JP2001215714A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve problems on a technique adaptable to reduction in the thickness of a film for lithography using far ultraviolet light and to provide a radiation sensitive resin composition capable of reproducing a desired resist pattern which retains satisfactory intrasurface uniformity, has high resolving power and collapses hardly even in a thin film process. SOLUTION: The radiation sensitive resin composition contains an Si- containing resin having a velocity of dissolution in an alkali developing solution increased by the action of an acid, a photo-acid generating agent and a solvent and has <=6.0 mPa.sec viscosity at 25 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type radiation-sensitive resin composition for use in an ultra-microlithography process such as the production of an VLSI or a high-capacity microchip and other photofabrication processes. More specifically, the present invention relates to a positive-type radiation-sensitive resin composition having high resolution and less pattern collapse used in a thin film process.

[0002]

2. Description of the Related Art In recent years, with the increase in integration and speed of LSI, miniaturization of patterns has been required. As one of means for miniaturizing a pattern, there is a method of shortening the wavelength of exposure light used for forming a resist pattern.
6Mbit DRAM (processing dimension 0.25μm or less) DRAM
In the mass production process of (dynamic random access memory), a short wavelength KrF excimer laser (248n) is used as an exposure light source instead of i-line (365nm).
The use of m) is currently under active consideration. However, in order to manufacture a DRAM having an integration degree of 1 G or more, which requires a finer processing technology (processing size of 0.2 μm or less), a light source having a shorter wavelength is required. In particular, an ArF excimer laser (193 nm) is used. Photography has recently been considered.

Here, in the case of lithography using short-wavelength light of 220 nm or less typified by an ArF excimer laser, a photoresist is required to have new characteristics that cannot be satisfied by conventional materials in order to form a fine pattern. . For this reason, various resist materials having high sensitivity and high resolution have been developed. These radiation-sensitive resin compositions are all of high sensitivity and high resolution, but it is difficult to form a fine pattern with a high aspect ratio in view of the mechanical strength of the pattern obtained therefrom. there were.

[0004] Further, many radiation-sensitive resin compositions using polyhydroxystyrene as a base resin and having sensitivity to far ultraviolet rays, electron beams and X-rays have been proposed. However, in order to form a pattern having a high aspect ratio on a stepped substrate, a two-layer resist method is excellent, whereas all of the above resist materials are based on a single-layer resist method, and the problem of a substrate step difference still exists. At present, there is a problem of light reflection from the substrate and a problem of difficulty in forming a pattern having a high aspect ratio.

On the other hand, conventionally, it has been known that a two-layer resist method is excellent for forming a pattern having a high aspect ratio on a stepped substrate. Further, it is also known that in order to develop a two-layer resist film with a general alkali developer, it is necessary to include a high molecular silicone compound having a hydrophilic group such as a hydroxy group or a carboxyl group. . However, in the case of a silanol in which a hydroxyl group is directly bonded to a high molecular silicone compound even if it has a hydrophilic group, a cross-linking reaction occurs due to an acid, and thus application to a radiation-sensitive resin composition has been difficult.

In recent years, as a silicone-based radiation-sensitive resin composition which solves these problems, a part of the phenolic hydroxyl group of polyhydroxybenzylsilsesquioxane which is a stable alkali-soluble silicone polymer is replaced with t-Bo.
A silicone-based radiation-sensitive resin composition has been proposed in which a resin protected by the c group is used as a base resin, and this is combined with an acid generator (JP-A-7-118865,
SPIEvol. 1952 (1993) 377).

Among such compositions, Japanese Patent Application Laid-Open No. H10-324 is an example of a two-layer resist having high sensitivity and high resolution and particularly suitable for forming a pattern having a high aspect ratio.
No. 748.

[0008] However, in order to achieve Si-containing deep ultraviolet lithography which is applied even after the design rule of 0.13 μm, further higher resolution is required.

