminal end. Other additions are dense if the positive photosensitive composition of the present invention If necessary, it can contain dyes, plasticizers, foreign ingredients (D) a surfactant, a sensitizer, and a compound that can help dissolve in the developing solution. The compound that can be used to help dissolve in the developing solution used in the present invention is a low-S compound that has two or more desired compounds. OH group or one or more groups, and its molecular weight is L000 or lower. When compounds having a carboxyl group are used, for the same reasons as above, they are most preferably alicyclic or aliphatic compounds. The best addition amount is preferably from 2 to 50% by weight. A more preferred range is <5 to 30% by weight, and (B) can be decomposed under the action of an acid to increase the alkali developer. The solubility of the resin is the benchmark. When the amount exceeds 50-136-this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 548523 V. Description of the invention (134) When the% of the weight is developed, The quality is deteriorated and the pattern is deformed during development. Such a molecule! A phenol compound of 1,000 or less can be easily obtained by, for example, JP-A-4-12293 8, JP-A-2-2853 1, Related methods disclosed in U.S. Patent No. 4,916,210 and EP 219,294 Obtained. / Examples of fluorenyl lipid% or aliphatic compounds include carboxylic acid derivatives having a cholesterol 2 configuration, such as cholic acid, deoxycholic acid or lithocholic acid, adamantane dicarboxylic acid derivatives, adamantane Dicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexanedicarboxylic acid ', but the present invention is not limited thereto. The interface different from the component (D) fluorine-containing surfactant and / or silicon-containing surfactant may also be used. An active agent is added to the photosensitive composition according to the present invention. Specific examples of the surfactant that can be used in the present invention include non-ionic surfactants such as polyoxyethyl ethers (such as polyoxyethylene lauryl) Ether, polyoxyethyl stearyl ether, polyoxyethyl cetyl ether and polyoxyethyl oleyl ether), polyoxyethyl aryl aryl ether (such as polyoxyethyl octyl ether) And polyoxyethylene nonylpanyl ether), polyoxyethylene · polyoxypropylene block copolymers, sorbitan fatty acid esters (such as sorbitan monolaurate, sorbitan Monopalmitate, sorbitan monostearate, sorbitol ^ oleate, sorbitan trioleate, and mountain Sugar anhydride tristearate) and polyoxyethyl sorbitan fatty acid esters (such as polyoxyethyl sorbose S pre-anhydride monolaurate, polyoxyethylene sorbitan monopalmate Acid esters, polyoxyethyl sorbitan monostearate, polyoxyethyl sorbitol ^ dioleate, and polyoxyethyl sorbitan tristearate). · These surfactants can be added individually or in a combination of two or more of them. -137 This paper is suitable for China National Standard (CNS) A4 size (210 X 297 mm). Binding 548523 A7 B7

V. Description of the method of use The positive green composition of the present invention is coated on a substrate to form a thin film. The film thickness is preferably from 0.2 to 1.2 m. Inorganic substrates that can be used in the present invention include conventional bare si substrates, sog substrates, and substrates with antireflection coatings described below. As needed, commercially available inorganic or organic antireflection coatings can be used in the present invention. Typical coating types are titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and organic coating types, including light absorbers and polymer materials as anti-reflection coatings. The former requires film-forming equipment, such as vacuum coating equipment, CVD equipment, or sputtering equipment. For example, an anti-reflective coating containing a condensation product of a diphenylamine derivative and a formic acid-modified melamine resin is disclosed in 〖ρ-Β_7 · 696η (n JP-B used in this case—the word means "have been examined" The published patent application) of the testable resin and light absorbing agent is disclosed in US Patent No. 5,294,680, which contains the reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent, and is disclosed in JP-A-6. -1 1 863 1 An anti-reflective coating containing a resin adhesive and a cross-linking agent of hydroxymethyl melamine matrix. It is disclosed in jp-A winter 丨 8656. It has a carboxylic acid group, epoxy group and light absorption in the same molecule Based acrylate resin type anti-reflection coating, anti-reflection coating disclosed in JP-A-8-87115 containing hydroxymethylmelamine and benzophenone-based light absorbing agent, and JP4U 79509 containing polyethylene Alcohol resins and anti-reflection coatings of low-molecular-weight light absorbers are examples of organic anti-reflection coatings. In addition, DUV-30 series, DUV-40 series manufactured by Brewer Technology, and AC manufactured by ARC25 and Chypre -2, AC-3, AR19 and -138-This paper applies the Chinese national standard (CNS) A4 (210X297 mm) 548523 A7 B7 V. Description of the invention (136) AR20 can be used as a base anti-reflective coating. I All use the appropriate coating method to use the spinner or applicator to apply the above-mentioned resist. The coating liquid is applied to a substrate (such as a stone / silicon dioxide coating) used in the manufacture of such precision integrated circuit components (or, if necessary, the above-mentioned substrate anti-reflection coating is provided) to make the coating film Exposure, baking, and development through a specified mask, so a good resist pattern can be obtained. The irradiation light is preferably light with a wavelength from 50 nm to 250 microns. In particular, KrF excimer laser (248 nm ), ArF excimer laser (193 micrometers), F2 excimer laser (157 nanometers), x-rays, electron beams, etc. As examples, alkaline aqueous solutions such as inorganic alkali metals such as sodium hydroxide, hydrogen can be used. Potassium oxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, etc., primary amines such as ethylamine, n-propylamine, etc., secondary amines such as diethylamine, di-n-butylamine, etc., tertiary amines Such as diethylamine, methyl monoethylamine, etc., alcohol amines such as dimethylethanolamine, triethanolamine, etc. As a developing solution, a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. and a cyclic amine such as pirro, or pyridine, etc. In addition, an appropriate amount of an alcohol or a surfactant may be added to the above-mentioned base 0 Examples in water-based aqueous solutions The present invention will be described in detail by reference to the following examples, but the present invention should not be construed as being limited to this. Synthetic examples of the acid generator t into the example 1 raw agent π-3) ^ will be 50 Gram dibenzylidene is contained in 800 ml of benzene, and 200 g of aluminum chloride is added to -139-This paper size applies to China National Standard (CMS) A4 (210 X 297 mm)

Binding

548523 A7 — _ B7 V. Description of the invention (137) Put it in and heat the solution under reflux for 24 hours. The reaction solution was slowly poured into 2 liters of water, and 400 ml of concentrated sulfuric acid was added thereto, followed by 70 °. 〇 Heat for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate, filtered, and an ammonium iodide aqueous solution obtained by dissolving 200 g of ammonium iodide in 400 ml of water was added thereto. The precipitated powder was filtered, washed with water, then washed with ethyl acetate, and dried to obtain 70 g of triphenylphosphonium iodide. Triphenylphosphonium iodide (17.6 g) was dissolved in 1000 ml of methanol and 2.5 mg of silver oxide was added to the obtained methanol solution, followed by stirring at room temperature for 4 hours. After stirring, the reaction solution was filtered and a methanol solution containing 25 g of perfluoro-n-octanoic acid was added thereto. The reaction solution was concentrated with acid and the precipitated oily product was dissolved in ethyl acetate, washed with water, dried and concentrated with acid, thereby obtaining 20.5 g of the target product. Synthesis Example 2 Synthesis of acid generator α-5) containing bis (third butylphenyl) sulfide (80 mmol), bis (third butylphenyl) iodine, perfluoron-butanesulfonate (20 mmol) and copper benzoate (4 mmol) were stirred at 130 ° C for 4 hours under a nitrogen stream. The reaction solution was allowed to cool down, 100 ml of ethanol was added thereto and the precipitate was removed. The filtrate was concentrated, and 200 ml of diethyl ether was added to the filtrate, so Shen Dian produced powder, and the precipitate was taken into consideration, washed with diethyl ether, and then dried to obtain the target product. In the same manner as above, other acid generators (I) were synthesized using triphenyl perfluorobutane sulfonate and triphenyl trifluoride (product of Midori Kagaku Co., Ltd.). Jincheng Example 3 -140-The paper size is in accordance with China National Standard (CNS) A4 size (210 X 297 mm) 548523 A7 B7 V. Description of the invention (138) Benzomethyl methyl tetrahydro 4 phenperfluorobutanesulfonate The combination of acid πππ2 and 1) will drop tetrahydro57 phenphene (53. 2 g) to 400 liter Ethyl Ether and slowly add 100 g of benzyl bromide bromide to 300 ml. The solution obtained by Ewe and was given Luo solution for 3 hours at room temperature 'so Shen Dian produced powder. The reaction solution was poured into 1,500 ml of ethyl acetate, and the powder was filtered off and dried to obtain 137 g of benzamidine methyltetrahydrothiophene bromide. Dissolve potassium perfluorobutane sulfonate (60 g) in a mixed solvent containing 200 ml of water and 200 ml of methanol and dissolve 49.5 g of benzamidine methyltetrahydroorphine in 300 ml of water. The obtained solution was added to the above solution. The aqueous solution was extracted twice with 200 ml of chloroform, and the organic phase was washed with water and concentrated, thereby obtaining a crude product. Distilled water (300 ml) was added to the product obtained above, followed by heating at 100 ° C for 30 minutes, and then cooling it, so that the solid product was removed by precipitation. The precipitate was filtered and reslushed with diisopropyl ether: 77 g of benzamidinemethyltetrahydropyrophene perfluorobutanesulfonate were thus obtained. Synthetic Example 4 Methyl methyl tetrahydro p-sphene full-air octanoic acid sodium salt (TI-3)) &lt; Compound (III-3) can be borrowed from benzamidine methyl tetragas in the same manner as above Synthesis of p-phene and perfluorooctanoic acid. Synthesis Example 5: Benzoyl S &amp; f-based tetrahydromethylphenazine triphosphate (II 1-2); ^ Compound (III-2) can be benzyl bromide methyl tetrabromide in the same manner as above chlorine. Sephen is synthesized by the exchange of trifluoromethanesulfonic acid salt. Other compounds can also be synthesized in the same way as the corresponding halogenated benzyl methyl group and thioether compounds to synthesize halogenated benzamidine methyl hydrazone, and then blocked with acid -141-this paper applies Chinese national standard &lt; CNS) A4 Specifications (210 X 297 gong) 548523 A7 ___B7 V. Description of the invention (139) (Salt) Obtained by salt exchange. Synthesis of the synthetic acid generator_IM (). Tetrahydropyrophene (Π. 8 g) was dissolved in 100 ml of Ewe and 20 g of 1-bromo-3,3-dimethyl-2-butane. The ketone was slowly added to the above solution. The reaction was stirred at room temperature for 2 days, and the powder precipitated. After adding 100 ml of ethyl acetate to the reaction solution, the powder was filtered, washed with ethyl acetate, and dried, thereby obtaining 24 g of 2- pendantoxy-3,3-dimethylbutyltetrahydrophene bromide. Compound. Potassium perfluorobutane sulfonate (10 g) was dissolved in a mixed solvent containing 500 ml of water and 100 ml of methanol and 7.7 g of 2- pendantoxy-3,3-dimethylbutane A solution obtained by dissolving methyltetrahydro-4phene bromide in 50 ml of methanol was added to the above solution. The aqueous solution was extracted twice with 100 torr gas, and the organic phase was washed with water and concentrated, thereby obtaining an oily product. The above-obtained product was concentrated again with ethyl acetate, whereby a solid product was obtained. The solid product was filtered and reslurried with diisopropyl ether, thereby obtaining 9 g of 2- pendantoxy-3,3-dimethylbutyltetrahydro-4phene perfluorobutanesulfonate. According to the synthesis method disclosed in JP-A-8-27102, 2-oxocyclohexylmethyl (2-noryl), trifluoromethanesulfonate (IM) was synthesized. Other acid generators without a stilbene matrix can be obtained by reacting a corresponding sulfide compound with a drawn alkyl group to synthesize stilbene, and then performing a salt exchange with the acid (salt). Synthesis of Resin Synthesis Example 1 Synthesis of Resin II) (Quai | Type 丨 -142-548523 A7 B7

V. Description of the invention (14) 2-ethyl-2-adamantyl methacrylate and butyrolactone methylpropionate are dissolved in a mixed solvent at a ratio of 55/45 to prepare 100 ml of solid A solvent with a concentration of 20%, wherein the mixture solution is a 5/5 ratio of methyl ethyl ketone / tetrahydrocran. Add 2 mol% of V-65 (made by Wako Pure Chemical Industry) to the above solution and add the mixed solution dropwise to 0 ml of methyl ethyl ketone which has been heated under nitrogen flow at 60 C for more than 4 hours in. After the dripping was stopped, the reaction solution was heated for 4 hours, and then V-65 was added in an amount of 1 mole% and the solution was stirred for 4 hours. After the reaction is complete ', the reaction solution is cooled to room temperature, crystallized in a 3 liter i / i ratio of distilled water / isopropyl alcohol mixed solvent, and the precipitated resin tincture is recovered as a white powder. The composition ratio of the polymer obtained by CnNMR was 46/54. The weight-average molecular weight measured by GPC and calculated by the standard polyphenylene terephthalate term was 10,700. Resins (2) to (15) were synthesized in the same manner as in Synthesis Example 1. The composition ratios and molecular weights of the resins (2) to (15) are shown in Table 1 below. The repeating units 1, 2, 3, and 4 in the table are the order of the structures from left to right. -143-This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 548523 A7 B7 V. Description of the invention (141) Table 1 Resin number repeating unit 1 (mol%) Repeat unit 2 (mol%) ) Repeating unit 3 (mol%) Repeating unit 4 (mol%) Molecular weight I 2 53 40 7 13,400 3 46 34 20 9,400 4 42 31 27 8,300 5 49 42 9 9,900 6 42 30 28 10,3〇07 39 35 26 8,900 8 46 22 30 2 12,900 9 42 20 32 6 11,600 10 46 42 12 9,200 11 38 32 30 11,300 I 12 42 18 38 2 13,800 1 13 38 31 29 2 11,100 I 14 50 31 19 11,700 I 15 35 6 16 43 13,200 | -144-

