JPH0962006A - Positive type photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the shrinkage of a film and the reduction of film thickness at the time of development and to ensure satisfactory sensitivity and profile, high resolving power and shelf stability for the time from exposure to heating by using a compd. having an enol ether group and a compd. having an acidic group in a three-component chemical amplification type resist. SOLUTION: An alkali-soluble resin, a compd. having at least one enol ether group represented by the formula, a compd. having an acidic group, a low molecular compd. having an acid-decomposable group and a mol.wt. of <=3,000, a compd. which is decomposed and generates an acid when irradiated with active light or radiation and a solvent are incorporated. In the formula, each of R1 -R3 is H, optionally substd. alkyl, cycloalkyl or aryl and two of them may bond to each other to form a satd. or unsatd. ring. When the resultant positive type photoresist compsn. is applied to a substrate and dried by heating to form a coating film, the purpose can be more effectively attained.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive photoresist composition used in semiconductor manufacturing processes such as the above, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes.

[0002]

2. Description of the Related Art Positive photoresist compositions include:
Generally, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, US Pat. No. 3,666,47 as “Novolak-type phenolic resin / naphthoquinonediazide-substituted compound”.
3, U.S. Pat. No. 4,115,128 and U.S. Pat. No. 4,173,470, and the most typical composition is "cresol-formaldehyde novolac resin / trihydroxybenzophenone-1,2- An example of "naphthoquinone diazide sulfonate" is Thompson "Introduction to Microlitho".
graphy ”) (ACS Publishing, No. 219, p112-1)
21). In such a positive photoresist consisting essentially of a novolak resin and a quinonediazide compound, the novolak resin gives high resistance to plasma etching, and the naphthoquinonediazide compound acts as a dissolution inhibitor. Then, naphthoquinonediazide has the property of losing its dissolution inhibiting ability by generating carboxylic acid upon irradiation with light, and increasing the alkali solubility of the novolak resin.

[0003] From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide-based photosensitive material have been developed and put into practical use.
Sufficient results have been achieved in line width processing down to about 2 μm. However, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs, processing of ultrafine patterns having a line width of half a micron or less has been required. In order to achieve this required resolving power, the exposure equipment used in photolithography has been using shorter and shorter wavelengths, and now far-ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.)
Is being considered. When a conventional resist consisting of novolak and naphthoquinonediazide compound is used for lithographic pattern formation using far ultraviolet light or excimer laser light, light is strongly absorbed in the far ultraviolet region of novolak and naphthoquinonediazide. It is difficult to reach, and only a low-sensitivity, tapered pattern can be obtained.

One of the means for solving such a problem is as follows.
U.S. Pat. No. 4,491,628; EP 249,
No. 139 and the like. The chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as deep ultraviolet light, and the reaction using the acid as a catalyst dissolves the active radiation irradiated area and the non-irradiated area in the developing solution. This is a pattern forming material that changes the properties and forms a pattern on a substrate.

Examples of such a combination include a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( JP-A-5120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1)
No. 33429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain. (JP-A-56-17345), a combination with a tertiary alkyl ester compound (JP-A-60-3625), and a combination with a silyl ester compound (JP-A-60-10247).
No.) and a combination with a silyl ether compound (Japanese Unexamined Patent Publication No.
0-37549, JP-A-60-112446) and the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, a system which is stable at room temperature over time but decomposes by heating in the presence of an acid to solubilize with an alkali is disclosed in, for example, JP-A-59-45439 and JP-A-60-3625. JP-A-62-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, Polym. Eng. Sce., Volume 23,
1012 (1983); ACS. Sym. 242, 11 (1984); Semico
nductor World 1987, November issue, p. 91; Macromolecule
s, vol. 21, p. 1475 (1988); SPIE, vol. 920, p. 42 (19)
88) and the like, and a combination system of a compound which generates an acid upon exposure to light and an ester or carbonate compound of a tertiary or secondary carbon (for example, t-butyl, 2-cyclohexenyl). These systems also have high sensitivity,
Moreover, since the absorption in the Deep-UV region is smaller than that of the naphthoquinone diazide / novolak resin system, it can be an effective system for shortening the wavelength of the light source. However, in a system that is stable at room temperature with time, but decomposes by heating in the presence of an acid to solubilize with an alkali, although it has excellent storage stability, it is affected by the time until heating after exposure (PE
D: post exposure delay), that is, the acid generated by photolysis is contaminated and deactivated by a basic substance such as ammonia gas in the environment over time, resulting in a so-called T-Top-shaped pattern and a decrease in resolution. was there.

The positive chemically amplified resist is a three-component system comprising an alkali-soluble resin, a compound that generates an acid upon exposure to radiation (photoacid generator), and a compound that inhibits dissolution of the alkali-soluble resin having an acid-decomposable group. And a two-component system comprising a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble, and a photoacid generator. In the case of a two-component system, the content of acid-decomposable groups in the resin increases, so there is a problem that the resist film shrinks due to baking after exposure. On the other hand, in the case of the three-component system, there is a problem that the dissolution inhibiting property with respect to the alkali-soluble resin is insufficient, so that the film loss during development is large and the resist profile is significantly deteriorated.

Further, an enol ether compound and an acidic group,
An image forming method comprising a linear polymer having a hydroxyl group and a photoacid generator is known (JP-A-5-100428, JP-A-5-100429, JP-A-6-148889,
JP-A-6-230574, JP-A-7-140662
No. 7-140670, JP-A 7-14655
2, JP-A-7-146557). However, in this case, since the difference in solubility between the unexposed area and the exposed area is small, a high-resolution positive image cannot be formed, further the film loss during development is large, and the resist pattern has a tapered shape and a rectangular profile. There were problems such as not being able to obtain it.

[0009]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to reduce film shrinkage due to baking after exposure and film loss during development, to have good sensitivity and profile and high resolution, and to heat up after exposure. The object of the present invention is to provide a positive photoresist composition which is stable during storage, that is, is not easily affected by a basic substance such as ammonia that is likely to be exposed during storage, and a coating film using the same.