As one means for solving this problem, application of a thin film process in which the used film thickness of the resist is reduced has been studied. This is expected to improve performance such as resolution and depth of focus.

However, the existing Si-containing chemically amplified photoresist has various problems in thinning. That is, although the cause was not clear, it was found that the in-plane uniformity could not be obtained and various performances were degraded, and it was not possible to satisfactorily cope with the thin film process. Further, if the film thickness is increased in order to maintain the in-plane uniformity, the resolution is not satisfactory and the pattern collapses. This is a fact that cannot be conceived from past experience, and therefore, a radiation-sensitive resin composition that can maintain sufficient in-plane uniformity even in a thin film process and can obtain a desired sensitivity and resolution without pattern collapse. Is required.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the technical problem corresponding to the thinning of lithography using far ultraviolet light, and more specifically, to provide a sufficient in-plane even in a thin film process. It is an object of the present invention to provide a radiation-sensitive resin composition that maintains uniformity, has high resolution, has little pattern collapse, and can reproduce a desired resist pattern.

[0012]

Means for Solving the Problems The present inventors have conducted intensive studies on various existing body-type chemically amplified radiation-sensitive resin compositions, and as a result, adjusted the composition to have a specific viscosity using the following composition. As a result, it has been found that the object of the present invention is achieved, and the present invention has been achieved. That is, the above object is achieved by the following composition. (1) It has the property of increasing the dissolution rate in an alkaline developer by the action of an acid, and further contains a resin containing an Si element, a photoacid generator, and a solvent, and has a viscosity at 25 ° C. of 6 0.02 mPa · sec or less. (2) The viscosity at 25 ° C. is 0.9 to 5.0 mPa · se.
The radiation-sensitive resin composition according to the above (1), which is within the range of c. (3) The viscosity at 25 ° C. is 1.5 to 4.5 mPa · se.
The radiation-sensitive resin composition according to the above (1), which is within the range of c. (4) The resin (1) to (1), wherein the resin containing a Si element is a polymer containing a repeating unit represented by the following general formula (1) and having a group that is decomposed by the action of an acid.
The radiation-sensitive resin composition according to any one of (3).

[0013]

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[Wherein, Z is a divalent or hexavalent carbon atom having 5 to 1 carbon atoms.
2 monocyclic or polycyclic hydrocarbon groups or bridged cyclic hydrocarbon groups, R ¹ is a linear, branched or cyclic unsubstituted or substituted alkyl or alkenyl group having 1 to 8 carbon atoms Is shown. R ² represents an acid-decomposable group. m is 0 or a positive integer, n
Is a positive integer and is a number satisfying m + n ≦ 5. x
Is a positive integer. p1 and p2 are positive numbers, q is 0 or a positive number, and 0 <p1 / (p1 + p2 + q) ≦ 0.9, 0 <
p2 / (p1 + p2 + q) ≦ 0.9, 0 ≦ q / (p1 +
p2 + q) ≦ 0.7, which satisfies p1 + p2 + q = 1. In the carboxyl group in the repeating unit, 90% or less of the hydrogen atoms of the carboxyl group are substituted by a crosslinking group having a C—O—C group represented by the following general formula (2a) or (2b). It may be crosslinked inside and / or between molecules.

[0015]

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(Wherein R ³ and R ⁴ are each a hydrogen atom or carbon atom 1)
And represents a linear, branched or cyclic alkyl group of from 8 to 8. R
³ and R ⁴ may combine with each other to form a ring. When forming a ring, the total number of carbon atoms of both R ³ and R ⁴ is 1 to
8, both of them represent a linear or branched alkylene group. R ⁵ is a linear or branched alkylene group having 1 to 10 carbon atoms, and d is 0 or an integer of 1 to 10. A is
A (c ′ + 1) -valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a hetero atom interposed;
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c ′ is an integer of 1 to 7. )]