Order

Line This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7

548523 A7 B7

548523

A B7 ^ Ming said Mingfa 44

H2 C

Is one = 0, C—C 丨 c: 丨 〇 H2 C ⑼

3 Η

Outside 1 = 0 C——CICIO -π2 C

π3 CICIC—O I H2 c

H3I o Η I II cIcIc = 丨 〇Iπ2 c

Π3 C—c Ic = I 〇1 2 Η c == 0 1— / (\

CH3l? -R ° o H2 c 534X0

H3l = 0〉 c—c—o—o i H2 c 2) -147-This paper size applies Chinese National Standard (CNS) A4 specification (2ΙΟ X 297 public capital) 548523 A7 B7 5. Description of the invention (CH3 CH3

CH CH '—CH2-〒 一 ch2—c — 00 00

CH2—c 3 ch2—c--ch2—c—

(13) NH • CH2 — C. c = 〇

(14) H3l = 0? C — cIc: —〇 — c ^ _ o HI IIc—c10 — o I _2c

2 H c

o

-148-This paper size applies Chinese National Standard (CMS) A4 specification (210X297 cm) 548523 A7 B7 146) 5. Description of the invention (synthesis example 2 resin Π 6) (main bismuth gas ·) ^ Tertiary butyl carboxylate, butyrolactone orthobornene carboxylate and maleic acid (mol ratio 40 / 10/50) and THF (60% by weight, at reaction temperature) can be separated The flask was heated at 60 t under a stream of nitrogen. When the reaction temperature was stable, 2 mol% free radical initiator V_601 (made by Wakopure Chemical Industry) was added to initiate polymerization. The heating system was performed for 12 hours The obtained reaction mixture was diluted twice with tetrahydrofuran, and then put into a mixed solvent of hexane / isopropyl alcohol (丨 / 1), so a white powder was precipitated. The precipitated matter was dried and dried, thereby obtaining a resin (16). The weight-average molecular weight measured by GPC and calculated from the polyphenylene terephthalate of the resin (丨 6) was 8,3 00. The original butyl norbornene carboxylic acid tertiary butyl ester / orthobornene in the resin (16) was confirmed by NMR spectrum The molar ratio of the repeating units of butyrolactone carboxylate / maleic anhydride is 42/8/50. Synthetic resins (17) to (27) were synthesized in the same manner as in Example 2. The composition ratios and molecular weights of the resins (Π) to (27) are shown in Table 2. The alicyclic smoke unit i, 2 in the table And 3 is the order of each structure from left to right. -149-This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 cm) 548523 A7 B7 V. Description of the invention (147) Table 2 Resin cycloaliphatic hydrocarbon Units of alicyclic alkane monoalicyclic alkane monomaleic anhydride molecular weight number (mol%) position (mol%) position (mol%) (mol%) 17 35 15 50 8,200 18 20 30 50 8,600 19 36 14 50 9,100 20 31 19 50 7,900 21 35 5 10 50 8,300 22 33 17 50 8,500 23 38 12 50 8,900 24 31 6 13 50 8,10025 33 7 10 50 9,100 26 40 10 50 9,300 34 16 50 8,800 -150-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) 548523 A7 B7 Five invention descriptions (148 resins (16) to (27) the structure is shown below) &gt; = 0 (16) coo- coo- c〇〇 麻 〇〇COO'M-COO n C〇〇Ό t) 0 ο &quot; Ό (18) COOCH2CH2COOC (CH3> 3

(19) OCOCH, COO. Ch3 CH3 0 〇y (20) lid COO — C — CH2_C — CH I II CH, 〇

c〇〇ch2ch2〇ch2ch2〇ch &lt;

, Z &gt;. / 广 0 (2 丨) 〇c〇ch3 coo · -151-The size of this paper is applicable to China National Standard (CNS) A4 (210X297) 綮 548523 A7

This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 548523

Synthetic solid __ (2 8) of the synthetic j mix &amp; original borneol with a molar ratio of 35/35/20/10 Hexyl_2-propyl acrylate was placed in a reaction vessel and dissolved in tetrahydrofuran to prepare a solution with a solid content of 60%. The solution was heated at 65 t under a stream of nitrogen. When the reaction temperature is stable, Mole% free radical initiator V-601 (made by Wako Pure Chemical Industries) is added to initiate polymerization. After heating for 8 hours, the obtained reaction mixture was diluted twice with tetrahydrofuran, and then put into five times the volume of the reaction mixture in hexane, whereby a white powder was precipitated. The precipitate was filtered and dissolved in methyl ethyl ester, and then re-dissolved in a five-fold volume of a mixed solvent of hexane / third butyl methyl ether (1/1).重量 The weight average molecular weight measured by GPC and calculated by the polystyrene term of resin (28) is 12,100. NMR spectrum confirmed that the molar ratio of the composition of the resin (28) Borneol / Malay feSf / Thirty-Butyl Acrylate / 2-methylcyclohexyl-2-propylpropionate was 32/39 / 19/10. Resins (29) to (4 1) were synthesized in the same manner as in Synthesis Example 3. The composition ratios and molecular weights of the resins (29) to (4 1) are shown in Table 3 below. -153-This paper size applies to China National Standard (CNS) M specifications (210 x 297 public goods)

Hold

548523 A7 B7 V. Description of the invention (151) Table 3 Resin series 5 Tiger original borneol acetic acid § f (Meth) acrylate dosage 29 20/15 40 15/10 1 1,900 30 32 37 20/8/3 10,500 31 16 21 36/27 13,900 32 15 22 34/29 12,300 33 17 20 33/30 12,400 34 18 24 32/26 13,000 35 15 19 36/30 12,700 36 15 20 29/10/26 13,100 37 17 21 31/31 12,800 38 18 17/3 30/32 13,300 39 16 19 31/12 / 11/11 12,600 40 20 22 58 14,700 41 23 28 35/14 13,300 -154-This paper size applies Chinese National Standard (CNS) A4 specifications (21 〇x 297 mm) 548523 A7 B7 Five invention descriptions (152 resins (28) to (41) The structure is shown below. —CH-CH— ch2--ch-1 ch3 · 〇-c-ch3 c-II 〇 (28) ch3

CH2 — CH— * CH ^ C — 0—C — CH2CH3 II I 〇 CH, (29) equipment * —ch2-ch— Ch3

Ic—0—c II 〇

Order

—CH-CH-

——CH2 ~ CH— 1 CH 3 C —0 —C —CH2CH3 (30) 〇CH3 line—ch2 ~ ch— c—0 II 0 C —〇 一 (〇Η2〇Η2〇> 2〇Η3 o — CH- CH — CH,

(31) • CH2 — CH- c—〇_ II 〇 • ch2-ch—o = co -155-The paper scale is applicable to China National Standard (CNS) A4 (210 x 297 male and double) 1 —CH2—CH &quot; 548523 A7 B7 Fifth invention description (153 —CH-CH—, 乂 (CH2 — CH —— * CH2CH3 C—〇_II 〇 氺 —CH2—CH— (32) 〇 = c I 〇CH, CH, • C〇 〇

(33) 〇 — CH-CH — —-CH? —CH— · * CH3 I I c—〇—c— II I 〇 ch3 * —CH2— CH—I c—o-II 〇 o (34)

OH — CH-CH —, people entering

0- Ό -156-This paper · size applies to Chinese National Standard (CNS) A4 (210 x '297 mm) 548523 A7 B7 V. Description of the invention (⑸ —CH—CH— 人 乂 〇CH. I ^ • CHfC — 氺 ch2ch3 c—o- II 0

• CH2 — CHIo = c I0 (36)

0 b

CH—CH — One CH-CH--CH2 — CH— * CH2CH3 C —o-

II 〇 * —CH〇-CH- (38) C 〇 · II o -157-This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) 548523 A7 B7 V. Description of the invention (155) — —CH — CH ——— CH2 —CH— * CH ·: People enter. 'C —0 —C II 0 CH3 ο (39) CH2 —CH——CH Fly—CH2 — CH · • CH2 —CH—— CH3 C —〇 · II o

c-o-II 0 h3c

C 〇 II 〇

0- 一 ^ CH-CH— —CH2 — CH · C = 0 (40)

OH —1 ~ r— —CH-CH —Clever. Enter —CH2 —CH —— * Ic = o

C41)

-158-This paper size applies the Chinese National Standard (CNS) A4 specification ('210 x 297 public expense) 548523 A7 B7 156 V. Description of the invention Synthesis of synthetic real tree J purpose (42) (Mole ratio is 20/20 / 35/25 of original norbornene carboxylic acid tert-butyl ester, Malay § paternal sex, 2-methyl-2-adamantyl acrylate and orthobornyl lactone propionate were put into the reaction vessel and It is dissolved in a mixed solution of methyl ethyl ketone / tetrahydrofuran (1/1) to produce a solid solution containing 60% of the falling liquid. The solution is heated at $ 5 ° C in a nitrogen stream. When the reaction temperature is stable, 3 mole% free radical initiator V-601 (made by Wako Pure Chemical Industry) was added to initiate polymerization. After 12 hours of heating and heating, the reaction mixture was put into hexane of five times the volume of the reaction mixture. Therefore, a white powder was precipitated. The white powder was dissolved in a methyl ethyl ketone / tetrahydrofuran meaning solvent and put into a five-fold volume of hexane / methyl tert-butyl ether to precipitate a white powder. The precipitate was filtered. This procedure was repeated and dried to obtain resin (42). Once measured by RI analysis and as tree The weight calculated from the polyphenylene terephthalate of lipid (42) ^ The average molecular weight is U, _. The amount of residual monomers is 0.4%. It is confirmed by the orbital spectrum that Zhongyuan Borneol / Maleic Acid / 2 methyl, 2 _ Donkey Kong Bakelite Proton Original Borneol | Morr, which is composed of saccharic acid s, is synthesized in the same manner as in Synthesis Example 4. Suppose M3) to (66). Resins (43) to (66) &lt; composition ratio and molecular weight are shown in Table 4 and Table 4. -159-

548523 A7 B7 V. Description of the invention (157) Table 4 Resin No. Acrylic Acid Hydrocarbon Formula (III) Monomer (Acid Anhydride) Propionic Acid Monomer Molecular Weight 43 24 29 3 1/16 12,300 44 21 28 32/29 1 1,100 45 22 27 28/23 1 1,300 46 27 3 1 24/18 10,700 47 32 38 20/10 9,700 48 31 35 21/13 9,200 49 29 35 20/16 8,900 50 35 39 23/3 8,700 51 28 36 22/14 10,600 52 28/8 44 20 9,100 53 30/6 42 22 7,700 54 46 47/3 4 6,300 55 37/6 48 9 6,800 56 34/10 51 5 7,400 57 41 43 10/6 6,700 58 39 42 1 1/8 8,800 59 36 42 10/12 9,300 60 39 43 14/4 9,800 61 38 42 15/5 9,300 62 24 27 25/24 12,600 63 19 24 40/17 9,500 64 29 32 34/5 10,400 65 20 25 26/5 / 24 13,400 66 16 24 32/24/4 12,700 -160-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7

548523 A7 B7

548523 A7

The paper scale is applicable to China National Standard (CNS) A4 (210 x 297 cm) 548523 A7 B7

548523 A7 B7

This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

k 548523 A7 B7

V. Description of the invention (163) Synthesis example i after ill? 1) Synthesis (propenyl type \ 2-adamantyl-2-propyl methacrylate, butyrolactone acrylate and monomer of the present invention It was fed at 48/22/30 ratio and dissolved in a 1/1 ratio of methyl ethyl ketone / tetrahydrofuran solvent to prepare 100 ml of a solution with a solid content of 35%. 2 mole% V-65 (Wak. (made by pure chemical industry) and 2 mol% of hydrogen thioethanol are added to the above solution and the mixed solution is added dropwise to 10 ml of methyl ethyl ketone which has been heated at 65 ° C in a nitrogen stream for more than 4 hours. Stop After dripping, the reaction solution was heated for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, crystallized in a mixed solvent of 2 liters of methanol / isopropyl alcohol ratio of 3/1, and the precipitated white powder was filtered. The powder was then slurried with 丨 liter of methanol and the resin was recovered (7 丨). The composition ratio of the polymer obtained by NMR was 49/22/29. Measured by Gpc and calculated by the standard polyphenylene terephthalate term The weight-average molecular weight was 8 ⑻. In the same manner as in Synthesis Example 5, resins (72) to (80) were synthesized. The composition ratios and molecular weights of the lipids (72) to (80) are shown in the following Table 5. The repeating units i, 2 and 3 in the table are the order of the structures from left to right. Μ 548523 A7 B7 V. Invention Explanation () Table 5 Resin repeating unit 1 Repeating unit 2 Repeating unit 3 The repeating molecular weight number of the present invention (mole%) (mole%) (mole%) Unit (mole%) 72 51 21 28 8,3〇〇 73 40 10 18/8/24 7,400 74 47 15 12 26 8,30.075 51 11 25 13 7,900 76 49 9 20 22 8,800 77 51 20 4 25 8,100 78 39 15 10 36 8,200 79 46 28 8 18 8,600 80 48 20 32 7,200

Packing f -167-Wood paper size applicable to China National Standard (CNS) A4 (210X297 mm) 548523 A7 B7

548523 A7 B7 V. Description of the invention (166)

CH, ch3 CH--CHo-C-I C = 〇

(74)

CH, ch2

CH2 — CH--CH2 ~ · CH--CH2 —C — I I I c = o ^ c = oi. (75)

• ch2-c--ch2-ch--CH2—CH—

c = o

OH

(76)