[0010]

Means for Solving the Problems The present inventors have paid careful attention to the above-mentioned various characteristics, and as a result of diligent studies, as a result, (A) an alkali-soluble resin, (B) at least an enol ether group represented by the following general formula (a) A compound having one,

[0011]

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(In the formula (a), R _{1 to} R ₃ may be the same or different and each is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group. Group, and two of them may combine to form a saturated or unsaturated ring.) (C) Compound having an acidic group (D) Molecular weight 3,000 having an acid-decomposable group The above object was achieved by a positive photoresist composition comprising the following low molecular weight compound (E), a compound (F) that decomposes upon irradiation with actinic rays or radiation to generate an acid.

In the above positive photoresist composition, the blending ratio of the component (B) and the component (D) to the total solid content is 5 (wt%) ≤ [B + D] ≤70 (wt%), and 5 (wt%). %) ≦ 100D / [B + D] ≦ 80 (wt%) It is preferable to satisfy the relational expression.

Furthermore, the above-mentioned object can be achieved more effectively by a coating film obtained by coating the above-mentioned positive photoresist composition on a substrate and heating and drying.

The present invention uses a compound having an enol ether group and a compound having an acidic group in a three-component chemically amplified resist comprising an alkali-soluble resin, an acid-decomposable dissolution inhibiting compound and a photo-acid generator. , Which is completely different from the conventionally known technology. That is, it has been surprisingly found that by using a compound having an enol ether group and a compound having an acidic group together with an acid-decomposable dissolution inhibiting compound, extremely excellent performance (high γ value, high resolution) is shown. Came to complete.

In the above positive photoresist composition, the blending ratio of the component (B) and the component (D) to the total solid content is more preferably 10 (wt%) ≤ [B + D] ≤65 (wt%) 10. (Wt%) ≦ 100D / [B + D] ≦ 70 (wt%), particularly preferably 20 (wt%) ≦ [B + D] ≦ 60 (wt%) 15 (wt%) ≦ 100D / [B + D] ≦ 60 (% By weight). If the proportion of [B + D] is less than 5% by weight, the residual film rate is remarkably lowered, and if it exceeds 70% by weight, the sensitivity and the solubility in a solvent are lowered.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The enol ether group-containing compound of the above component (B) will be described. In the enol ether group of the general formula (a), when R ₁ , R ₂ and R ₃ are aryl groups, generally 4 to
It has 20 carbon atoms and is an alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, acyloxy group, alkylmercapto group, aminoacyl group, carboalkoxy group, nitro group, sulfonyl group, cyano group or halogen atom. May be replaced by. When R ₁ , R ₂ and R ₃ represent an alkyl group, they represent a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, a halogen atom, a cyano group, an ester group, Oxy group,
It may be substituted with an alkoxy group, an aryloxy group or an aryl group. When R ₁ , R ₂ and R ₃ represent a cycloalkyl group, they generally represent a cycloalkyl group having ₃ to 15 carbon atoms, and include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group,
It may be substituted with an alkylmercapto group, aminoacyl group, carboalkoxy group, nitro group, sulfonyl group, cyano group or halogen atom.

The saturated or unsaturated ring formed by combining any _{two of} R ₁ , R ₂ and R ₃ is preferably a cycloalkyl group or a cycloalkenyl group,
They usually represent 3 to 8, preferably 5 or 6 ring members. In the present invention, among the enol ether groups represented by the general formula (a), preferred are enol ethers in which one of R ₁ , R ₂ and R ₃ is a methyl group or an ethyl group and the rest are hydrogen atoms. Groups, more preferably R
₁ , a vinyl ether group in which R ₂ and R ₃ are all hydrogen. Various compounds containing one or more enol ether groups or preferably two or more enol ether groups can be used in the present invention, but they have a boiling point of 60 ° C. or more under atmospheric pressure. It is a compound. Preferred compounds of the component (B) include the following general formula (b)
Alternatively, a vinyl ether compound represented by (c) may be used.

[0019]

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Here, A represents an m-valent alkyl group, aryl group or heterocyclic group, and B represents -CO-O- or -NHC.
OO- or -NHCONH- is shown, and R ₄ has 1 to 1 carbon atoms.
10 is a linear or branched alkylene group, n is 0 or an integer of 1 to 10, and m is an integer of 2 to 6. The compound represented by the general formula (b) is exemplified by Stephen C. Lapin,
Polymers Paint Color Journal, 179 (4237), 321 (198
It can be synthesized by the method described in 8), that is, the reaction of polyhydric alcohol or polyhydric phenol with acetylene, or the reaction of polyhydric alcohol or polyhydric phenol with halogenated alkyl vinyl ether. Specific examples thereof include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol. Divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether,
Triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether , 1,2-di (vinyl ether methoxy) benzene, 1,2-di (vinyl ether ethoxy) benzene, and the following general formula (b-
The compounds represented by 1) to (b-42) may be mentioned, but the invention is not limited thereto.

[0021]

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[0022]

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[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

[Chemical 12]

[0030]

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On the other hand, the compound represented by the general formula (c) (when B = CO-O-) can be produced by reacting a polyvalent carboxylic acid with a halogenated alkyl vinyl ether. Specific examples thereof include terephthalic acid diethylene vinyl ether, phthalic acid diethylene vinyl ether, isophthalic acid diethylene vinyl ether, phthalic acid dipropylene vinyl ether, terephthalic acid dipropylene vinyl ether, isophthalic acid dipropylene vinyl ether,
Examples thereof include, but are not limited to, maleic acid diethylene vinyl ether, fumaric acid diethylene vinyl ether, and itaconic acid diethylene vinyl ether. Further, vinyl ether compounds preferably used in the present invention include the following general formulas (d) and (e)
Alternatively, a vinyl ether group-containing compound synthesized by a reaction of a vinyl ether compound having an active hydrogen represented by (f) and the like and a compound having an isocyanate group can be given.