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The resin in the present invention has a property that the dissolution rate in an alkali developing solution is increased by the action of an acid.
It is a resin containing an element (hereinafter, also referred to as a polymer silicone compound). The polymeric silicone compound contains a group that is decomposed by the action of an acid (also referred to as an acid-decomposable group) and a Si element (silicon atom). Here, the Si element may be included as a Si element-containing substituent in the side chain in the high molecular silicone compound, or may be included in the resin skeleton.
In the present invention, the Si element is preferably included in the skeleton of the resin. As such a skeleton containing an Si element,
A siloxane skeleton and a silsesquioxane skeleton can be preferably mentioned, and a silsesquioxane skeleton is particularly preferable. The acid-decomposable group contained in the high molecular silicone compound can be variously selected as long as it is a group that is decomposed by the action of an acid, and preferably includes an acid-decomposable group represented by R ² described below. . The polymer silicone compound is preferably a polymer silicone compound having a repeating unit represented by the above general formula (1).

[0018]

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(Wherein Z is a divalent or hexavalent C 5-12 carbon atom)
And R ¹ represents a linear, branched or cyclic unsubstituted or substituted alkyl group or alkenyl group having 1 to 8 carbon atoms, wherein R ¹ is a monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group. R
² represents an acid-decomposable group, m is 0 or a positive integer, n is a positive integer (an integer of 1 or more), and is a number satisfying m + n ≦ 5. x is a positive integer. p1 and p2 are positive numbers, q is 0 or a positive number, and 0 <p1 / (p1 + p2 + q) ≦
0.9, 0 <p2 / (p1 + p2 + q) ≦ 0.9, 0 ≦
q / (p1 + p2 + q) ≦ 0.7, p1 + p2 + q = 1
Is a number that satisfies. )

Here, Z is a divalent or hexavalent carbon atom having 5 to 12 carbon atoms.
Specific examples of the monocyclic or polycyclic hydrocarbon group or the bridged cyclic hydrocarbon group include the following hydrocarbon groups, but are not limited thereto. That is, as the hydrocarbon group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, a cycloheptanetriyl group, a cyclohexanetetrayl group, a cyclohexanepentyl group, a cyclohexane Hexayl group, cyclooctanediyl group, cyclonanonediyl group, cyclodecanediyl group, cyclooctanetriyl group, cyclonanantriyl group, cyclodecanetriyl group, norbornanediyl group, isobornanediyl group, norbornanetriyl group , Isobornantriyl group, adamantanediyl group,
Tricyclo [5,2,1,0 ^2,6 ] decanediyl group, adamantanetriyl group, tricyclo [5,2,1,0]
^2,6 ] decantriyl group, tricyclo [5,2,1,0
^2,6 ] decanemethylenediyl group, tricyclo [5,2,
1,0 ^2,6 ] decanemethylenetriyl group and the like. A preferred example is a high molecular silicone compound having a repeating unit represented by the following general formula (3).

[0021]

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(Where R ¹ , R ² , m, n, x, p1, p
2 and q have the same meanings as above. Examples of the linear, branched or cyclic unsubstituted alkyl or alkenyl group having 1 to 8 carbon atoms for R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert group. -Butyl group, cyclohexyl group,
Examples thereof include a cyclopentyl group, a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the substituted alkyl group or alkenyl group include those in which part or all of the hydrogen atoms of these unsubstituted alkyl groups or alkenyl groups are substituted with, for example, a cyano group, a nitro group, or an alkoxy group having 1 to 5 carbon atoms. be able to. X is an integer, and is 1 to 3, especially 1 to
2 is preferred. In the above formula (1), p1 and p2 are positive numbers, q is 0 or a positive number, and is a number satisfying p1 + p2 + q = 1. That is, p1, p2, and q are respectively a p1 repeating unit, a p2 repeating unit, and q of the compound of the present invention.
Shows the ratio of repeating units of the formula: 0 ≦ q /
(P1 + p2 + q) ≦ 0.7, especially 0 ≦ q / (p1 + p
2 + q) ≦ 0.6, and when it exceeds 0.7, it becomes insoluble in alkali, and thus is not suitable as a base polymer for resist. If q / (p1 + p2 + q) is too low, the heat resistance may decrease. Also, 0 <p1 /
(P1 + p2 + q) ≦ 0.9, more preferably 0.3 <
p1 / (p1 + p2 + q) ≦ 0.8, and 0 <p2 /
(P1 + p2 + q) ≦ 0.9, more preferably 0.2 <
p2 / (p1 + p2 + q) ≦ 0.7. When p1 becomes 0, the contrast of the alkali dissolution rate becomes small and the resolution may be deteriorated. On the other hand, if it exceeds 0.9, it will not be soluble in alkali, cause a change in film thickness, stress in the film or the generation of bubbles during alkali development, and the adhesion to the substrate because the number of hydrophilic groups decreases. May be inferior.