-169-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7

548523 A7 B7 V. Description of the invention (π8 Synthesis Example 6 Combination of resin (8 1) (The original borneol 莫 carboxylic acid third butyl vinegar with a molar ratio of 30/30/20/20, maleic anhydride h methyl J-Kangang Pengji Acrylic Acid Vinegar and the acryl monomer of the present invention are placed in a reaction vessel and dissolved in a mixed solution of methyl ethyl ketone / tetrahydrofuran (8/2) to prepare a solution with a solid content of 60%. Heat the ▲ 'solution in a nitrogen stream at 65 ° C. 稳定 When the reaction temperature is stable, 20% of 4% moles of free radical initiator V-601 (made by Wako Pure Chemical Industry) is used in 6 hours. The base solution was added dropwise to the above solution. After the dropwise addition was completed, the reaction solution was heated for 4 hours. Then the reaction mixture was put into a 3 / i mixed solution of hexane / methyl tert-butyl ether of five times the volume of the reaction mixture. White powder was precipitated. Then Shen Dianwu was dissolved in five times the volume of tetrahydrofuran and white powder was precipitated. The precipitate was filtered. The procedure was repeated and dried to obtain resin (81). Measured by RI analysis and more The weight average molecular weight calculated for the polystyrene term of resin (8 υ is 9,700. Residual The remaining monomer amount is 0.2%. Based on the NiMR spectrum, it is confirmed that the original norbornene / maleic anhydride / 2-methyl-2-adamantyl propionate S and fej / propionate monomer are used in the resin (8 1). The molar ratio of the bulk composition is 22/3 0/2 5/22 3. The resins (82) to (99) were synthesized in the same manner as in Synthesis Example 6. The resins (82) to (99) &lt; composition ratio and molecular weight The series are shown in the following Table 6. The order of each structure of the alicyclic 晞 te, (VIII) monomer (anhydride) and the allyl system from left to right. -171-This paper is in accordance with the Chinese National Standards (CNS) ) A4 specification (21 ^ 77 ^ 7 ^ 7 548523 A7 B7 V. Description of the invention (169) Table 6 Resin number Alicyclic fluorene units (mole%) Monomer of formula (VIII) (anhydride) (mol%) C Monocarboxylic acid monomer (mol%) Monomer of the present invention (mol%) Molecular weight 82 28 35 20/8 9 9,300 83 27 34 27 12 9,800 84 39 42 19 8,30.085 36 40 8 4/2 / 10 10,400 86 30 36 16 18 10,100 87 25 30 20/6 19 10,900 88 32 36 10/4/18 10,100 89 25/5 34 24 12 9,600 90 32/6 40 8 14 10,600 91 22 27 37 14 11,400 92 18 24 34 24 13,000 93 15 20 28 12/5/20 12,800 94 16 22 42 20 12,300 95 22 28 32 18 14,400 96 20 26 32/10 12 13,100 97 20 23 31 26 12,900 98 18 20/3 31 28 13,200 99 1 ---- -1 10/12 26 33 19 14,100 -172-wood Paper size applies to Chinese National Standard (CMS) A4 (210 X 297 mm) 548523 A7 B7

548523 A7 B7

548523 A7 B7 V Description of the invention (172)

(88)

(89)

c〇〇 一 ch2ch2〇ch3 (90)

-175-This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 male f) 548523 A7 B7

548523 A7 B7

548523 A7

This paper size is applicable to China National Standard (C NS) A4 (210 x 297 mm) 548523 A7 _ B7 V. Description of the invention (176) Preparation examples of resists 1-1 to 1-80, [N1 to 11- 80 and III-1 to [11-66 and Comparative Examples 1-1 to 1-4, II-1 to II-4, III-1 to III-4 Dissolve each component shown in Tables 7 to 17 below and prepare The solution with a solid content concentration of 12% by weight was filtered through a Tenon filter with a pore size of 0.1 micron. Each of the prepared compositions was evaluated as described below. The results obtained are shown in Tables 18 to 28. -179-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 male: t) 548523 A7 B7 V. Description of the invention (177) ) Acid generator (III) (g) Other (g) Alkali (g) Surfactant (0.03 g) Weight ratio of solvent M (1) 1-2 (0.1) III-2 (0.5) DBN (0.02) Wl Al / Bl (95/5) 1-2 (2) 1-8 (0.15) III-l (0.6) TPI (0.03) Wl A1 (100) [-3 (3) Ml (0.15) 111-11 ( 0.5) TPSA (0.02) W-2 Al / Bl (90/10) 1-4 (4) 1-5 (0.2) III-15 (0.2) al (Ol) HEP (0.01) W-2 A3 / B2 ( 80/20) 1-5 (5) 1-14 (0.1) ΙΙΙ-2 (0.4) TPI (0.03) W-3 A2 / B1 (90/10) 1-6 (6) 1-13 (0.2) 111 -12 (0.3) DIA (0.01) W-3 A4 / B1 (90/10) 1-7 ⑺ Ml (0.15) 111-17 (0.15) DIA (0.007) W-4 Al / Bl (50/50) 1 -8 ⑻ 1-10 (0.2) III-1 (0.4) DBN (0.02) W-4 Al / Bl (90/10) 1-9 (9) 1-8 (0.1) 111-1 (0.7) LCB ( l) TPI (0.03) Wl A5 / B2 (90/10) 1-10 (10) '1-8 (0.15) 111-14 (0.2) TPI (0.02) Wl Al / Bl (95/5) 1-11 (Π) 1-11 (0.05) ΙΜ4 (0.7) TPI (0.03) W-2 Al / Bl (90/10) 1-12 (12) 1-5 (0.2) III-l (0.3) TPI (0.03) W-2 Al / Bl (95/5) 1-13 (13) 1-14 (0.1) III-1 (0,5) a5 (0.2) TPI ( 0.03) W-3Al / Bl (95/5) 1-14 ^ 14) M3 (0.2) III-4 (0.3) DBN (0.02) W-3 Al / Bl (95/5) 1-15 (15 ) Ml (0.15) 111-16 (0.2) TPI (0.03) W-4 Al / Bl (80/20) 1-16 (16) MO (0.2) 111-1 (0.15) DIA (0.01) W-4 Al / Bl (80/20) 1-17 (17) M2 (0.1) 111-1 (0.1) TPI (0.03) W-4 Al / Bl (95/5) 1-18 (18) 1-12 (0.2) III-8 (0.4) DCMA (0.01) W-4 Al / Bl (95/5) 1-19 (19) Μ (0.2) 111-13 (0.5) TPI (0.02) W-4 Al / Bl (95 / 5) 1-20 (20) Μ 7 (0.05) III-8 (0.5) TPI (0.03) W-4 Al / Bl (95/5) 1-21 (21) 1-2 (0.1) ΙΙΙ-2 ( 0.5) DBN (0.02) Wl Al / Bl (95/5) 1-22 (22) 1-8 (0.15) III-1 (0.6) TPI (0.03) Wl Al / Bl (80/20) 1-23 ( 23) 1 (0.1) 111-11 (0.6) TPSA (0.02) W-2 Al / Bl (90/10) 1-24 (24) IO (0.2) 111-15 (0.2) al (Ol) HEP ( 0.01) W-2 A3 / B2 (80/20) 1-25 (25) "-14 (0.1) ΙΙΙ-2 (0.4) TPI (0; 03) W-3 A2 / B1 (90/10)

Hold

k -180-This paper wave scale is applicable to China National Standard (CNS) A4 (21 {) χ 297 mm) 548523

Table 8 Examples of resin acid generators Acid generators Number of other interfacial active solvents (10 g) (Π) (m) (g) (g) Weight ratio of sex agent (g) (g) (0.03 t) 1-26 ---- 『6) 1-13 (0.2) ΙΠ-12 (0.3) DIA (O.Ol) W-3 A4 / B1 (90/10) .1-27 (27) 1-11 (0.15) Π -17 (0.15) DIA (0.007) W-4 Al / Bl (50/50) 1-28 (28) 1-10 (0.2) mi (0.4) DBN (0.02) WA Al / Bl (90/10) 1 -29 (29) 1-8 (0.1) mi (0.7) LCB (l) TPI (0.03) Wl A5 / B2 (90/10) 1-30 (30) 1-8 (0.15) in-14 (0.2) TPI (0.02) Wl Al / Bl (95/5) 1-31 (31) 1-11 (0,1) 111-14 (0.5) TPI (0.03) W-2 Al / Bl (90/10) 1- 32 (32) 1-5 (0.2) ΙΠ-1 (0.3) TPI (0.03) W-2 Al / Bl (95/5) W3 (33) 1-14 (0.1) ΙΠ-1 (0.5) a5 (0.2 ) TPI (0.03) W-3 Al / Bl (95/5) — 1-34 — 1-13 (0,2) 014 (0.3) DBN (0.02) W-3 Al / Bl (95/5) 1- 35 (35) 1-11 (0.15) 111-16 (0.2) TPI (0.03) W-4 Al / Bl (80/20) U ^ L (36) 1-10 (0,2) ΙΠ-1 (0.15 ) DIA (0.01) W-4 Al / Bl (80/20) 1-37 (37) 1-12 (0.1) mi (oi) TPI (0.03) W-4 Al / Bl (95/5) I 1- 38 (38) 1-12 (0.2) ffl-8 (0.4) DCMA (O.Ol) WM Al / Bl (95/5) 1-39 (39) _I · 1 (0.2) ΓΙΠ-13 (0.5) TPI (0.02) W-4 Al / Bl (95/5) 1-40 (40) Η7 (0.05) m- 8 (0.5) TPI (0.03) W-4 Al / Bl (95/5) 1-41 (41) — 1-2 (0 · 1) ΙΠ-2 (0.5) DBN (0,02) Wl Al / Bl (95/5) 1-42 (42) 1-8 (0.15) ffl-1 (0.6) TPI (0.03) Wl Al / Bl (80/20) 1-43 (43) Ml (0,1) ΙΠ- 11 (0.6) TPSA (0.02) W-2 Al / Bl (90/10) 1-44 * (44) 1-5 (0.2) III-15 (0.2) al (Ol) HEP (0.01) W-2 A3 / B2 (80/20) 145 (45) 1-14 (0.1) ΠΙ-2 (0.4) TPI (0.03) W-3 A2 / B1 (90/10) 1-46 (46) M3 (0.2) 111- 12 (0.3) DIA (0.01) W-3-A4 / B1 (90/10) 1-47 (47) Ml (0.15) ΠΙ-17 (0.15) DIA (0.007) W-4 Al / Bl (50 / 50) 1-48 (48) MO (0.2) mi (0.4) DBN (0.02) W-4 Al / Bl (90/10) 1-49 (49) 1-8 (0.1) III-1 (0.7) LCB (l) TPI (0.03) Wl A5 / B2 (90/10) 1-50 (50) `` -8 (0.15) 111-14 (0.2) TPI (0.02) Wl Al / Bl (95/5) -181- The size of this paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) 548523 A7 B7 V. Description of the invention (179) M Example number resin (10 g) Acid generator (II) (g) Acid generator m (g ) Others ( G) Alkali (g) Surfactant (0.03 g) Weight ratio of solvent 1-51 (51) 1-11 (0.05) m-14 (0.7) TPI (0.03) W-2 Al / Bl (90/10) 1-52 (52) 1-5 (0.2) mi (0.3) ΤΉ (0.03) W-2 Al / Bl (95/5) 1-53 (53) 1-14 (0.1) ffl-l (0.5) a5 (0.2) ΤΡΙ (0.03) W-3 Al / Bl (95/5) 1-54 (54) 1-13 (0.2) m-4 (0.3) DBN (0.02) W-3 Al / Bl (95/5 ) 1-55 (55) 1-11 (0.15) m-16 (0.2) TPI (0.03) W-4 Al / Bl (80/20) 1-56 (56) 1-10 (0.2) ffl-l ( 0.15) DIA (O.Ol) W-4 Al / Bl (80/20) 1-57 (57) 1-12 (0.1) mi (oi) ΤΡΙ (0.03) W-4 Al / Bl (95/5) 1-58 (58) 1-12 (0.2) ΙΠ-8 (0.4) DCMA (O.Ol) W4 Al / Bl (95/5) 1-59 (59) H (0.1) m-13 (0.5) ΤΡΙ (0.02) W4 Al / Bl (95/5) 1-60 (60) 1-17 (0.05) m-8 (0.5) TPI (0.03) W-4 Al / Bl (95/5) 1-61 (61 ) 1-2 (0.1) m-2 (0.5) DBN (0.02) Wl Al / Bl (95/5) 1-62 (62) 1-8 (0.15) mi (0.6) ΤΡΙ (0.03) Wl Al / Bl (80/20) 1-63 (63) 1-11 (0.1) ffl-l 1 (0.6) TPSA (0.02) W-2 Al / Bl (90/10) 1-64 (64) 1-5 (0.2 ) ΠΜ5 (0.2) al (0.1) HEP (0.01) W-2 A3 / B2 (80/20) 1-65 (65) 1-14 (0.1) m-2 (0.4) ΤΡΙ (0.03) W-3 A2 / B1 (90/10) 1-66 (66) 1-13 (0.2) m-12 (0.3) DIA (0.01) W-3 A4 / B1 (90/10) 1-67 (1) 1-1 (0.1) m-15 (0.2) DBN (0.02) Wl '' Al (100) 1-68 (3) 1-11 (0.15) m-19 (0.3) TPI (0.03) Wl Al (100) 1- 69 (4) 1-5 (0.2) m-23 (0.4) TPSA (0.02) W-2 Al / Bl (80/20) 1-70 ⑹ 1-12 (0.2) m-25 (0.2) al (0.1 ) HEPI (O.Ol) W-2 Al / Bl (80/20) 1-71 ⑺ 1-11 (0.2) m-i5 (〇.i) TPI (0.03) W-3 A1 / B2 (80/20 ) 1-72 (11) 1-17 (0.1) m-46 (0.3) DIA (0O1) W-3 A1 / B2 (80/20) 1-73 (13) 1-7 (0.1) ΠΙ40 (0 · 3) DIA (0.007) W4 A3 / B2 (80/20) 1-74 (14) 1-8 (0.15) 冚 -38 (0.5) DBN (0.02) W-4 A2 / B2 (90/10) 1- 75 (15) 1-12 (0.1) m-33 (0.2) LCB (l) TPI (0.03) Wl Al / B4 (95/5)