[0032]

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Here, R ¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms. As the compound containing an isocyanate group, for example, the compounds described in Handbook of Crosslinking Agents (published by Taisei, 1981) can be used. Specifically, triphenylmethane triisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-
Tolylene diisocyanate, polymethylene polyphenyl isocyanate, polyisocyanate type such as hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylol propane, adduct of hexamethylene diisocyanate and water, xylene di Examples thereof include polyisocyanate adduct types such as adducts of isocyanate and trimethylolpropane.

By reacting the above-mentioned isocyanate group-containing compound with the active hydrogen-containing vinyl ether compound, various compounds having a vinyl ether group at the terminal can be prepared.
Examples of the compound having a vinyl ether group used in the present invention are listed below, but the scope of the present invention is not limited thereto.

[0035]

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[0036]

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[0037]

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The above-mentioned compounds having at least two vinyl ether groups can be used alone, but may be used as a mixture of several kinds. The compound having an enol ether group, which is the component (B) of the present invention, has an action of thermally reacting with a hydroxyl group and / or an acid component in the component constituting the present invention to form an acetal bond or a crosslinked structure based on an acetal bond. Show. Acid-decomposable compounds (acid-decomposable dissolution inhibitors) used in chemically amplified resists include those that decompose at room temperature due to the acid generated by photolysis and that are stable at room temperature over time, but in the presence of acid, Some are decomposed by heating. Since the former is relatively unstable, there is a problem that the stability during storage of the resist solution is poor. On the other hand, the latter has excellent storage stability, but is affected by aging until heating after exposure (PED: post exposure de
lay), that is, the acid generated by photolysis is contaminated and deactivated by a basic substance in the environment over time, and it is known that there is a problem that a so-called T-Top pattern is formed and the resolution is lowered.

The present invention solves these problems all at once. In the present invention, a stable acid-decomposable compound was used, and by introducing a compound having an enol ether group into it, the effect of PED could be suppressed. It is considered that this is because the enol ether group and the hydroxyl group and / or the acidic group reacted to form an acetal structure. However, since this acetal structure is formed only by heating after coating, the acetal structure is There are no storability problems.

The compound having an acidic group added as the component (C) has reactivity with the enol ether group and also has a catalytic action when the enol ether group and the hydroxyl group react with each other, but at the same time, it has a basic property in the environment. It also has the effect of suppressing contamination from substances (suppresses the influence of PED). Furthermore, the greatest effect of the present invention is that by using an acid-decomposable compound (dissolution inhibiting compound) and a compound having an enol ether group in combination, extremely excellent performances (high γ, high resolution) that cannot be obtained by each alone are exhibited. It is in. Examples of the compound having an acidic group which is the component (C) of the present invention include a low molecular compound and a high molecular compound having a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group and the like. A low molecular weight compound having a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, etc. in the molecule has a molecular weight of 2,000.
The following aliphatic compounds, aromatic compounds, alicyclic compounds and heterocyclic compounds can be mentioned. Of these,
The following compounds can be illustrated as preferable examples, but the present invention is not limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

[Chemical 21]

Among these, more preferable are:
(H-1), (h-3), (h-5), (h-6),
(H-8), (h-10), (h-11), (h-1
3), (h-14), (h-16), (h-17),
(H-18), (h-19), (h-20), (h-2
2), (h-23), (h-30) and (h-36). Further, as particularly preferable ones, (h-3), (h-6), (h-14), (h-1)
9), (h-22) and (h-23). Furthermore, (h-22) and (h-23) can be mentioned as those which particularly exert the effects of the present invention and exhibit the most excellent performance.

The polymer compound having an acidic group which is the component (C) of the present invention can be synthesized by a known method for obtaining a polymer compound. For example, an acid component, preferably a carboxylic acid group or a sulfonic acid group, There is a method of polymerizing a vinyl monomer having a phosphoric acid group, a sulfonamide group, or the like, or copolymerizing a vinyl monomer having an acid component with another vinyl monomer. It can also be obtained by copolymerizing a vinyl monomer having an acidic group, preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, etc. with a vinyl monomer having a hydroxyl group.
If necessary, another vinyl monomer may be copolymerized. Examples of the vinyl monomer containing an acidic component include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, isocrotonic acid, p-vinylbenzoic acid, p-vinylbenzenesulfonic acid, p-vinylcinnamic acid, maleic acid. Examples thereof include monomethyl ether and maleic acid monoethyl ether.

Examples of the vinyl monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, p-2-hydroxyethyl styrene, N- (2-hydroxyethyl) maleimide, p-hydroxystyrene and N-. (4-hydroxyphenyl) methacrylamide and the like can be mentioned. Examples of other monomers copolymerizable with the above monomers include acrylonitrile, acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, butyl methacrylate, styrene, benzyl acrylate,
Benzyl methacrylate, vinyl benzoate, vinyl chloride, vinylidene chloride, vinyl acetate, N- (4-
Examples thereof include sulfamoylphenyl) methacrylamide, N-phenylphosphonylmethacrylamide, butadiene, chloroprene, and isoprene. A preferable copolymerization ratio of the vinyl monomer containing an acidic component, the vinyl monomer containing a hydroxyl group, and the other copolymerizable monomer is 5 to 80: 2 to 80: 0 to 97 by weight%.
Range.

These polymer compounds can be used alone, but may be used as a mixture of several kinds. The molecular weight of the polymer compound is generally 2,000 to 1,000,000,
It is preferably 2,500 to 200,000. Also,
As the polymer compound used in the present invention, those having an acidic group and a hydroxyl group in one polymer chain as described above are preferable, but with a specific developing solvent, a polymer having an acidic group has the same effect. It can also be obtained in a mixture of a compound and a polymer compound having a hydroxyl group. Further, in the present invention, when the component (C) is a polymer compound having an acidic group or a polymer compound having an acidic group and a hydroxyl group, it is possible to use the alkali-soluble resin as the component (A). good. When the component (C) of the present invention is a low molecular weight compound, the amount of the component (C) added is generally 1 to 55% by weight, preferably 1.5 to 30% by weight based on the total solid content of the photosensitive composition.
It is in the range of% by weight. On the other hand, when the component (C) is a polymer compound, the amount of the component (C) added is generally 3 to 90% by weight, preferably 5 to 5% by weight based on the total solid content of the photosensitive composition.
70% by weight.