As the acid-decomposable group for R ² , various ones are selected, and in particular, a group represented by the following general formula (4), a group represented by the following general formula (5), and a tertiary group having 4 to 20 carbon atoms. The alkyl group is preferably one or two or more groups selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

[0024]

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In the formula, R ⁶ and R ⁷ represent a hydrogen atom or a group having 1 to 1 carbon atoms.
8, preferably 1 to 6, more preferably 1 to 5, a linear, branched or cyclic alkyl group, and R ⁸ has 1 to 18 carbon atoms, preferably 1 to 10, more preferably 1 to ⁸ carbon atoms.
A monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom, wherein R ⁶ and R ⁷ , R ⁶ and R ⁸ , R ⁷ and R ⁸ may form a ring, When a ring is formed, R ⁶ , R ⁷ , R
^{And 8} represents a linear or branched alkylene group having 1 to 18, preferably 1 to 10, and more preferably 1 to ⁸ carbon atoms. R ⁹ has 4 to 20, preferably 4 to 15, carbon atoms;
More preferably, it is a tertiary alkyl group having 4 to 10 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and 4 to 20 carbon atoms, preferably 4 to 15, more preferably 4 to 15.
Oxoalkyl group of 10 to 10 or a group represented by the above general formula (4). A is an integer of 0 to 6.

R⁶, R⁷Linear or branched having 1 to 8 carbon atoms
Or, as a cyclic alkyl group, R ¹With what was explained in
Similar groups are mentioned.

R ⁸ represents a linear, branched or cyclic alkyl group, phenyl group, p-methylphenyl group, p-methylphenyl group,
Unsubstituted or substituted aryl groups such as alkoxy-substituted phenyl groups such as ethylphenyl group and p-methoxyphenyl group; aralkyl groups such as benzyl group and phenethyl group; and those groups having an oxygen atom or bonded to a carbon atom Examples of such groups include an alkyl group represented by the following formula, in which a hydrogen atom is substituted by a hydroxyl group, or two hydrogen atoms are substituted by an oxygen atom to form a carbonyl group.

[0028]

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Examples of the tertiary alkyl group having 4 to 20 carbon atoms for R ⁹ include a tert-butyl group, a 1-methylcyclohexyl group, a 2- (2-methyl) adamantyl group, and a te-butyl group.
An rt-amyl group and the like can be mentioned.

Examples of the trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butyl group and the like. Examples of the oxoalkyl group having 4 to 20 carbon atoms are , 3-
An oxocyclohexyl group, a group represented by the following formula, and the like are given.