Binding

Line-182-This paper size applies the Chinese National Standard (CMS) A4 specification (210 x 297 mm) 548523 A7 B7 V. Description of the invention (18〇 Table 10 Example number resin (10 g) Acid generator (Π) (g ) Acid generator (III) (g) Others (g) Test (g) Surfactant (0.03 l) Weight ratio of solvent 1-76 (26) 1-21 (0.1) ΙΠ-32 (0.5) TPI (0.02 ) Wl Al (100) 1-77 (31) 1-10 (0.2) ΠΙ-23 (0.3) TPI (0.03) W-2 Al / Bl (80/20) 1-78 (35) 1-11 (0.15 ) Π-42 (0.3) TPI (0.03) W-2 Al / Bl (80/20) 1-79 (42) 1-12 (0.2) 111-60 (0.2) a5 (0.2) TPI (0.03) W- 3 A1 (100) 1-80 (3) 1-11 (0.15) Π-40 (0.3) DBN (0.02) W-3 Al / A4 (95/5) Comparative Example 1-1 (1) 1-2 ( 0.1) DBN (0.02) Wl Al / Bl (95/5) 1-2 (1) ΙΠ-2 (0.5) DBN (0.02) Wl Al / Bl (95/5) 1-3 0) 1-2 (0.1 ) ΠΙ-2 (0.5) Wl A1 (100) 1-4 (1) 1-2 (0.1) 111-2 (0.5) DBN (0.02) Al / Bl (95/5) | -183-This paper applies China National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7 V. Description of the invention (181)

All Example No. Resin (10 g) Acid generator (Π) (g) Acid generator (ΙΠ) (g) Other (g) Test (g) Surfactant_g) Weight ratio of solvent II-1 (1 ) Π-2 (0.5) ΠΠ-2 (0.2) DBN (0.02) Wi A1 / B 1 (95/5) II-2 (2) II-1 (0.6) III-1 (0.5) TPI (0.03) Wl Al (100) II-3 (3) 11-11 (0.6) 111-11 (0.7) TPSA (0.02) W-2 Al / Bl (90/10) Π-4 (4) Π-15 (0.2) 111 -15 (0.3) al (Ol) HEP (0.01) W-2 A3 / B2 (80/20) Π-5 (5) Π-2 (0.4) ΠΠ-2 (0.4) TPST (Ol) TPI (0.03) W-3 A2 / B1 (90/10) Π-6 Π Π-12 (1) ΙΠ-12 (0.1) DIA (O.Ol) W-3 A4 / B1 (90/10) Π-7 ⑺ Π- 17 ((λ6) ΙΠ-17 (0.15) DIA (0.007) W-4 Al / Bl (50/50) Π-8 Π Π-1 (0.4) mi (0.4) DBN (0.02) W-4 Al / Bl (90/10) Π-9 (9) Π-1 (0.7) ΙΠ-1 (0.7) LCB (l) TPI (0.03) Wl A5 / B2 (90/10) U-10 00) Π-14 (0.8 ) 01-14 (0.2) TPI (0.02) Wl Al / Bl (95/5) 11-11 (Π) Π-14 (0.7) Π-14 (0.7) TPI (0.03) W-2 Al / Bl (90 / 10) 11-12 (12) Π-1 (0.5) mi (0.3) TPI (0.03) W-2 Al / Bl (95/5) 11-13 ------ _ Π-1 (0.5) mi (0.3) a5 (0.2) TPI (0.03) W- 3 Al / Bl (95/5) Π-14 (14) Π-4 (0.5) ΙΠ-4 (0.3) DBN (0.02) W-3 Al / Bl (95/5) ιαΓ _〇5) _ Π- 16 (0.2) 111-16 (0.2) TPI (0.03) W-4 Al / Bl (80/20) Π-16 (16) Π-1 (0.6) ΙΠ-1 (0.15) DIA (0.01) W4 Al / Bl (80/20) Π-17 (17) Π-1 (0.1) mi (0.7) TPI (0.03) W-4 Al / Bl (95/5) Π-18 (18) Π-8 (0.4) ΙΠ -8 (0.6) DCMA (0.01) W4 Al / Bl (95/5) 11-19 (19) IM3 (0.7) m-13 (0.3) TPI (0.02) W-4 Al / Bl (95/5) 11 -20 a α-8 (0.5) III-8 (0.5) TPI (0.03) W4 Al / Bl (95/5) 11-21 (21) ΙΙ-2 (0.5) III-2 (0.2) DBN (0.02) Wi Al / Bl (95/5) U-22 --- _ΙΙ-1 (0.6) in-1 (0.5) TPI (0.03) Wl Al / Bl (80/20) 11-23 ---------- _ (23 ) _ JM 1 (0.6) 111-11 (0.7) TPSA (0.02) W-2 Al / Bl (90/10) 11-24 _〇4) U-15 (0.2) 111-15 (0.3) al (0.1 ) HEP (0.01) W-2 A3 / B2 (80/20) 11-25 U-2 (0.4) ΙΠ-2 (0.4) TPST (Ol) TPI (0.03) W-3 A2 / B 1 (90/10 )

A4 specifications (210X 297 mm) -184-548523 A7 B7 V. Description of the invention (182 Table 12 Example No. Resin (10 g) Acid generator (Π) (g) Acid generator ⑽ (g) Other (g) (G) Surfactant (0.03 t) weight ratio of solvent 11-26 (26) ΙΙ-12 ⑴ ΙΠ-12 (0.1) DIA (0.01) W-3 A4 / B1 (90/10) 11-27 (27 ) 11-17 (0.6) 111-17 (0.15) DIA (0.007) W-4 Al / Bl (50/50) 11-28 (28) Π-1 (0.4) III · 1 (0.4) DBN (0.02) W-4 Al / Bl (90/10) 11-29 (29) II-1 (0.7) ffl-1 (0.7) LCB (i) TPI (0.03) Wl A5 / B2 (90/10) 11-30 ( 30) 11-14 (0.8) 111-14 (0.2) TPI (0.02) Wl Al / Bl (95/5) 11-31 (31) Π-14 (0.7) ΠΠ-14 (0.7) TPI (0.03) W -2 Al / Bl (90/10) 11-32 (32) U-1 (0.5) ΙΠ-1 (0.3) TPI (0.03) W-2 Al / Bl (95/5) Π-33 (33) Π -1 (0.5) m-1 (0.3) a5 (0.2) TPI (0.03) W-3 Al / Bl (95/5) 11-34 (34) ΙΙ-4 (0.5) 111-4 (0.3) DBN ( 0.02) W-3 Al / Bl (95/5) Π-35 (35) Π-16 (0.2) m-16 (0.2) TPI (0.03) W4 Al / Bl (80/20) 11-36 (36) Π-1 (0.6) ffl-1 (0.15) DIA (0.01) W-4 Al / Bl (80/20) 11-37 (37) Π-1 (〇.1) ffl-1 (0.7) TPI (0.03) W-4 Al / Bl (95/5) 11-38 (38) 11-8 (0.4) Π-8 (0.6) DCMA (O.Ol) W-4 Al / Bl (95/5) Π-39 (39) Π-13 (0.7) m-13 (0.3) TPI (0.02) W-4 Al / Bl (95/5) I 1140 Γ (40) Π «8 (0.5) 111-8 (0.5 ) TPI (0.03) W-4 Al / Bl (95/5) U-41 (41) Π-2 (0.5) ΠΙ-2 (0.2) DBN (0.02) Wl Al / Bl (95/5) 11-42 (42) Π-1 (0.6) ffl-1 (0.5) TPI (0.03) Wl Al / Bl (80/20) 1143 (43) IM 1 (0.6) 111-11 (0.7) TPSA (0.02) W-2 Al / Bl (90/10) 11-44 (44) Π-15 (0.2) m-15 (0.3) al (Ol) HEP (0.01) W-2 A3 / B2 (80/20) 11-45 (45 ) ΙΙ-2 (0.4) ΙΠ-2 (0.4) TPST (Ol) TPI (0.03) W-3 A2 / B1 (90/10) '' 146 (46) 11-12 (1) 01-12 (0.1) DIA (0.01) W-3 A4 / B1 (90/10) II-47 ΤΤ λ η JL17 (0,6) 01-17 (0.15) DIA (0.007) W-4 Al / Bl (50/50) 11-48 Τ I Λί \ (0.4) III -1 (0.4) DBN (0.02) W-4 Al / Bl (90/10) 11-49 (49) (0.7) III-1 (0.7) LCB (l) TPI (0.03 ) Wl A5 / B2 (90/10) 11-50 ^ 14 (0.8) m-14 (0.2) TPI (0.02) Wl Al / Bl (95/5)

(CNS) A4 specification (210X297 mm) 548523 A7 B7 V. Description of the invention (183) Table 13 Example number resin (10 g) Generator (II) (gram) Acid generator (III) (gram) Other (gram) Test (g) Surfactant (0.03 g; weight ratio of L solvent 11-51 (51) 11-14 (0.7) 111-14 (0.7) TPI (0.03) W-2 Al / Bl (90/10) Π -52 (52) Π-1 (0.5) III-1 (0.3) TPI (0.03) W-2 Al / Bl (95/5) 11-53 (53) II-1 (0.5) ΙΠ-1 (0.3) a5 (0.2) ΤΡΙ (0.03) W-3 Al / Bl (95/5) 11-54 (54) Π-4 (0.5) ΠM (0.3) DBN (0.02) W-3 Al / Bl (95 / 5) 11-55 (55) Π-16 (0.2) ΙΠ-16 (0.2) TPI (0.03) W4 '' Al / Bl (80/20) 11-56 (56) II-1 (0.6) ΙΠ-1 ( 0.15) DIA (0.01) W-4 Al / Bl (80/20) 11-57 (57) Π-1 (0.1) Π-1 (0 · 7) TPI (0.03) W-4 Al / Bl (95 / 5) 11-58 (58) Π-8 (0.4) ΠΙ-8 (0.6) DCMA (O.Ol) W-4 Al / Bl (95/5) 11-59 (59) Π-13 (0.7) ΠΙ -13 (0.3) ΤΡΙ (0.02) W4 Al / Bl (95/5) 11-60 (60); Π-8 (0.5) ΠΙ-8 (0.5) ΤΡΙ (0.03) W-4 Al / Bl (95 / 5) 11-61 (61) Π-2 (0.5) ΠΙ-2 (0.2) DBN (0.02) Wl Al / Bl (95/5) 11-62 (62)) Π-1 (0.6) ΙΠ-1 (0.5) TPI (0.03) Wl Al / Bl (80/20) 11-63 (63) Π-11 (0.6) ΙΠ-11 (0.7) TPSA (0.02) W-2 Al / Bl (90/10) Π-64 (64) Π-15 (0.2) ΠΙ-15 (0.3) al (Ol) HEP (0.01) W-2 A3 / B2 (80/20) Π-65 (65) Π-2 (0.4) Π1-2 (0.4) TPST (Ol) TPI (0Ό3) W-3 A2 / B1 (90/10) 11-66 (66) 11-12 (1) ΙΠ-12 ( 0.1) DIA (0.01) W-3 A4 / B1 (90/10) 11-67 (1) 11-1 (1) ΙΠ-15 (0.2) DBN (0.02) Wl A1 (100) 11-68 (3) Π-8 (0.3) ΠΙ-19 (0.3) TPI (0.03) Wl A1 (100) 11-69 (4) '' Π-10 (0.6) ΙΠ-23 (0.4) TPSA (0.02) W-2 Al / Bl (80/20) LI-70 ⑹ Π-9 (0.2) ΙΠ-25 (0.2) al (Ol) HEP (0.01) W-2 Al / Bl (80/20) 11-71 ⑺ 11-19 (0.2) ΠΠ-15 (0.1) TPST (Ol) TPI (0.03) W-3 A1 / B2 (80/20) [1-72 (Π) U-11 (0.1) ΠΙ-46 (0.3) DIA (0.01) W- 3 A1 / B2 (80/20) Π-73 (13) 'Π-14 (0.3) 11140 (0.3) DIA (0.007) W4 A3 / B2 (80/20) 11-74 (14) 11-16 (0.7 ) ΠΠ-38 (0.3) DBN (0,02) W4 A2 / B2 (90/10) 11-75 (15) U-17 (0.2) UI-33 (0.5) LCB (l) TPI (0.03) Wl 1 Al / B4 (95/5)