The low molecular weight compound having a molecular weight of 3,000 or less and having an acid-decomposable group, which is the component (D) of the present invention, has at least two groups capable of being decomposed by an acid in its structure. A compound having at least 10, preferably at least 11, and more preferably at least 12 bond atoms excluding the acid-decomposable group, or at least 3 acid-decomposable groups at the position most distant from each other. , At least 9 bond atoms excluding the acid-decomposable group, preferably at least 1 at the position where the distance between the acid-decomposable groups is the longest.
Compounds via 0, more preferably at least 11, are preferred. Also, the preferable upper limit of the number of bonding atoms is 50.
The number is more preferably 30. In the present invention, when the acid-decomposable dissolution-inhibiting compound has three or more, preferably four or more acid-decomposable groups, and even when the compound has two acid-decomposable groups, the acid-decomposable groups are mutually present. If they are separated by a certain distance or more, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved. In addition, the distance between the acid-decomposable groups in the present invention is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, in the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms each,
The compound (3) has 12 bonding atoms.

[0050]

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The acid-decomposable dissolution inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably one acid-decomposable group on one benzene ring. It is a compound composed of a skeleton having an acid-decomposable group. Further, the molecular weight of the acid-decomposable dissolution-inhibiting compound of the present invention is 3,000 or less, preferably 500 to 3,000.
0, more preferably 1,000 to 2,500.

In a preferred embodiment of the present invention, the group containing an acid-decomposable group --COO--A ⁰ or --O--B ⁰ is --R ⁰ --COO--A ⁰ or --Ar--O. -B
^And a group represented by ⁰ . Where A ⁰ is −C
(R ⁰¹ ) (R ⁰² ) (R ⁰³ ), —Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), or —C (R ⁰⁴ ) (R ⁰⁵ ) —O—R ⁰⁶ group is shown. B
⁰ represents an A ⁰ or -CO-OA ⁰ group. R ⁰¹ , R ⁰² ,
R ⁰³ , R ⁰⁴ and R ^{05, which} may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. Provided that at least two of R ⁰¹ to R ⁰³ is a group other than a hydrogen atom, and, R ⁰¹ to R
Two groups of ⁰³ and R ^{04 to} R ⁰⁶ may combine to form a ring. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- is a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

Here, the alkyl group is preferably a group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cycloalkyl group. Is preferably a group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and the alkenyl group is 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Four aryl groups are preferable, and the aryl group has 6 to 1 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl groups, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Acyl such as alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, aralkyl group such as benzyl group, phenethyl group, cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, valeryl group, etc. Groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group and a butenyloxy group, an aryloxy group such as the above aryl group and a phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

Preferred are silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, tertiary alkyl ether group, tertiary alkyl ester group and tertiary alkyl carbonate group. More preferably, a tertiary alkyl ester group, a tertiary
A primary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

Preferably, JP-A-1-289946,
JP-A 1-289947, JP-A-2-2560,
Kaihei 3-128959, JP-A-3-158855,
JP-A-3-179353, JP-A-3-191351
No. 3, JP-A-3-200251, JP-A-3-2000025
No. 2, JP-A-3-200253, and JP-A-3-2002.
54, JP-A-3-200255, and JP-A-3-259.
149, JP-A-3-279958, and JP-A-3-27
No. 9959, JP-A-4-1650, and JP-A-4-165.
1, JP-A-4-11260, and JP-A-4-12356.
Japanese Patent Application Laid-Open No. 4-12357, Japanese Patent Application No. 3-33229.
Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-32043
No. 8, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-52732.
Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-10454
No. 2, Japanese Patent Application No. 4-107885, Japanese Patent Application No. 4-1078
89, No. 4-152195, etc.
If some of the phenolic OH groups of polyhydroxy compounds
Or all of the groups shown above, -R ⁰-COO-A⁰Or
B⁰Included are compounds that are group-bonded and protected.

More preferably, JP-A 1-289946
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

Specific examples of preferable compound skeletons are shown below, but the present invention is not limited thereto.

[0058]

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[0059]

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[0060]

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[0061]

[Chemical formula 26]

[0062]

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[0063]

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[0064]

[Chemical 29]

[0065]

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[0066]

[Chemical 31]

[0067]

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[0068]

[Chemical 33]

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

[Chemical 40]

[0076]

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R in the compounds (1) to (63) is a hydrogen atom,

[0078]

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Represents However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
Need not be the same group.

Examples of the alkali-soluble resin used in the present invention include novolac resin, hydrogenated novolac resin, acetone-pyrogallol resin, polyhydroxystyrene, hydroxystyrene-styrene copolymer, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene. -N-substituted maleimide copolymer, partial O-alkylated product of polyhydroxystyrene or O-
Examples thereof include an acylated product, a styrene-maleic anhydride copolymer, a carboxyl group-containing methacrylic resin and its derivative. It is also possible to use a resin in which some or all of the phenolic hydroxyl groups contained in these resins are replaced with acid-decomposable groups. However, the present invention is not limited to these. Particularly preferred alkali-soluble resins are novolak resins and polyhydroxystyrene. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
-Cresol, p-cresol, o-cresol and other cresols, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol and other xylenols, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2- Alkoxyphenols such as methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxyphenol and the like, 2-methyl-4-isopropylphenol. Bis-alkylphenols etc., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more, but are not limited thereto. It is not something to be done.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde. , O-chlorobenzalthehydr,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and its acetal form, such as chloroacetaldehyde diethyl acetal, can be used, and among these, formaldehyde is preferably used. These aldehydes are
They are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The novolak resin thus obtained preferably has a weight average molecular weight of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
The range is 000. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography.