[0031]

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Specific examples of the acid-decomposable group represented by the above formula (4) include, for example, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1
-Isobutoxyethyl group, 1-sec-butoxyethyl group, 1-tert-butoxyethyl group, 1-tert-
An amyloxyethyl group, a 1-ethoxy-n-propyl group,
1-cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-
Examples thereof include a linear or branched acetal group such as an ethyl group and a 1-ethoxy-1-methyl-ethyl group, and a cyclic acetal group such as a tetrahydrofuranyl group and a tetrahydropyranyl group, and preferably an ethoxyethyl group and a butoxyethyl group. And ethoxypropyl groups. On the other hand, as the acid-decomposable group of the above formula (5), for example, tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group , 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

In the above general formula (1), more than 0 mol% and not more than 90 mol%, preferably more than 0 mol% and not more than 80 mol%, more preferably 1 to 60 mol% of all hydrogen atoms of the carboxyl group. % Is represented by the general formula (2a) or (2
It may be crosslinked intramolecularly and / or intermolecularly by a crosslinking group having a C—O—C group shown in b). In the present invention, a polymer compound having a crosslinking group is preferable.

The polymer compound having a cross-linking group will be described in more detail. As the polymer silicone compound, some hydrogen atoms of carboxyl groups of a silicone resin having a repeating unit represented by the following general formula (3a) are used. Intramolecular and intramolecular by a cross-linking group having a C—O—C group, which is partially substituted by an acid-decomposable group and obtained by reacting a part of the remaining carboxyl groups with an alkenyl ether compound and / or a halogenated alkyl ether compound. /
Or a high molecular weight silicone compound which is cross-linked between molecules and whose total amount of the acid-decomposable group and the cross-linking group is more than 0 mol% and not more than 80 mol% on average of the entire carboxyl group in the formula (1). can do.

[0035]

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(Wherein, R ¹ has 1 to 8 carbon atoms as described above)
Represents a linear, branched or cyclic unsubstituted or substituted alkyl group or alkenyl group. x is a positive integer. p, q
Is a positive number, 0 ≦ q / (p + q) ≦ 0.6, p + q =
It is a number that satisfies 1. )

In the above equation (3a), p and q are positive numbers and satisfy p + q = 1. That is, p, q
Represents the ratio of the repeating unit of p and the repeating unit of q in the compound of the present invention, and 0 ≦ q / (p + q) ≦
0.6, particularly preferably 0 ≦ q / (p + q) ≦ 0.5. In this case, if q / (p + q) ≦ 0.6, it becomes insoluble in alkali, and thus is not suitable as a base polymer for resist. If q / (p + q) is too low, the heat resistance may decrease. Therefore, it is more preferable that q / (p + q) be 0.2 or more. Incidentally, p and q can be arbitrarily controlled for the pattern dimension and the pattern shape by appropriately selecting their values within the above range.

Specific examples of such a high molecular silicone compound include a part of a carboxyl group represented by R of a silicone resin having a repeating unit represented by the following general formula (3b) and an alkenyl ether compound and / or a halogenated compound. C obtained by reaction with an alkyl ether compound
The compound is cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a -OC group, and the total amount of the acid-decomposable group and the cross-linking group is an average of 0 mol% of the entire carboxyl group in the formula (1).
And at most 80 mol%.

[0039]

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(Wherein R is a carboxyl group or COOR
^{2 wherein} at least one of R is a carboxyl group. R ¹ represents a linear, branched or cyclic unsubstituted or substituted alkyl or alkenyl group having 1 to 8 carbon atoms, and R ² represents an acid-decomposable group. x is a positive integer. m ′ is 0 or a positive integer, n ′ is a positive integer, and is a number that satisfies m ′ + n ′ ≦ 5. p3 is a positive number, p4 is 0 or a positive number, q
Is 0 or a positive number, and 0 <p3 / (p3 + p4 + q) ≦
0.8, 0 ≦ q / (p3 + p4 + q) ≦ 0.6, 0.4
≦ (p3 + p4) / (p3 + p4 + q) ≦ 1, p3 + p
This is a number that satisfies 4 + q = 1. Note that p3 + p4 = p
And p is as described above. In addition, examples of the crosslinking group having a C—O—C group include those represented by the following general formula (2a) or (2b).