Binding

Line-186-This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 548523 A7 B7 V. Description of the invention (tear) Table 14 Example number resin (10 g) Acid generator (II) (g) Acid Generator (III) (g) Other (g) Test (g) Surfactant _g) Weight ratio of solvent 11-76 (26) 11-20 (0.3) IU-32 (0.5) TPI (0.02) Wl Al (100) 11-77 (31) U-10 (0.2) ΙΠ-23 (0.3) TPI (0.03) W-2 Al / Bl (80/20) 11-78 (35) 11-9 (0 · 15) ΠΙ-42 (0.3) TPI (0.03) W-2 '' Al / Bl (80/20) Π-79 (42) Π-8 (0.2) ΠΙ-60 (0.2) a5 (0.2) TPI (0 · 03) W-3 A1 (100) Π-80 (3) 11-11 (0.3) Π-40 (0.3) DBN (0.02) W-3 Al / A4 (95/5) Comparative example II-1 (1) Π- 2 (0.5) DBN (0.02) Wl Al / Bl (95/5) II-2 (1) ΙΠ-2 (0.2) DBN (0.02) Wl Al / Bl (95/5) Π-3 (1) Π- 2 (0 · 5) ΠΙ-2 (0.2) DBN (0.02) Al / Bl (95/5) U4 (1) 11-2 (0.5) ΠΙ-2 (0.2) Wl A1 (100) -187-Paper Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 at public expense) 548523 A7 B7 V. Description of the invention (185) Table 15 Examples of acid generator acid Other Numbers of Bioactive Resin Basic Compounds Interface Active Solvents (1) (g) (11) (g) (10 g) (g) Agent (0.03 g) Weight Ratio (g) [II-1 1-2 (0.1 ) U-2 (0.5) (〇 DBN (0.02) Wl A1 / B 1 (95/5) III-2 1-8 (0.15) II-1 (0.6) (2) TPI (0.03) Wl A 1 (100 ) III-3 Ml (0.1) 11-11 (0.6) (3) TPSA (0.02) W-2 A 1 / B 1 (90/10) III4 1-5 (0.2) Π-15 (0.2) (4) HEP (0.01) W-2 A3 / B2 (80/20) al (Ol) III-5 1-14 (0.1) II-2 (0.4) (5) TPI (0.03) W-3 A2 / B1 (90 / 10) III-6 1-13 (0.2) 11-12 (0.3) (6) TPA (O.Ol) W-3 A4 / B1 (90/10) ΠΙ-7 1-11 (0.15) Π-17 ( 0.15) ⑺ TPA (0.007) W-4 Al / Bl (50/50) ΙΠ-8 1-10 (0.2) Π-1 (0.4) ⑻ DBN (0.02) W-4 Al / Bl (90/10) III -9 1-8 (0.1) Π-1 (0.7) (9) TPI (0.03) Wl A5 / B2 (90/10) LCB (l) ΙΠ-10 1-8 (0.15) Π-14 (0.2) ( 10) TPI (0.02) Wl Al / Bl (95/5) III-11 1-11 (0.05) Π-14 (0.7) (Π) TPI (0.03) W-2 Al / Bl (90/10) III- 12 1-5 (0.2) Π-1 (0.3) (12) TPI (0.03) W-2 Al / Bl (95/5) ΠΙ-13 1-14 (0.1) Π-1 (0.5) (13) TPI (0.03) W-3 Al / Bl (95/5) a5 (0.2) III-14 1-13 (0.2) Π-4 (0.3) (14) DBN (0.02) W-3 Al / Bl (95/5) ΙΠ-15 1-11 (0.15) 11-16 (0.2) (15) TPI (0.03) W-4 Al / Bl ( 80/20) ΙΠ-16 1-10 (0.2) Π-1 (0.15) (16) TPA (0.01) W-4 Al / Bl (80/20) III-17 1-12 (0.1) II-l ( 0.1) (Π) TPI (0.03) W-4 Al / Bl (95/5) ΠΙ-18 1-12 (0.2) U-8 (0.4) (18) DCHA (O.Ol) W-4 Al / Bl (95/5) III-19 1-1 (0.1) Π-13 (0.5) (19) TPI (0.02) W-4 Al / Bl (95/5) [11-20 1-17 (0.05) U- 8 (0.5) (20) TPI (0.03) W4 Al / Bl (95/5) III-21 1-2 (0.1) U-2 (0.5) (21) DBN (0.02) Wl Al / Bl (95/5 ) III-22 1-8 (0.15) IM (0.6) (22) TPI (0.03) Wl Al / Bl (80/20) III-23 Ml (0.1) II-11 (0.6) (23) TPSA (0.02) W-2 Al / Bl (90/10) ΙΠ-24 1-5 (0.2) 11-15 (0.2) (24) HEP (0.01) W-2 A3 / B2 (80/20) al (Ol) III- 25 1-14 (0.1) II-2 (0.4) (25) TPI (0.03) W-3 A2 / B1 (90/10) -188-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7 V. Description of the invention (Table 16) Example No. Acid generator W (g) Acid generator ⑼ (g) Resin (ίο g) Alkali ten compounds (g) Surfactant (0.03 (G) Weight of solvent than others (g) III-26 M3 (0.2) 11-12 (0.3) (26) TP A (0.01) W-3 A4 / B1 (90/10) III-27 1-11 (0.15 ) 11-17 (0.15) (27) TPA (0.007) W-4 A1 / B 1 (50/50) III-28 1-10 (0.2) II-1 (0.4) (28) DBN (0.02) W- 4 Al / Bl (90/10) III-29 1-8 (0.1) U-1 (0.7) (29) TPI (0.03) Wl A5 / B2 (90/10) LCB (l) ΠΙ-30 1-8 (0.15) Π-14 (0.2) (30) TPI (0.02) Wl Al / Bl (95/5) ΠΙ-31 Μ 1 (0.05) Π-14 (0.7) (31) TPI (0.03) W-2 Al / Bl (90/10) III-32 1-5 (0.2) Π-1 (0.3) (32) ΤΡΙ (0.03) W-2 Al / Bl (95/5) ΠΙ-33 1-14 (0.1) Π -1 (0.5) (33) TPI (0.03) W-3 Al / Bl (95/5) a5 (0.2) III-34 1-13 (0.2) Π-4 (0.3) (34) DBN (0.02) W -3 Al / Bl (95/5) ΠΙ-35 1-11 (0.15) 11-16 (0.2) (35) TPI (0.03) W-4 Al / Bl (80/20) III-36 1-10 ( 0.2) Π-1 (0.15) (36) TPA (0.01) W-4 Al / Bl (80/20) Π-37 1-12 (0.1) Π-1 (0.1) (37) TPI (0.03) W- 4 Al / Bl (95/5) ΠΙ-38 1-12 (0.2) Π-8 (0.4) (38) DCMA (O.Ol) W-4 Al / Bl (95/5) ΠΙ-39 1-1 (0.1) 11-13 (0.5) (39) TPI (0.02) W-4 Al / Bl (95/5) ΙΠ-40 1-17 (0.05) Π-8 (0.5) (40) TPI (0.03) W-4 Al / Bl (95/5) ΠΙ-41 1-2 (0.1) Π-2 (0.5) (41) DBN (0.02) Wl Al / Bl (95/5) III-42 1-8 (0.15) U-1 (0.6) (42) TPI (0,03) Wl Al / Bl (80/20) IIM3 1-11 (0.1) Π- 11 (0.6) (43) TPSA (0.02) W-2 Al / Bl (90/10) III44 1-5 (0.2) Π-15 (0.2) (44) HEP (0.01) W-2 A3 / B2 (80 / 20) al (Ol) III-45 1-14 (0.1) Π-2 (0.4) (45) TPI (0.03) W-3 A2 / B1 (90/10) III-46 1-13 (0.2) 11 -12 (0.3) (46) TPA (0.01) W-3 A4 / B1 (90/10) ΠΙ-47 1-11 (0.15) Π-17 (0 · 15) (47) ΤΡΑ (0.007) W-4 Al / Bl (50/50) III-48 1-10 (0.2) II-1 (0.4) (48) DBN (0.02) W-4 Al / Bl (90/10) 111-49 1-8 (0.1) Π-1 (0.7) (49) TPI (0.03) Wl A5 / B2 (90/10) LCB (l) III-50 1-8 (0.15) 11-14 (0.2) (50) TPI (0.02) Wl Al / Bl (95/5) -189-This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 public) 548523 A7 B7 V. Description of the invention (187)-Table 17 Examples of acid generators Resin Alkali-Soluble Interfacial Resin Sword (g) (Π) (g) (10 g) ( ） Sex agent weight ratio (g) (0.03 g) III-51 1-11 (0.05) 11-14 (0.7) (51) TPI (0.03) W-2 Al / B 1 (90/10) III-52 1 -5 (0.2) II-1 (0.3) (52) TPI (0.03) W-2 Al / Bl (95/5) ΠΙ-53 1-14 (0.1) II-1 (0.5) (53) TPI (0.03 ) W-3 Al / Bl (95/5) a5 (0.2) III-54 1-13 (0.2) 11-4 (0.3) (54) DBN (0.02) W-3 Al / Bl (95/5) III -55 1-11 (0.15) 11-16 (0.2) (55) TPI (0.03) W-4 Al / Bl (80/20) III-56 1-10 (0.2) Π-1 (0.15) (56) TPA (O.Ol) W-4 Al / Bl (80/20) ΙΠ-57 1-12 (0.1) 11-1 (0.1) (57) TPI (0.03) W-4 Al / Bl (95/5) ΠΠ-58 1-12 (0.2) 11-8 (0.4) (58) DCMA (O.Ol) W-4 Al / Bl (95/5) ΠΠ-59 1-1 (0.1) 11-13 (0.5) (59) TPI (0.02) W-4 Al / Bl (95/5) ΠΙ-60 1-17 (0.05) 11-8 (0.5) (60) TPI (0.03) W-4 Al / Bl (95/5 ) ΠΙ-61 1-2 (0.1) Π-2 (0.5) (61) DBN (0.02) Wl Al / Bl (95/5) 111-62 1-8 (0.15) II-1 (0.6) (62) TPI (0.03) Wl Al / Bl (80/20) ΠΙ-63 1-11 (0.1) 11-11 (0.6) (63) TPSA (0.02) W-2 Al / Bl (90/10) UI-64 1 -5 (0.2) 11-15 (0.2) (64) HEP (0.01) W-2 A3 / B2 (80/20) al (0.1) III-65 1- 14 (0.1) 11-2 (0.4) (65) TPI (0.03) W-3 A2 / B1 (90/10) Π-66 1-13 (0.2) 11-12 (0.3) (66) TPA (O. Ol) W-3 A4 / B1 (90/10) Comparative Example 1-2 (0.1) (1) DBN (0.02) Wl Al / Bl (95/5) Example mi Comparative Example 11-2 (0.5) (1) DBN (0.02) Wl Al / Bl (95/5) Example m-2 Comparative Example 1-2 (0.1) II-2 (0.5) (1) DBN (0.02) Al / Bl (95/5) f Column III- 3 Comparisons 1-2 (0.1) II-2 (0.5) (1) Wl Al (lOO) Example IIM -190-This paper applies the Chinese National Standard (C NS) A4 specification (210 x 297 male) 548523 A7 B7 _ 5. Description of the invention () The abbreviations in the table are as follows: 〇8 "1,5-diazine bicyclo [4.3.0] non-5-ene butan? 1: 2,4,5-triphenylimidazole TPSA: triphenylphosphonium acetate HEP: N-hydroxyethylhexahydropyridine DIA: 2,6-diisopropylaniline DCMA: dicyclohexylmethylamine LCB : Tertiary butyl lithocholic acid TPA: Triphenylamine TPST: Triphenylsulfonium perfluorobutane sulfonate W1: Megafac F176 (manufactured by Dainippon Chemical & Ink Co., Ltd., fluorine atom matrix) W-2 : Megafac R08 (manufactured by Dainippon Ink & Chemical Co., Ltd., fluorine-based and silicon-based) W-3: polysiloxane polymer KP-34 1 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-4 · · Troy Sol S-366 (manufactured by Troy Chemical Industries, Ltd.) The abbreviations of the solvents are as follows. In the case where multiple solvents are used, the ratios are described in the table by weight ratio. A1: Propylene glycol methyl ether acetate A2: 2-heptanone A3: Ethyl ethoxypropionate A4: γ-butyrolactone A5: Cyclohexanone-191-Applicable Chinese national standard (CNS) Α4 size (210 X 297 male I)

Installation line 548523 A7 -------__ V. Description of the invention (189) A6: Butyl acetate B 1 ·· Propylene glycol methyl ether B2: Ethyl lactate g Image evaluation '(1) DOF (Defocus exposure Tolerance) Using a spin coater, the entire ARC25 anti-reflection layer manufactured by Brewer Technology Co., Ltd. was uniformly coated at a thickness of 600 angstroms on a hexamethyldisilazane-treated substrate, and the substrate was placed on a hot plate It was dried at 100 t for 90 seconds, and then heated and dried at 190 T for 240 seconds. Thereafter, each photosensitive composition was coated on a substrate with a spin coater, and dried for 90 seconds (Examples 丨 "to 1-80 and Comparative Examples 1-1 to I-4 at 14 °. (:, Examples 11] to 11-8〇 and comparative examples to π-4 at 130 ° C, examples III-1-1 to III-66 and comparative example III] to m-4 at 135 ° C) 'Thus obtained a thickness of 0.40 microns Resist film. Here the resist film is exposed through a photomask using an ArF excimer laser stepper (ISi, να: 0.6 (^ ❾force ^ / ^ area irradiation) to complete the exposure “exposure leap second ^ example ^ ～ to ^ 80 and Comparative Examples 1-1 to I · 4 at m ° C, Examples 丨 Bu 丨 to ⑴⑽ and Comparative Examples II-1 to II-4 at 13 (TC, Examples III-1 to III-66 and Control Example: After the film was heated to 135 ° C, the resist film was immediately heated on a hot plate. In addition, the resist was developed at 23 ° C with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide 60 In 13 seconds, "wash with pure water for 30 seconds and dry" to obtain a resist pattern. With the required exposure of 0.1 3 microns line-and-interval (1/1), a defocus exposure tolerance of 0.13 microns can be seen (2) The width of the lateral leaves aRC25 anti-reflection manufactured by ewer technology company 192-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548523