Two or more kinds of these alkali-soluble resins in the present invention may be mixed and used.

The compound (photoacid generator) used in the present invention which decomposes upon irradiation with actinic rays or radiation to generate an acid (photoacid generator) includes a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization and a dye. A class of photo-decoloring agents, photo-discoloring agents, known compounds which generate an acid upon exposure to light used in micro resists and the like and mixtures thereof can be appropriately selected and used. For example, SISchlesinger,
Photogr. Sci. Eng., 18, 387 (1974), TSBal etal,
Polymer, 21, 423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055, 4,069,056 and Re 27,992.
No. 3, ammonium salts described in Japanese Patent Application No. 3-140,140, D.
C. Necker et al, Macromolecules, 17, 2468 (1984), C.
S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p47
8 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055 and 4,06
Phosphonium salts described in 9,056 etc., JV Crivello eta
1, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng.
News, Nov. 28, p31 (1988), European Patent 104,143,
U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,84
No. 8, iodonium salts described in JP-A-2-296,514, J.
V.Crivello et al, Polymer J.17, 73 (1985), JVCriv
ello et al. J. Org. Chem. 43, 3055 (1978), WRWatt
et al, J. Polymer Sci., Polymer Chem. Ed., 22, 178
9 (1984), JVCrivello et al, Poiymer Bull., 14, 279
(1985), JVCrivello et al, Macromorecules, 14 (5), 1
141 (1981), JVCrivello et al, J. Polymer Sci., Pol
ymer Chem. Ed., 17, 2877 (1979), European Patent No. 370,693
No. 3, No. 3,902,114, No. 233,567, No. 297,443, No. 29
7,442, U.S. Pat.Nos. 4,933,377, 161,811 and 41
0,201, 339,049, 4,760,013, 4,734,444
No. 2,833,827, German Patent No. 2,904,626, No. 3,604,
Sulfonium salts described in 580, 3,604,581, etc., JV
Crivello etal, Macromorecules, 10 (6), 1307 (1977),
JVCrivello et al, J. Polymer Sci., Po1ymer Chem.
Ed., 17, 1047 (1979) and other selenonium salts, CSW
en eta1, Teh, Proc. Conf. Rad. Curing ASIA, p 478
Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60. -239736
No. 61-169835, 61-169837, 62-62.
-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, and the like, K. Mei
er et al, J. Rad. Curing, 13 (4), 26 (1986), TPGill
eta1, Inorg. Chem., 19, 3007 (1980), D.Astruc, Acc.
Chem. Res., 19 (12), 377 (1896), S. Hayase et al.
J. Polymer Sci., 25, 753 (1987), E. Reichmanis eta
l, J. Polymer Sci., Polymer Chem, Ed., 23, 1 (198
5), QQZhu etal, J. Photochem., 36, 85, 39, 317 (1
987), B. Amit et al, Tetrahedron Lett., (24) 2205 (197
3), DHR Barton et al, J. Chem Soc., 3571 (1965),
PMCollins et al, J. Chem. Soc., Perkin I, 1695 (19
75), M. Rudinsteinetal, Tetrahedron Lett., (17), 1
445 (1975), JWWalker et al, J. Am. Chem. Soc., 11
0, 7170 (1988), SCBusman et al, J. Imaging Techno
l, 11 (4), 191 (1985), HM Houlihan et al, Macormolec
ules, 21, 2001 (1988), PMCollins et al, J. Chem. S
oc., Chem. Commun., 532 (1972), S. Hayase et al, Macr
omolecules, 18, 1799 (1985), E. Reichmanis et al, J.
Electrochem. Soc., Solid State Sci. Technol., 130
(6), FMHoulihan et al, Macromolcules, 21, 2001 (19
88), European Patent Nos. 0290,750, 046,083, 156,535
No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,71
0, 4,181, 531, JP-A-60-198538, JP-A-53-13
3022, etc., a photo-acid generator having an o-nitrobenzyl type protecting group, M.TUNOOKA et al, Polymer Preprints Japa
n, 35 (8), G. Berner et al, J. Rad. Curing, 13 (4), W.
J. Mijs et al, Coating Technol, 55 (697), 45 (1983), A
kzo, H. Adachietal, Polymer Preprints, Japan, 37
(3), European Patent Nos. 0199,672, 84515, 199,672
No. 044,115, No. 0101122, U.S. Pat.No. 618,564
No. 4,371,605, 4,431,774, JP-A-64-18143
No. 2, JP-A No. 2-245756, Japanese Patent Application No. 3-140109, etc., compounds that generate sulfonic acid by photolysis, represented by imino sulfonates, etc., described in JP-A No. 61-166544, etc. The disulfone compound can be mentioned.

Further, a group generating an acid by these light,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, MEWoodhouse etal, J. Am. Chem.
Soc., 104, 5586 (1982), SPPappas et al, J. Imagin
g Sci., 30 (5), 218 (1986), S. Kondo etal, Makromol.
Chem., Rapid Commun., 9, 625 (1988), Y. Yamada et al.
Makromol. Chem., 152, 153, 163 (1972), JVCrivell
o etal, J. Polymer Sci., Polymer Chem. Ed., 17, 38
45 (1979), U.S. Patent No. 3,849,137, German Patent No. 391440.
7, JP-A-63-26653, JP-A-55-164824, JP-A-62-6
Compounds described in 9263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, VNR Villai, Synthesis, (1), I
(1980), A. Abad et al, Tetrahedron Lett., (47) 4555 (1
971), DHR Barton et al, J. Chem. Soc., (C) 329 (197
0), U.S. Pat. No. 3,779,778, European Patent 126,712, and the like, which generate an acid by light can also be used.

Among the compounds which decompose to generate an acid upon irradiation with actinic rays or radiation, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
1) an oxazole derivative or a general formula (PA
An S-triazine derivative represented by G2).

[0089]

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In the formula, R ¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group or --CY ₃ . Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0091]

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[0092]

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[0093]

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(2) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4).

[0095]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for the aryl group, and a substituent for the alkyl group. It is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, or an alkoxycarbonyl group.

Z ⁻ represents a counter anion, for example, BF ₄ ⁻ ,
_{^{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

Also, two of R ³ , R ⁴ , and R ⁵ and A
r ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0101]

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[0102]

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[0103]

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[0104]

[Chemical 51]

[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and for example, JWKnapcz.
yk et al, J. Am. Chem. Soc., 91, 145 (1969), ALMay
coketal, J. Org. Chem., 35, 2532 (1970), E. Goethas
et al, Bull. Soc. Chem. Belg., 73, 546 (1964), HML
eicester, J. Ame. Chem. Soc., 51, 3587 (1929), JV
Crivello etal, J. Polym. Chem. Ed., 18, 2677 (198
0), US Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101331.

(3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

[0115]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0117]

[Chemical formula 61]

[0118]

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[0119]

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[0120]

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[0121]

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The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.0 based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 0.01 to 40% by weight, preferably 0.0
It is used in an amount of 1 to 20% by weight, more preferably 0.1 to 5% by weight.

If necessary, the composition of the present invention further comprises a compound having two or more phenolic OH groups for promoting the solubility in dyes, pigments, plasticizers, surfactants, photosensitizers and developers. Etc. can be included. Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103,
Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black B
Y, oil black BS, oil black T-505
(All manufactured by Orient Chemical Industry Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170).
B), malachite green (CI42000), methylene blue (CI52015) and the like.

Further, a spectral sensitizer as described below is added to the composition of the present invention by sensitizing it to a wavelength region longer than deep ultraviolet where the photo-acid generator used does not have absorption.
Alternatively, sensitivity can be imparted to the g-line. Suitable spectral sensitizers include, specifically, benzophenone, p, p '
-Tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzil, acridine orange, benzoflavin,
Cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene,
Benzoquinone, 2-chloro-4-nitroaniline, N-
Acetyl-p-nitroaniline, p-nitroaniline,
N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone,
2-tert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9
-Benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3'-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), coronene and the like, but not limited thereto.

The composition of the present invention is dissolved in a solvent which dissolves each of the above components and coated on a support. Examples of the solvent used here include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate. , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethyl Formamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used as simple substances. Or mixed to use. The concentration of the total solid content dissolved in the solvent is generally 10% by weight to 50% by weight.

A surfactant may be added to the above solvents. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether,
Polyoxyethylene nonylphenol ether and other polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers
Sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan mono Nonionic surfactants such as palmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters, Ftop EF301, EF303, EF352 ( Shin-Akita Kasei Co., Ltd., Megafac F171, F173 (Dainippon Ink Co., Ltd.), Florard FC430, FC431
(Manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorine-based surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polyflow No. 75, No. 95 (Kyoeisha Oil and Fat Chemical Co., Ltd.)
Manufactured). The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

Applying the composition of the present invention onto a substrate (eg, silicon / silicon dioxide coating) as used in the production of precision integrated circuit devices by a suitable coating method such as a spinner or coater, and drying by heating. The coating film obtained by the method has excellent performance as described above. Here, the heating condition is 80 to 160 ° C, preferably 100 ° C to 1
40 ° C. After forming the coating film, a good resist pattern can be obtained by exposing through a predetermined mask, baking and developing.

As the developer for the photosensitive composition of the present invention,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and tertiary amines such as triethylamine and methyldiethylamine. Use alkaline aqueous solutions of triamines, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0129]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto. Synthesis Example (1) Synthesis of Compound (b-11) Bisphenol-A10 was added to a 1-liter three-necked flask.
7.2 g (0.47 mol) and sodium methylate (28
% Methanol solution) (199.1 g, 1.03 mol) was added, to which 300 ml of methanol was added, and the mixture was stirred at room temperature for 1 hour. Methanol was distilled off from the reaction solution under reduced pressure to dryness. Tetraethylammonium iodide 4 g, potassium iodide 2 g, and PEG-300 2 g were added,
Add 256 g of chloroethyl vinyl ether,
The mixture was stirred under heating under reflux for 48 hours. Ethyl acetate and silica gel were added to the reaction solution, and the mixture was stirred, filtered, and then ethyl acetate and chloroethyl vinyl ether were distilled off under reduced pressure to give a bisphenol-A-divinyl ether compound as a white powder.
Obtained in 20 g (70% yield). The structure was confirmed to be divinyl ether by ¹ HNMR.

Synthesis Example (2) Synthesis of Compound (b-42) 127.3 g of α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene was placed in a one-liter three-necked flask. (0.3 mol) and sodium methylate (28% methanol solution) 199 g (1.0
(3 mol), 300 ml of methanol was added thereto, and the mixture was stirred at room temperature for 1 hour. Methanol was distilled off from the reaction solution under reduced pressure to dryness. Tetraethylammonium iodide 4
g, potassium iodide 2 g, PEG-300 2 g, respectively, and chloroethyl vinyl ether 350
g was added, and the mixture was stirred with heating under reflux for 48 hours. Ethyl acetate and silica gel were added to the reaction solution, and the mixture was stirred and filtered, and then ethyl acetate and chloroethyl vinyl ether were distilled off under reduced pressure to obtain α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-. 142 g (yield 75%) of a triisopropylbenzene-trivinyl ether compound was obtained as a yellow oily substance, and its structure was confirmed to be trivinyl ether by ¹ HNMR.