The cold layer is covered with a thickness of 600 angstroms, with a 3 &amp; one, $ 膺 AX overlaid on the substrate which has been treated with methyldisilazane, and the substrate is dried on the hot plate at 100t. 90 seconds, then left to dry at 190 ° C for 240 seconds. Xizhi, ν &gt; "Persons are in, after and after, each photosensitive animal composition is coated on a substrate with a spin coater, and dried for 90 seconds (Examples 丨 to ⑽ and Comparative Examples 1-1) To I · 4 at 140 ° C, Examples Comparative Examples ⑹ to ⑹ At 130 ° C, Reward Examples III-1 to III-66 and Comparative Examples Ι •• to ni-4s135Qc), so a 0.40 micron thick resist was obtained Thin film. Here, the resist film passes through a dot phase shift mask with a penetration of 6% and is exposed by ArF excimer laser stepping (ISI Corporation, NA · 0.6) and exposed for 90 seconds (examples to and Comparative Examples 1-1 to I-4 are at i4o, Examples mI-8〇 and Comparative Examples Η] to II-4 are at 130 ° C, Examples 111-1 to 111-66 and Comparative Examples are to 1 35 ° C) immediately after heating the resist film on a hot plate. In addition, the resist was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 2 3 C for 60 seconds, washed with pure water for 30 seconds, and dried, thereby obtaining a contact hole pattern. The ideal exposure dose Eop is the exposure dose with an exposure hole of .18 microns opened with a mask size of 1 / 2.20 microns, and the side leaflet can be obtained from the following formula. The relative exposure Es, this value is used as the lateral lobe amplitude. The higher the value, the higher the lateral leaf resistance. Lateral leaf width (〇 / 〇) = [(Es-Eop) / Eop] x 100 (3) Particles. The prepared photosensitive composition was left at 4 ° C for 1 week, and manufactured by Lyon Corporation. The particle counter counts the number of particles with a particle size of 0 2 microns or larger in the solution. __-193-Paper & Ruler General Chinese National Standard (CDn grid (2ΐ〇χ 297 公 楚) 548523 A7 B7 V. Description of the invention () Table 18 Example label DOF (micron) Side leaf width (%) Particle 1-1 0.6 2 1 &lt; 5 1-2 0.6 24 5 1-3 0.6 26 &lt; 5 1-4 0.8 29 &lt; 5 1-5 0.8 25 &lt; 5 1-6 0.8 30 &lt; 5 1-7 0.6 28 &lt; 5 1-8 0.8 3 1 &lt; 5 1-9 0.7 22 &lt; 5 1-10 0.9 32 &lt; 5 1-11 0.7 21 &lt; 5 1-12 0.8 27 &lt; 5 M3 0.6 22 &lt; 5 1-14 0.8 29 &lt; 5 1-15 0.7 28 &lt; 5 1-16 0.8 26 &lt; 5 1-17 0.9 33 &lt; 5 1-18 0.7 30 &lt; 5 1-19 0.8 29 &lt; 5 1-20 0.8 25 &lt; 5 1-21 0.8 24 &lt; 5 1-22 0.7 24 &lt; 5 1-23 0.8 24 &lt; 5 1-24 0.9 33 &lt; 5 1-25 0.8 29 &lt; 5 -194 -This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 public goods) 548523 A7 B7 V. Description of the invention (192) Table 19 Example label DOF (micron) Side leaf width (%) Particles 1-26 0.8 3 1 &lt; 5 1-27 0.8 30 &lt; 5 1-28 0.7 29 &lt; 5 1-29 0.8 25 &lt; 5 1-30 0.7 28 &lt; 5 1-3 1 0.8 24 &lt; 5 1-32 0.8 29 &lt; 5 1-33 0.9 26 &lt; 5 1-34 0.9 33 &lt; 5 1 -35 0.8 31 &lt; 5 1-36 0.7 28 &lt; 5 1-37 0.8 30 &lt; 5 1-38 0.7 28 &lt; 5 1-39 0.8 29 &lt; 5 1-40 0.7 26 &lt; 5 1-41 0.6 24 &lt; 5 1-42 0.8 27 &lt; 5 1-43 0.8 27 &lt; 5 1-44 0.9 34 &lt; 5 1-45 0.8 28 &lt; 5 1-46 0.9 33 &lt; 5 1-47 0.8 3 1 &lt; 5 1-48 0.8 30 &lt; 5 1-49 0.8 26 &lt; 5 1-50 0.8 3 1 &lt; 5 -195-This paper size applies to China National Standard (CNS) A4 (210X297 mm) 548523 A7 B7 V. Description of the invention (193) Table 20 Example label DOF (micron) Side leaf width (%) Particles 1-51 0.7 25 &lt; 5 1-52 0.8 30 &lt; 5 1-53 0.8 24 &lt; 5 1- 54 0.8 30 &lt; 5 1-55 0.8 3 1 &lt; 5 1-56 0,7 28 &lt; 5 1-57 0.7 29 &lt; 5 1-58 0.7 30 &lt; 5 1-59 0.7 25 &lt; 5 1 -60 0.7 25 &lt; 5 1-61 0.7 25 &lt; 5 1-62 0.7 27 &lt; 5 1-63 0.7 25 &lt; 5 1-64 0.9 34 &lt; 5 1-65 0.8 30 &lt; 5 1-66 0.6 35 &lt; 5 1-67 0.8 36 &lt; 5 1-68 0.9 38 &lt; 5 1-69 0.8 37 &lt; 5 1-70 0.9 39 &lt; 5 1-71 0.8 45 &lt; 5 1-72 0.9 41 &lt; 5 ______ 1-73 0.8 40 &lt; 5 1-74 0.9 38 &lt; 5 1-75 0.8 37 -196-this paper size is applicable National Standard (CNS) A4 specification (210 X 297 mm) 548523 A7 B7 V. Description of the invention (194) Example label DOF (micron) Side leaf width (%) Particle 1-76 0.8 45 &lt; 5 1-77 0.9 41 &lt; 5 1-78 0.8 40 &lt; 5 1-79 0.9 38 &lt; 5 1-80 0.8 37 &lt; 5 Comparative Example 1-1 0.4 16 &lt; 5 1-2 0.5 12 &lt; 5 1-3 0.3 9 &lt; 5 1-4 0.4 10 145 -197-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7 V. Description of the invention (195) Table 22 Example label DOF (micron) side Leaf amplitude (%) Particles 11-1 0.6 23 &lt; 5 II-2 0.6 25 10 II-3 0.7 27 &lt; 5 II-4 0.8 34 &lt; 5 II-5 0.7 29 &lt; 5 II-6 0.8 30 &lt; 5 ΪΙ-7 0.7 28 &lt; 5 II-8 0.8 32 &lt; 5 II-9 0.7 27 &lt; 5 11-10 0.7 26 &lt; 5 II-1 1 0.7 25 &lt; 5 11-12 0.8 32 &lt; 5 11-13 0.7 23 &lt; 5 11-14 0.8 33 &lt; 5 11-15 0.8 29 &lt; 5 11-16 0.8 35 &lt; 5 11-17 0.9 34 &lt; 5 11-18 0.7 34 &lt; 5 11 -19 0.8 35 &lt; 5 11-20 0.8 38 &lt; 5 11-21 0.8 39 &lt; 5 11-22 0.8 40 &lt; 5 11-23 0.8 40 &lt; 5 [1-24 0.9 45 &lt; 5 11- 25 0.9 44 &lt; 5

Pretend

-198-This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 548523 A7 B7 V. Description of invention (196) Table 23 Example label DOF (micron) Side leaf width (%) Particle 11 -26 0.8 38 &lt; 5 11-27 0.8 41 &lt; 5 11-28 0.7 37 &lt; 5 11-29 0.8 38 &lt; 5 11-30 0.7 37 &lt; 5 II-3 1 0.8 37 &lt; 5 11- 32 0.8 38 &lt; 5 11-33 0.9 41 &lt; 5 11-34 0.9 40 &lt; 5 11-35 0,8 37 &lt; 5 11-36 0.7 36 &lt; 5 11-37 0.8 37 &lt; 5 11- 38 0.7 35 &lt; 5 11-39 0.8 36 &lt; 5 11-40 0.7 35 &lt; 5 11-41 0.7 35 &lt; 5 11-42 0.8 38 &lt; 5 11-43 0.8 37 &lt; 5 11-44 0.9 45 &lt; 5 11-45 0.9 46 &lt; 5 11-46 0.9 46 &lt; 5 11-47 0.8 39 &lt; 5 11-48 0.8 40 &lt; 5 11-49 0.8 41 &lt; 5 11-50 0.8 39 &lt; 5

Pretend

-199-The size of this paper is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7 V. Description of the invention (197) Table 24 Example label DOF (micron) Side leaf width (%) Particles 1 0.8 38 &lt; 5 11-52 0.8 37 &lt; 5 11-53 0.8 38 &lt; 5 11-54 0.8 37 &lt; 5 11-55 0.8 38 &lt; 5 11-56 0.8 39 &lt; 5 11-57 0.7 39 &lt; 5 11-58 0.7 38 &lt; 5 11-59 0.7 38 &lt; 5 11-60 0.7 38 &lt; 5 11-61 0.7 39 &lt; 5 11-62 0.7 41 &lt; 5 11-63 0.7 40 &lt; 5 11-64 0.9 45 &lt; 5 11-65 0.9 48 &lt; 5 11-66 0.6 41 &lt; 5 11-67 0.8 36 &lt; 5 11-68 0.9 35 &lt; 5 11-69 0.8 40 &lt; 5 11-70 0.9 38 &lt; 5 11-71 0.8 39 &lt; 5 11-72 0.9 37 &lt; 5 11-73 0.8 41 &lt; 5 11-74 0.9 35 &lt; 5 11-75 0.8 36 &lt; 5 -200 -This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 548523 A7 B7 V. Description of the invention (198) Table 25 Example label DOF (micron) Side leaf width (%) Particles 11-76 0.8 35 &lt; 5 11-77 0.9 36 &lt; 5 11-78 0.8 37 &lt; 5 11-79 0.9 38 &lt; 5 11-80 0.8 37 &lt; 5 Comparative Example IM 0 .5 18 &lt; 5 II-2 0.4 15 &lt; 5 II-3 0.5 20 98 II-4 0.2 8 ^ _ -201-This paper size applies to China National Standard (CNS) Λ4 (210 X 297 mm) 548523 A7 B7 V. Description of the invention (199) Table 26 Example label DOF (micron) Side leaf width (%) Particle III-1 0.6 21 &lt; 5 III-2 0.6 22 5 III-3 0.7 27 &lt; 5 III-4 0.8 31 &lt; 5 III-5 0.8 26 &lt; 5 III-6 0.8 28 &lt; 5 III-7 0.7 25 &lt; 5 III-8 0.8 30 &lt; 5 III-9 0.7 26 &lt; 5 III-10 0.9 25 &lt; 5 ΙΪΙ-1 1 0.7 23 &lt; 5 IIM2 0.8 30 &lt; 5 III-13 0.6 21 &lt; 5 III-14 0.8 31 &lt; 5 III-15 0.7 28 &lt; 5 III-16 0.8 33 &lt; 5 III -17 0.9 32 &lt; 5 III-18 0.7 32 &lt; 5 III-19 0.8 34 &lt; 5 III-20 0.8 36 &lt; 5 III-21 0.8 37 &lt; 5 III-22 0.8 39 &lt; 5 [11- 23 0.8 38 &lt; 5 III-24 0.9 43 &lt; 5 [11-25 0.8 42 &lt; 5 m binding

Line-202-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 cm) 548523 A7 B7 V. Description of the invention (200) Table 27 Example number DOF (microns) Side leaf width (% ) Particles ΙΙΙ-26 0.8 36 &lt; 5 ΙΙΙ-27 0,8 39 &lt; 5 ΙΙΙ-28 0.7 34 &lt; 5 ΙΙΙ-29 0.8 37 &lt; 5 ΙΙΙ-30 0.7 36 &lt; 5 ΙΙΙ-31 0.8 36 &lt; 5 ΙΙΙ-32 0.8 37 &lt; 5 ΙΙΙ-33 0.9 40 &lt; 5 ΙΙΙ-34 0.9 38 &lt; 5 ΙΙΙ35-36 0.8 36 &lt; 5 ΙΙΙ-36 0.7 34 &lt; 5 ΙΙΙ-37 0.8 36 &lt; 5 ΙΙΙ-38 0.7 34 &lt; 5 ΙΙΙ-39 Γ 0.8 35 &lt; 5 ΙΙΙ-40 0.7 33 &lt; 5 ΙΙΙ-41 0.7 33 &lt; 5 ΙΙΙ-42 0.8 36 &lt; 5 ΙΙΙ-43 0.8 36 &lt; 5 ΙΙΙ -44 0.9 43 &lt; 5 ΙΙΙ-45 0.9 44 &lt; 5 ΙΙΙ-46 0.9 44 &lt; 5 ΙΙΙ-47 0.8 37 &lt; 5 ΙΙΙ-48 0.8 39 &lt; 5 ΙΙΙ-49 0.8 40 &lt; 5 ΙΙΙ-50 0.8 38 &lt; 5 -203-This paper size applies Chinese National Standard (CNS) A4 (21ϋ X 297mm) 548523 A7 B7 V. Description of the invention (201) Table 28 Example number DOF (micron) Side leaf width (%) Granule III-5 1 0.8 36 &lt; 5 III-52 0.8 35 &lt; 5 III-53 0.8 36 &lt; 5 III-54 0.8 35 &lt; 5 III-55 0.8 36 &lt; 5 III-56 0.8 37 &lt; 5 111 ^ 57 0.7 37 &lt; 5 111〇8 0.7 35 &lt; 5 ΠΙο9 0.7 36 &lt; 5 ΙΙΙ-60 0.7 35 &lt; 5 ΙΙΙ-61 0.7 37 &lt; 5 ΙΙΙ-62 0.7 40 &lt; 5 ΙΙΙ63-38 0.7 38 &lt; 5 ΙΙΙ-64 0.9 44 &lt; 5 ΙΙΙ-65 0.9 46 &lt; 5 ΙΙΙ-66 0.6 38 &lt; 5 Comparative Example III- 1 0.5 16 &lt; 5 Comparative Example III-2 0.7 14 &lt; 5 Comparative Example III-3 0.4 16 93 Control Example III-4 0.5 13 146 -204-This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297) 202) 5. Description of the invention From the above results, the following facts can be seen. Excellent lateral leaf resistance The composition of the present invention has a wide defocus exposure tolerance and produces almost no particles. On the other hand, the composition of the comparative example was inferior to the composition of the present invention in resistance to defocus exposure and particle generation. ^ / Use area to illuminate Temple B. The positive desensitization of a positive photosensitive compound of a specific example of the present invention has a wide tolerance for defocus exposure, and is mapped with a mesh phase shift mask. It is not easy to cause side leaves when it is formed, and it is aged and stored. Hardly produces particles. Preparation and composition of the resist composition are shown in Tables 29 to 3 (2 g), the resin (2 g), photoacid generator, organic basic compound (amine) (5 mg) and The required surfactant (10 mg) is blended as shown in Tables 29 to 31, dissolved in a solvent shown in Tables 29 to 31 at a solid content concentration of 14% by weight, and filtered through a pore size of 0 μm The filter was used to prepare Examples [VdSZVdO and Comparative Example π] and each positive-type resist composition in IV-2. In Comparative Example IV-1, a resin synthesized in accordance with Example 10 of Japanese Patent 3042618 was used, which had the structure shown below (equivalent to Resin A hereinafter). CH3

(Resin A, x = 0.7, y = 0.3, Mw = 9,500) -205-This paper is compliant with China National Standard (CNS) A4 (210 x 297 mm) 548523 A7 B7