Synthesis Example (3) Synthesis of Compound (D1) 20 g of the following compound (D1 ′) was added to tetrahydrofuran 40
Dissolved in 0 ml. Tert- this solution under a nitrogen atmosphere.
14 g of potassium butoxy potassium was added, and after stirring at room temperature for 10 minutes, 29.2 g of di-tert-butyl dicarbonate was added. The reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate layer was further washed with water and dried, after which the solvent was distilled off. The obtained crystalline solid was recrystallized (diethyl ether) and dried to obtain 25.6 g of compound example (31: R is all t-butoxycarbonyl group (t-BOC group)).

[0132]

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Synthesis Example (4) Synthesis of Compound (D2) 20 g of the above compound (D1 ′) was added to diethyl ether 400
dissolved in ml. To this solution, under a nitrogen atmosphere, 3,4-dihydro-2H-pyran (31.6 g) and a catalytic amount of hydrochloric acid were added,
The reaction was carried out under reflux for 24 hours. After completion of the reaction, a small amount of sodium hydroxide was added and the mixture was filtered. The solvent of the filtrate was distilled off, and the obtained product was purified by column chromatography and dried to obtain a compound example (31: R are all tetrahydropyranyl groups (THP groups)).

Synthesis Example (5) Synthesis of Compound (D3) 11.2 g (0.040 mol) of the above compound (D1 ′) in 120 ml of N, N-dimethylacetamide was added to 21.2 g (0.15 mol) of potassium carbonate. ), And bromoacetic acid t
-Butyl 27.1 g (0.14 mol) was added and 120
The mixture was stirred at 0 ° C for 7 hours. Thereafter, the reaction mixture was poured into 1.5 liters of water, and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate /
n-Hexane = 3/7 (volume ratio))) to obtain 30 g of a pale yellow viscous solid. By NMR, this compound Example (31: R are all -CH ₂ COOC ₄ H ₉ ^t group) was confirmed to be.

Synthesis Example (6) Synthesis of Compound (D4) 42.4 g (0.10 mol) of the following compound (D4 ') was dissolved in 300 ml of N, N-dimethylacetamide, and 49.5 g (0 0.35 mol), and 84.8 g (0.33 mol) of bromoacetic acid cumyl ester were added. Thereafter, the mixture was stirred at 120 ° C. for 7 hours. The reaction mixture was added to 2 liters of ion-exchanged water and extracted with ethyl acetate. The ethyl acetate extract was concentrated to synthesize Example (5).
Was purified in the same manner as in Example 1 and the compound examples (18: R were all —CH ₂ C
_{OOC (CH 3) 2 C 6} H 5 group) was obtained 70 g.

[0136]

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Synthesis Example (7) Synthesis of Compound (D5) 14.3 g (0.20 mol) of the following compound (D5 ') was added to a solution of 120 ml of N, N-dimethylacetamide in 21.2 g (0.15 mol) of potassium carbonate. ), And bromoacetic acid t
-Butyl 27.1 g (0.14 mol) was added and 120
The mixture was stirred at 0 ° C for 7 hours. Then, the reaction mixture is treated with water 1.5.
The mixture was added to liter and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), resulting in 24 g of a pale yellow powder. Got By NMR, this compound Example (62: R are all _{-CH 2 COO-C 4 H 9} t group) was confirmed to be.

[0138]

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Synthesis Example (8) Synthesis of Compound (D6) 20 g (0.0042 mol) of the above compound (D1 ′) was dissolved in 400 ml of tetrahydrofuran (THF). 9.3 g of potassium t-butoxide was added to this solution under a nitrogen atmosphere.
(0.083 mol) was added and after stirring at room temperature for 10 minutes,
19.5 g of di-t-butyl dicarbonate (0.087
Mol) was added. The reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate extract was concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 1 /
5 (volume ratio)), as a result of the fractional purification, the compound example (3
1: 2 R is a t-BOC group, 1 R is a hydrogen atom) 7
g was obtained.

Synthesis Example (9) Synthesis of Compound (D7) 48.1 g (0.10 mol) of the above compound (D1 ′) was dissolved in 300 ml of dimethylacetamide, and 22.1 g (0.16 mol) of potassium carbonate was added thereto. , And bromoacetic acid t-
Butyl 42.9 g (0.22 mol) was added. Then, it stirred at 120 degreeC for 5 hours. The reaction mixture was poured into 2 liters of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. The ethyl acetate extract was concentrated and fractionally purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 1/5 (volume ratio)). As a result, a compound example (31: 2 R It is -CH ₂ CO
10 g of an O—C ₄ H ₉ ^t group and one R is a hydrogen atom was obtained.

Synthesis Example (10) Synthesis of Compound (D8) 44 g (0.10 mol) of the following compound (D8 ′) was added to N, N.
-Dissolved in 300 ml of dimethylacetamide, 70.2 g (0.497 mol) of potassium carbonate and 89.8 g (0.464 mol) of t-butyl bromoacetate were added thereto. Thereafter, the mixture was stirred at 120 ° C. for 7 hours. Thereafter, the reaction mixture was poured into 1.5 liters of water, and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), which was a pale yellow powder. 135 g are obtained.
According to NMR, this is an example compound (60: R is all -CH
₂ COO—C ₄ H ₉ ^t group) was confirmed.

[0142]

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[Synthesis Example of Novolac Resin] 45 g of m-cresol, 55 g of p-cresol, 48 g of 37% aqueous formalin solution and 0.13 g of oxalic acid were placed in a three-necked flask and heated to 100 ° C. with stirring for 15 hours. It was made to react. Then, raise the temperature to 200 ℃ and gradually increase to 5mmHg.
Water, unreacted monomers, formaldehyde, oxalic acid, etc. were removed by reducing the pressure to. Next, the molten alkali-soluble novolak resin (NOV.3) was returned to room temperature and collected. The obtained novolak resin (NOV.3) had a weight average molecular weight of 6800 (in terms of polystyrene).