548523 A7 B7 V. Description of the invention (204) Table 29 Example number Resin photoacid generator (mg) Solvent surfactant amine IV-1 71 M / IIM2 (25/30) S1 1 1 IV-2 72 I-2 / II-4 (42/30) S1 4 2 IV-3 73 I-2 / II-1 (28/40) S1 / S5 (80/20) 2 3 IV-4 74 III-3 / II-7 (40 / 60) S1 / S7 (95/5) 5 4 IV-5 75 I-5 / II-5 (32/30) S1 / S2 (85/15) 3 5 IV-6 76 111-10 / 11-10 (45/48) S1 / S9 (92/8) 2 6 IV-7 77 I-6 / II-8 (40/40) S1 / S5 / S8 (80/13/7) 1 6 IV-8 78 I -3 / III-2 (40/20) S1 / S2 / S8 (75/15/10) 2 6 IV-9 79 III-3 / IM0 (62/20) S2 / S3 (60/40) 5 5 IV -10 80 IIM7 / II-9 (45/25) S2 / S6 (70/30) 5 3 IV-11 81 I-8 / IIM1 (36/25) S1 / S2 (82/18) 3 4/5 ( 1/1) IV-12 82 111-1 / 11-19 (68/35) S1 / S4 (65/35) 5 5 IV-13 83 1-10 / IIl · 1 (40/40) S1 / S5 ( 75/25) 2 4 IV-14 84 111-1 / 111-8 (50/20) S1 1 1 IV-15 85 I-11 / III-2 (34/15) S1 / S6 (80/20) 2 1 IV-16 86 III-1 / IM1 (63/30) S1 / S9 (90/10) 5 2 IV-17 87 I-12 / IIM (41/25) S1 / S8 (92/8) 5 3 IV -18 88 1-18 / 11-14 (40/35) S1 / S2 / S9 (78/18/4) 3 4 IV-19 89 I-17 / III-2 (37/30) S1 / S5 / S10 (75/20/5) 3 5 IV-20 90 111- 3 / 11-12 (55/60) Sl / S7 (93/7) 5 4/5 (2/1) IV-21 91 I-19 / III-7 (40/5) S1 / S6 / S8 (80 / 16/4) 5 4 IV-22 92 1-21 / 11-18 (30/60) S2 / S3 (70/30) 2 6 IV-23 93 1-20 / 11-14 (34/38) S2 / S6 / S9 (60/25/15) 1 6 IV-24 94 III-3 / IM1 (58/60) S2 / S6 (85/15) 3 5 IV-25 95 111-1 / 11-10 (60 / 45) S2 / S3 / S7 (70/22/8) 5 4 -207-This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 public and redundant) 548523 A7 B7 V. Description of the invention (205) Table 30 Example Resin Photoacid Generator (mg) Solvent Surfactant Amine IV-26 96 IIM / IM1 (60/60) S4 / S2 (80/20) 4 3 IV-27 97 I-21 / III-2 (20 / 30) S4 / S5 / S8 (65/35/5) 3 2 IV-28 98 1-15 / 11-19 (43/38) S4 / S2 / S9 (62/35/3) 2 1 IV-29 99 I-2 / III-5 (32/10) S4 / S5 (70/30) 1 2 IV-30 71 I-1 / III-4 (5/40) S1 / S6 (80/20) 1 4 IV- 31 72 1-6 / 111-6 (40/12) S2 / S3 / S8 (72/18/10) 5 5 IV-32 73 III-3 / II-7 (60/35) S1 / S6 / S9 ( 70/20/10) 5 5 IV-33 74 1-7 / 11-10 (38/15) S2 / S6 / S1 (75/20/5) 5 6 IV-34 75 1-11 / 11-8 ( 40/30) S4 / S2 (80/20) 5 6 IV-35 76 I-12 / IV-12 (39/11) S4 / S6 / S9 (75/18/7) 5 4 IV-36 77 III- 3 / II-12 (70/30) S4 / S5 (90/10) 3 5 IV-37 78 M3 / IM1 (40/28) S4 / S2 / S7 (80/16/4) 2 6 IV-38 79 IIM7 / II-13 (65/40) S4 / S6 (85/15) 1 1 IV-39 80 IV-1 / II-20 (48/40) S4 / S6 / S8 (78/18/4) 1 2 IV- 40 81 1-14 / 111-15 (36/30) S4 / S6 (75/25) 1 1 IV-41 82 IV-3 / II-22 (75/30) S4 / S6 / S7 (70/26 / 4) 2 1 IV-42 83 I-17 / 11-15 (34/48) S1 / S3 (70/30) 2 2 IV-43 84 111-14 / 11-14 (40/30) S1 / S2 / S8 (68/30/2) 3 4 IV-44 85 1-8 / 11-10 (42/35) Sl / S7 (92/8) 5 3 IV-45 86 M4 / III-1 (35/34) S1 / S2 / S7 (70/26/4) 5 4 IV-46 87 I-9 / II-11 (45/45) S2 / S6 / S7 (60/28/12) 5 3/5 (1/1 ) IV-47 88 I-7 / II-1 1 (33/60) S1 / S5 / S8 (65/30/5) 1 1/6 (1/1) IV-48 89 111-1 / 11-10 (58/40) S2 / S6 / S8 (60/30/10) 1 5 IV-49 90 M1 / II-I 1 (35/70) S1 / S5 / S9 (70/24/6) 1 4 IVoO 91 III-3 / II-8 (45/68) S4 / S2 / S7 (80/12/8) 1 2 -208-The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 548523 A7 B7 V. Description of the invention (206) Table 3 1 Example series 5 Tiger resin photoacid generator (mg) Solvent surfactant amine IV-51 92 1-12 / 111-2 (32/80) S1 / S5 / S8 (65 / 35/5) 5 2 IV-52 93 III-3 / II-7 (80/45) S1 / S6 / S9 (70/25/5) 5 3 IV-53 94 I-5 / III-2 (38/25) S4 / S6 / S7 (65/30/5) 3 4 IV-54 95 III-3 / II-8 (72/50) S4 / S6 / S8 (70/28/2) 3 5 IV-55 96 I-8 / II -9 (36/48) S4 / S2 / S7 (70/20/10) 1 6 IV-56 97 III-3 / II-10 (60/40) S4 / S6 / S9 (65/27/5) 1 6 IV-57 98 I-6 / III-1 (42/32) S1 / S7 (94/6) 2 4 IV-58 99 111-3 / 11-11 (62/40) S1 / S7 (96/4 ) 2 3 IV-59 71 1-8 / 11-12 (30/38) S1 1 IV-60 72 M0 / II-11 (32/60) S1 '5 Comparative Example IV-1 Resin A 1-1 (20 ) S1 Comparative Example IV-2 Resin B Compound (A) (50) S1 3 -209-This paper size applies Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) 548523 A7 B7

V. Description of the invention (207) W -1 · Megafac F 1 76 (manufactured by Dainippon Chemicals and Ink Co., Ltd., 7 atom ^, manufactured by fluorine atom matrix) Division A W-2: Megafac R08 (Dainippon Ink and Chemical Product Co., Ltd. 77 Co., Ltd., fluorine matrix and silicon matrix) Division A W-3: polysilicon polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Co., Ltd. W-4: Troy Sol S -366 (manufactured by Troy Chemical Industry Co., Ltd.) As an amine: 1: 1,5-diazinebicyclo [4.3.0] non-5 · ene (DBN) 2 ·· bis (1,2,2,6,6- Pentamethyl-4-hexahydropyridine) Sebacic acid Purpose 3: Tri-n-butylamine 4: Triphenyl Weijun 5: Antipyrine 6: 2,6-diisopropylaniline as solvent: S1: propylene glycol monomethyl ether acetate 52: ethyl lactate 53: butyl lactate 54: 2-heptanone S5: propylene glycol monomethyl ether S6: ethyl ethoxypropionate S7: γ-butyrolactone S 8: Ethylene carbonate S 9: Ethylene carbonate-210-This paper applies the Chinese National Standard (CMS) A4 specification (210X297 mm) 548523 A.7 B7

V. Description of the invention (208) Compound (A)

Evaluation test: A spin coater was used to coat ARC25 (manufactured by Brewer Technology) on a silicon wafer at a thickness of 30 nm and dried. Then, the prepared positive resist was combined by a spin coater. A chemical solution is coated thereon. Resins 71 to 80 were used for 90 seconds at 130 ° C, and other samples were dried at 140 ° C for 90 seconds. Thus, a positive-type photosensitive film having a thickness of about 0.4 micrometers was prepared. ArF excimer laser (193 亳 microns) was used to expose each resist. After exposure, heat treat samples using resins 71 to 80 at 120 C for 90 seconds, heat treat other samples at 130 ° C for 90 seconds, and then develop them with 2.38% by weight tetramethylammonium hydroxide hydrochloride solution to wash them with distilled water. A resist pattern profile is thus obtained. The resist pattern of the thus obtained wafer was observed with a scanning electron microscope (SEM) and evaluated as follows. The floor evaluation results are shown in Tables 32 to 35 below. The coefficient of variation of the line width caused by the exposure of the PED to the 0.1 3 micron line pattern (let /, let stand for 60 minutes at 23 C after exposure) is obtained from the following formula, and the pED foot-footing is obtained from Value for evaluation. -211-

548523 A7 B7 V. Description of the invention (209) PED stability (%) = | (line width of aging pattern after exposure (0.13 microns))-(line width of heat treated immediately after exposure)! / (〇 · 13 microns) x 10〇 PED adjusts the lapse of the mountain at any time. The stability of the PED was evaluated by allowing the positive resist composition to stand at 4 ° C for 1 week. The following formula can be used to obtain the double-action coefficient of the line width before and after storage, and the value can be used to evaluate the change of PED over time. PED change over time (%) = | (PED stability before aging (%))-(PET stability after aging (%)) | / (PED stability before aging (%)) x 1〇 〇 Sensitive action before and after aging. Therefore, the sensitivity of the positive resist composition was evaluated immediately after the preparation (exposure before aging) and after leaving it to stand at 4 ° C for 1 week (exposure before aging). The coefficient of variation of sensitivity can be evaluated by the value obtained according to the following formula. The coefficient of variation of the sensitivity (%) is called (exposure before aging)-(exposure after aging) | / (exposure before aging) x 100 side leaf resistance through the dot phase shift mask to analyze the 0.22 micron pattern It was 0.2 microns and a pattern of 0.18 microns was visible. Complete the assessment by the following criteria. 〇: No lateral leaves were seen at all. See slightly lateral leaves. X: Lateral lobes are clearly visible. Pitch dependence In the contact hole pattern (fine pattern) of 0.16 micrometers and the independent contact hole pattern (coarse pattern), a depth of focus overlap range that can tolerate 0.20 micrometers ± 10% is obtained. The larger this range is, the better the hole distance dependency is. Exposure width Tang -212-This paper is in accordance with China National Standard (CNS) A4 specifications (210X297 public goods) 548523 V. Description of the invention 210) A7 B7

The percentage (%) represents the value obtained by copying (the exposure range of the M6 micron ± ι% line width divided by the ideal exposure amount, and the copying exposure amount of 0.16 micron is used as the ideal exposure amount. This value The larger the change, the more the line width caused by the change in the exposure. / J ,. 专 Special film reduces the uniformity. The contact hole of 0.16 micrometers obtained above is etched with 8/2 chf3 / 〇2 plasma for 60 seconds. Observe the cross-section and surface of the obtained sample by SEM. The estimation is completed by the following standards. X: Pinhole-like defects (the part underneath the etching is not processed).-: Holes with cracks on the surface but no defects and accompanying deformation 〇: The surface is rarely cracked and the holes are not deformed. -213-This paper size is applicable to China National Standard for Scrubbing (CNS) A4 (210 X 297 mm) 548523 A7 B7 5. Description of the invention (211) Table 32 Example number PED Stability (%) Sensitivity change (%) PED change with aging (%) Mesh exposure latitude (side leaf resistance) Pitch dependence (micron) Exposure range (%) Thin film reduction uniformity IV-1 5 8 6 0 0.6 9-IV-2 5 9 6 0 0.5 7-IV-3 4 6 5 0 0.6 9-IV-4 4 6 5 0 0.6 9-IV-5 4 6 5 0 0.6 9-IV-6 4 6 5 0 0.6 9-IV-7 4 5 4 0 0.6 9-IV-8 4 5 4 0 0.6 9-IV-9 5 6 5 0 0.6 9-IV-10 5 6 5 0 0.6 9-IV-11 4 5 4 0 0.6 10 0 IV-12 4 7 5 0 0.6 10 0 IV-13 4 5 4 0 0.6 10 0 IV-14 4 7 5 0 0.6 10 0 IV-15 4 5 4 0 0.6 10 0 IV-16 4 5 4 0 0.6 10 0 IV-17 4 5 4 0 0.6 10, 1 IV-18 3 4 3 0 0.6 10-0 IV-19 3 4 3 0 0.6 10 0 IV-20 4 5 4 0 0.6 10 0 i Staple

Line-214-This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 548523 A7 B7 V. Description of invention (212) Table 33 Example number PED stability (%) Sensitivity change (%) PED with aging Variation (%) Mesh exposure latitude (side leaf resistance) Pitch dependence (micron) Exposure width (%) Film uniformity reduction IV-21 4 4 3 0 0.6 10 0 IV-22 4 5 4 0 0.6 10 0 IV-23 3 4 3 0 0.6 10 0 IV-24 4 5 4 0 0.6 10 0 IV-25 3 4 3 0 0.6 10 0 IV-26 4 5 4 0 0.5 8 0 IV-27 3 4 3 0 0.6 10 0 IV-28 3 4 3 0 0.6 10 0 IV-29 4 5 4 0 0.6 10 0 IV-30 5 7 5 0 0.6 10-IV-31 4 5 4 0 0.6 10-IV-32 4 5 4 0 0.6 10 -IV-33 4 5 4 0 0.6 10-IV-34 5 7 5 0 0.6 10-IV-35 4 5 4 0 0.6 10-IV-36 5 7 5 0 0.6 10-IV-37 4 5 4 0 0.6 10 -IV-38 5 7 5 0 0.6 10-IV-39 4 5 4 0 0.6 10-IV-40 4 5 4 0 0.6 10 0