Similarly, the following novolak resins having different monomer compositions were synthesized. NOV. 1 m-cresol / p-cresol = 65/35 Mw = 13,000 NOV. 2 m-cresol / p-cresol = 55/45 Mw = 8,500 NOV. 4 m-cresol / p-cresol / 3,5-xylenol = 20/55/28 Mw = 5,000 NOV. 5 m-cresol / 2,3,5-trimethylphenol = 50/63 Mw = 5,500

The novolak resin (NOV.
3) After completely dissolving 20 g in 60 g of methanol, 30 g of water was gradually added to this while stirring to precipitate a resin component. The upper layer was removed by decantation to collect the precipitated resin, which was heated to 40 ° C. and dried under reduced pressure for 24 hours to obtain an alkali-soluble novolak resin (NOV.
6) was obtained. The weight average molecular weight was 8,500 (converted to polystyrene).

80 g of m-cresol, p-cresol 2
0 g, 51 g of 37% formalin aqueous solution were charged into a three-necked flask and well stirred while heating in an oil bath at 110 ° C.,
2.4 g of zinc acetate dihydrate was added, and the mixture was heated with stirring for 5 hours. Then, 100 g of the same cresol mixture and 49 g of formalin aqueous solution were continuously charged into the same flask, and the mixture was further heated and stirred for 1 hour, then the temperature was lowered to 80 ° C. and 0.2 g of oxalic acid was added. Again, the temperature of the oil bath was maintained at 110 ° C., and the reaction was carried out under reflux for 15 hours. Thereafter, the content was poured into water containing 1% hydrochloric acid, and the reaction product was extracted with ethyl cellosolve acetate. Then, it was transferred to a vacuum still, the temperature was raised to 200 ° C., dewatered, and further distilled under reduced pressure of 2-3 mmHg for 2 hours to remove residual monomers. The molten polymer was recovered from the flask to obtain the target novolak resin (NOV.7, Mw = 7,700).

Examples 1 to 10 Resists were prepared using the compounds of the present invention shown in the above synthesis examples. The prescription at that time is shown in Table 1.

[Preparation and Evaluation of Photosensitive Composition] Each material shown in Table 1 was dissolved in 23 g of diglyme and filtered through a 0.2 μm filter to prepare a resist solution. This resist solution was applied onto a silicon wafer using a spin coater at a rotation speed of 3000 rpm, and the temperature was adjusted to 130 ° C. 6
It was dried on a vacuum adsorption type hot plate for 0 seconds to obtain a resist film having a film thickness of 1.0 μm. 2 on this resist film
48nm KrF excimer laser stepper (NA = 0.
45) was used for exposure. After the exposure, heating was performed on a vacuum adsorption type hot plate at 90 ° C. for 60 seconds, and immediately 2.
It was immersed in a 38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist profile. The shape of the resist
It is represented by the angle (θ) formed by the resist wall surface and the plane of the silicon wafer in the cross section of the resist pattern of 0.40 μm. The results are shown in Table-1.

The sensitivity was defined as the reciprocal of the exposure dose for reproducing a mask pattern of 0.60 μm, and shown by the relative value of the sensitivity of Comparative Example 1. The film shrinkage was expressed as a percentage of the ratio of the film thickness before and after exposure of the exposed portion and baking. The film loss (%) due to development was expressed as a percentage of the ratio of the film thickness of the unexposed area before and after development. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.60 μm. However, as the resolving power, the resolving power when heated and developed immediately after exposure and 0.1 ppm
Resolving power in the case of being left for 30 minutes in an atmosphere of ammonia concentration, heated and developed. Here, as a method of leaving it in an atmosphere with an ammonia concentration of 0.1 ppm, the ammonia gas concentration adjusting device shown in FIG. 1 was used. FIG. 1 mainly comprises a gas mixing chamber 1 and a sample chamber 2. First, from the ammonia gas tank 3 and the nitrogen gas tank 4 to the gas mixing chamber 1,
Mass flow meter 5 for ammonia gas and nitrogen gas,
Ammonia gas is introduced while adjusting the flow rate so that the concentration is 0.1 ppm. Each gas introduced into the gas mixing chamber 1 was agitated by an agitating means to make it uniform. Further, the substrate coated with the various photosensitive compositions obtained above was put in the sample chamber 2 and sucked so as to be a vacuum. Ammonia gas having a uniform concentration of 0.1 ppm was put into the sample chamber 2 and left for 30 minutes.

[0150]

[Table 1]

From the results shown in Table 1, it can be seen that the resist of the present invention has less film shrinkage due to baking after exposure and less film loss due to development, and has good sensitivity and profile and high resolution.

[0152]

EFFECT OF THE INVENTION The chemically amplified positive photoresist composition of the present invention and the coating film using the same have less film shrinkage due to baking after exposure and film loss after development, and have good sensitivity, profile and high sensitivity. It has a resolving power and is stable during storage until exposure and after heating, that is, it is hardly affected by a basic substance such as ammonia which is likely to be exposed during storage.

[Brief description of drawings]

FIG. 1 is a schematic view showing an ammonia gas concentration adjusting device.

[Explanation of symbols]

 1 Gas mixing chamber 2 Sample chamber 3 Ammonia gas tank 4 Nitrogen gas tank 5 Mass flow meter

Claims (3)

[Claims] 1. (A) an alkali-soluble resin; (B) a compound having at least one enol ether group represented by the following general formula (a): (In the formula (a), R _{1 to} R ₃ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group. , And two of them may combine to form a saturated or unsaturated ring.) (C) Compound having an acidic group (D) Low molecular weight of 3,000 or less having an acid-decomposable group A positive photoresist composition comprising a molecular compound (E), a compound (F) which decomposes upon irradiation with actinic rays or radiation to generate an acid (F). 2. The blending ratio of the component (B) and the component (D) to the total solid content is 5 (wt%) ≦ [B + D] ≦ 70 (wt%), and 5 (wt%) ≦ 100 D / [B + D ] <80 (weight%) The relational expression of these is satisfied, The positive photoresist composition of Claim 1 characterized by the above-mentioned. 3. A coating film obtained by applying the positive photoresist composition according to claim 1 onto a substrate and heating and drying.