Pretend

Line-215-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 male f) 548523 A7 B7 V. Description of the invention (213) Table 34 Example number PED Stability (%) Sensitivity change (%) PED varies with Aging change (%) Mesh exposure latitude (side leaf resistance) Pitch dependence (micron) Exposure range (%) Film uniformity reduction IV-41 3 4 3 0 0.6 10 0 IV-42 4 6 5 0 0.6 10 0 IV-43 3 4 3 0 0.6 10 0 IV-44 4 5 4 0 0.6 10 0 IV-45 3 4 3 0 0.6 10 0 IV-46 3 4 3 0 0.6 10 0 IV-47 3 4 3 0 0.6 10 0 IV-48 3 4 3 0 0.6 10 0 IV-49 3 4 3 0 0.6 10 0 IV-50 3 4 3 0 0.6 10 0 IV-51 3 4 3 0 0.6 10 0 IV-52 3 4 3 0 0.6 10 0 IV-53 3 4 3 0 0.6 10 0 IV-54 3 4 3 0 0.6 10 0 IV-55 3 4 3 0 0.6 10 0 IV-56 3 4 3 0 0.6 10 0 IV-57 4 5 4 0 0.6 10 0 IV-58 4 5 4 0 0.6 10 0 IV-59 6 10 7 0 0.4 6-IV-60 6 11 6 0 0.5 7--216-This paper size applies to China National Standard (CNS) A4 (210 X 297 public goods) 548523 A7 B7 V. Description of the invention (214) Table 3 5 Example PED Sensitivity PED decreases with the exposure width of the mesh depending on the exposure film No. Stability change Aging and volume change (low average width of lateral leaf (%) (%) dynamic (%) resistance) (micron) (%) uniformity control example 10 25 15 X 0.2 2 X IV-1 control Example 15 20 17 X 0.2 3 X IV-2 It is obvious from the above results that the composition of the present invention exhibits excellent performance in mesh exposure latitude, hole pitch dependence, and exposure range, and thus can prevent sensitivity caused by aging storage. change. In addition, the composition of the present invention exhibits excellent PED stability and stability of PED over time, so it can prevent PED changes caused by aging, and when the resin is oxidized and etched, the composition reduces the uniformity of the film. Also perform outstandingly. The composition of the second specific example of the present invention has latitude to far ultraviolet rays, especially to ArF excimer lasers with a wavelength of 193 nm, and exhibits extreme tolerance in mesh exposure latitude, hole pitch dependence, and exposure range. It can prevent sensitivity changes caused by aging storage. In addition, the composition of the present invention exhibits excellent PED stability, thereby preventing PED from changing due to aging, and the composition is also excellent in reducing the uniformity of the film when the resin is oxidized and etched. Therefore, the composition of the present invention can be perfectly used for the use of far ultraviolet rays, including -217-This paper size is applicable to National Standards (CNS) A4 specifications (210X 297 mm) 548523 A7 B7 V. Description of the invention (215)

ArF excimer laser exposure lithography. Foreign experts familiar with this technology and its spirit When the present invention has been described in detail with reference to specific examples thereof, it will be clearly understood that various changes and modifications can be made therein without departing from the scope. Each and every patent application that has been declared in this patent application is incorporated herein by reference in its entirety. -218-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm).

Claims (1)

548523 Patent application Fanyuan 1. A positive type photosensitive composition, comprising: (:) 1 Actinic rays and light shots can produce housing agents when irradiated; (β) pine nut grease has a single ring or Multi-day dagger J. Pingyi 4th J. Moon and sun bad hydrocarbon structure; and can be decomposed under the action of acid to increase the solubility in alkaline developer; (c) a test compound; and (D) — A surfactant containing at least one of a chlorine atom and a silicon atom; wherein the acid generator (A) comprises at least two selected from the group consisting of a sulfonium salt compound having no aromatic ring, a triarylsulfonium salt compound, and a benzamidine A group of compounds consisting of compounds of the methyl ilL salt structure. 2. The positive-type photosensitive composition as described in claim 1 of the patent scope, which comprises (E) a solvent warm compound, the mixture comprising: a solvent containing a #i group; and a solvent containing no group. 3. The positive-type photosensitive composition according to item 1 of the application, wherein the basic compound (C) contains at least one selected from the group consisting of an imidazole structure, a bi-bicyclic structure, a fluorene hydroxide structure, and a phosphonium salt structure. And aniline structure. 4. The positive-type photosensitive composition according to item 1 of the patent application scope, further comprising (F) a low-molecular-weight dissociation-inhibiting compound having a molecular weight of 3,000 or less; and one that can decompose by the action of an acid It is based on increasing the solubility in sexually humiliating shadows. 5. If the positive photosensitive composition is applied for item 1 in the scope of application, wherein the acid generator (A) contains a triarylsulfonium salt compound and has a styrylmethylsulfonium-methylfluorene-219 (CNS) A4 specification (210 X 297 mm) 548523 AB c D 6. Compounds with salt structure in the scope of patent application. 6. The positive-type photosensitive composition according to item 1 of the application, wherein the acid generator (A) comprises a phosphonium salt compound having no aromatic ring and a compound having a benzyl methyl phosphonium salt structure. 7. The positive-type photosensitive composition according to item 1 of the application, wherein the acid generator (A) comprises a sulfonium salt compound having no aromatic ring and a triarylsulfonium salt compound. 8. The positive-type photosensitive composition according to item 1 of the patent application range, wherein the resin (B) comprises at least one repeating unit selected from the group consisting of the following units: part of the structure includes the following formulae (pi), (pll) , (ΡΙΠ), (pIV), (pv), or (pVI) repeating units of alicyclic hydrocarbons; and repeating units represented by formula (II-AB): «11 卜 一 ', /?! (PI) ^ 12 —C-R13 _ r14 rio-ch 5 i— RR——cl IV) (P R21 20 This paper size applies to Chinese National Standard (CNS) A4 (2l0x 297 mm)) 48523 Application for patents "22『 23 〇-C —CH—C-r24 (pV) ^ 25 〇. 巧 ”II * \ 〆- 一 — ,, / —C—〇—Ρ ,, ('PVI) II Second Middle School Rh represents methyl, ethyl, n-propyl, isopropyl, n-butyl, well-butyl, or second butyl; z represents an alicyclic 1 group &lt; atom group that must be formed with a carbon atom; Ri2, Ri3 , Each independently represents a linear or branched alkyl group having from 1 to 4 carbon atoms, or an alicyclic alkyl group is known as R! 2, at least one of Rn and R14 represents an alicyclic hydrocarbon group, and R15 and R16 At least one represents an alicyclic hydrocarbon group; R, R19, R20, and Ru each independently represent a hydrogen atom, a straight or branched alkyl group having from 4 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that R17, At least one of R18, R! 9, Chi20 and Rh represents an alicyclic hydrocarbon group, and at least one of Chi ^ and ^! Represents a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group ; R22, R23, Chi24, and Rh each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R22, R23, R24, and R25 represents an alicyclic ring Hydrocarbyl Moreover, R23 and R24 can be bonded to each other to form a ring; Z: 'R11 r12 · -221-This paper is fully compliant with the Chinese National Standard (CNS) A4 specification (210 X 297 issued) 548523 AB CD Among which the scope of patent application is Rii and R! 2 each independently represent a hydrogen atom, a cyano group, a halogen atom, or a pit group that may have a substituent; Z 'represents an atomic group that must form an alicyclic structure with two lean atoms (c -C) The group may have a substituent. 9 ♦ For example, the positive photosensitive composition of the eighth item of the patent claim, wherein Z ′ in the formula (η _ ΑΒ) must form a bridge containing two carbon atoms (cc) together. The atomic group of the alicyclic structure may have a substituent. 10. The positive-type photosensitive composition according to item 8 of the patent application scope, wherein the compound represented by the formula (Π-AB) is represented by the formula (HA) or ( II-B) means: (Work 1-A) R Where R [3 ', R! 4, and Rbmw each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -C〇〇R5, a group that can be decomposed under the action of an acid, -C (= 0 ) -X-A'-Ri /, an alkyl group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent; R5 represents an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent, or is shown below -Y group; X represents an oxygen atom, a sulfur atom, -NH-, -NHS〇2-or -NHSO2NH-; A 'represents a single bond or a divalent linking group; R &quot;, R &quot;, R15 •, and R; At least -222-The meaning of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 548523 8 8 8 8 AB c D 6. The scope of patent application can be bonded to each other to form a ring; n represents 〇 or 1; RU, which represents -CO〇H, -C00r5, -CN, hydroxy, alkoxy which may have a substituent, co-NH_R6, -CO-NH-S〇2-R6 or shown below · Γ group; ^ represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent; -Y group: Wherein Han 2 to RW each independently represent a hydrogen atom or an alkyl group which may have a substituent, and a and b each represent 1 or 2. 11. A positive-type photosensitive composition comprising: (A)-a compound that generates an acid when irradiated with one of actinic rays and radiation; and (B 1)-an alkali that can be increased under the action of an acid A resin in a soluble developer, wherein the resin has a repeating unit of a group represented by the following formula (Vl), (V-2), (V-3), or (V-4); and an aliphatic Cyclic hydrocarbon group: -223-The size of this paper conforms to the national standard (CNS) A4 specification (210X 297 mm) 548523 Λ8 B8 C8 Rlb, R2b, R3b, 1141) and 1151) each independently represent a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an alkenyl group which may have a substituent; Rlb, R2b 'R3b Two of R4l ^ R5b can be bonded to form a ring, wherein the acid generator (A) contains at least two compounds selected from the group consisting of a triarylsulfonium salt compound, a compound having a benzamidinemethylsulfonium salt structure, and no aromatic A group of compounds consisting of sulfonium salt compounds. Line 12: The positive change photosensitive composition according to item η of the patent application range, wherein the resin (B) contains at least one repeating unit selected from the group consisting of the following units: part of the structure includes the following formula (pi), (pll ), (Pin), (piv), (pV) or (pVI) repeat unit of alicyclic hydrocarbon, and the repeat unit represented by formula (Η-AB): 1 **-: LC- \ / iz. : RICIR1 2 1 R1 ην ο ^ (PI -224-This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 praise) 548523 ,, where Ru represents methyl, ethyl, n-propyl, isopropyl, n-butyl, well-butyl, or second butyl; Z represents an alicyclic hydrocarbon foot atom group that must be formed with a carbon atom; R 丨2. Rl3, Rl4, each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R! 2, 1113, and 14 is an alicyclic hydrocarbon group, And at least one of r15 and r16 represents an alicyclic hydrocarbon group; each of r, Rm, and Ru independently represents a hydrogen atom, and has a straight or branched alkyl group from 丨 to 4: atom 9, or an alicyclic hydrocarbon group, provided that At least one of R, R! 9, Rm and Ru represents an alicyclic hydrocarbon group, and 7RI9 and 8r '-225-this paper size applies to China National Standard (CNS) A4 (210 X 297 mm) M8523 A8 B8 Medium to / one represents a straight-chain or branched alkyl / 'or cyclic hydrocarbon group having from 4 to 4 carbon atoms; R22, R23, R24, and R25 each independently represent a group having 2 from 1 to 4 carbon atoms A straight-chain or branched alkyl group, or an alicyclic hydrocarbon group, with the proviso that at least one of R22, R23, and "5" represents an alicyclic hydrocarbon group, and R23 and R24 may be bonded to each other to form a ring; (Gonggongyi AB) where the rule ... and Ru 'each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group which may have a substituent; Z, which must form an alicyclic ring with two carbon atoms (c_c) Atomic group of the structure, which may have a substituent. 13. If the positive-type photosensitive composition according to item 12 of the application, wherein Z1 in formula (II-AB) represents an atomic group that must form a bridge-containing alicyclic structure together with two carbon atoms (cc), It may have a substituent. 14. The positive-type photosensitive composition according to item 2 of the patent application range, wherein the compound represented by formula (II-AB) is represented by formula (II · A) or (Π · Β): Lu gutter (ΙΙ-Β) This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 548523 A8 B8 C8 The scope of the patent application is that R! 3, R! 4 ', and RhU6' each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR5, and can be decomposed under the action of an acid. CpCO-X-A'-Rp ', an alkyl group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent; I represents an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent or is shown below _γ group; X represents an oxygen atom, a sulfur atom, -NΗ-, -NHS02- or -NHS02NH-; A, represents a single bond or a monovalent linking group, at least two of R13 ', Ri4', R15 'and R16' Can be bonded to each other to form a ring; η represents 0 or 1; r! 7, represents -COOH, -COOR5, -CN, hydroxyl, alkoxy which may have a substituent, -C0-NH-R6,- C0-NH-S02-R6 or -Y group shown below; r6 represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent Wherein each of 'to' represents a hydrogen atom or an alkyl group which may have a substituent, and a and b each represent 1 or 2. 15. The positive-type photosensitive composition according to item 丨 丨 of the patent application scope, further comprising (C) a surfactant containing at least one of a gas atom and a silicon atom. 16. The positive photosensitive composition according to item 11 of the patent, which further comprises (D) a solvent mixture comprising at least one solvent selected from the following group A solvents; and 548523 AB c D 6. The scope of the patent application is at least one of the solvents selected from the group B solvents and the solvents selected from the group C solvents: Group A: propylene glycol monoalkyl ether acrylate, Group B: propylene glycol monoalkyl ether, lactic acid alkyl Esters and alkyl alkoxypropionates, group C: γ-butyrolactone, ethoxycarbonate and propylene carbonate. 17. The positive-type photosensitive composition according to item 11 of the patent application scope, further comprising (D) a solvent mixture, the mixture comprising: at least one lactic acid group; and at least an ester solvent and oxypropyl group. One of the sour vinegar. 18. The positive-type photosensitive composition according to item 17 of the patent application scope, wherein the solvent (D) further comprises at least one of γ-butyrolactone, ethylidene carbonate and propylene carbonate. 19. The positive-type photosensitive composition according to item 11 of the patent application scope, further comprising (D) a solvent mixture, the mixture comprising: at least one solvent selected from the following group D solvents; and at least one group E One of the solvents of the solvent and a solvent selected from the group F solvents: Group D: heptone; Group E: propylene glycol monoalkyl ether, alkyl lactate, and alkyl alkoxypropionate; Group F: γ-butane Esters, ethylene carbonate and propylene carbonate. -228-This paper size applies to China National Standards (CMS) A4 specification (210 X 297 mm)