[0041]

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(Wherein R ³ and R ⁴ are hydrogen atoms or carbon atoms 1)
And represents a linear, branched or cyclic alkyl group of from 8 to 8. Alternatively, R ³ and R ⁴ may form a ring, and when forming a ring, R ³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ⁵ is a linear or branched alkylene group having 1 to 10 carbon atoms, and d is 0 or an integer of 1 to 10. A represents a (c ′ + 1) -valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group (preferably a linear or branched C 1 to C 20 Alkylene group, alkyltriyl group, alkyltetrayl group, or arylene group having 6 to 30 carbon atoms), and these groups may have a heteroatom interposed therebetween, and hydrogen bonded to the carbon atom Some of the atoms may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O-
Or -NHCONH-. c ′ is an integer of 1 to 7. )

Here, examples of the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms are the same as those described above. A specific example of A will be described later. The crosslinking groups (2a) and (2b) are derived from alkenyl ether compounds and halogenated alkyl ether compounds described below. As is clear from the value of c ′ in the above formulas (2a) and (2b), the crosslinking group is not limited to divalent but trivalent to
It may be an octavalent group. For example, as a divalent crosslinking group, the following formulas (2a ′) and (2b ′)
Examples represented by the following formulas (2a ″) and (2b ″) are given.

[0044]

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A preferred crosslinking group is represented by the following general formula (2)
a ''') or (2b''').

[0046]

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(Wherein, R ³ , R ⁴ , R ⁵ , and d have the same meanings as described above. A ′ is a linear, branched or cyclic alkylene group having a c ″ valency and having 1 to 20 carbon atoms.) Represents an alkyltriyl group, an alkyltetrayl group, an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed;
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c ″ is 2-4, c ″ ′
Is an integer of 1 to 3. )

As a specific example of the polymer silicone compound of the above formula (3a) of the present invention, the following general formula (3a)
The hydrogen atom of the carboxyl group represented by R of the silicone resin having the repeating unit represented by c) is removed, and the terminal oxygen atom has a C—O—C group represented by the above general formula (2a) or (2b). Crosslinked intramolecularly and / or intermolecularly by a divalent or higher valent crosslinkable group, and the total amount of the acid-decomposable group and the crosslinkable group is more than 80 mol% on average exceeding 0 mol% of the whole carboxyl group in the formula (3a). Polymer silicone compounds having the following ratios can be mentioned.

[0049]

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(Wherein R is a carboxyl group or COOR
^{2 wherein} at least one of R is a carboxyl group. R ¹ is a straight, branched or cyclic unsubstituted or substituted alkyl or alkenyl of 1 to 8 carbon atoms, R ²
Represents an acid-decomposable group as described above. p31 is a positive number, p
32, p4, and q are 0 or a positive number, and 0 <p31 / (p
31 + p32 + p4 + q) ≦ 0.8, 0 ≦ p4 / (p3
1 + p32 + p4 + q) ≦ 0.8, 0 ≦ q / (p31 +
p32 + p4 + q) ≦ 0.6, 0.4 ≦ (p31 + p3
2 + p4) / (p31 + p32 + p4 + q) ≦ 1, p3
This is a number that satisfies 1 + p32 + p4 + q = 1. x is a positive integer. m ′ is 0 or a positive integer, n ′ is a positive integer, and is a number that satisfies m ′ + n ′ ≦ 5. Note that p31 + p32 = p3, where p3 is as described above. P31, p32, p4, and q indicate the numbers described above, and more preferably, the values of p31, p32, p4, and q are as follows.

[0051]

(Equation 1)

Examples of the polymer compound include those represented by the following formulas (3′-1) and (3′-2).

[0053]

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[0054]

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In the above formula, p41 and p42 are each 0 or a positive number. However, p41 and p42 never become 0 at the same time. p41 + p42 = p4. Equation (3 '
-1) indicates an intermolecular bond, and formula (3'-2) indicates a state of an intramolecular bond, and these may be used alone or in combination. Here, p41 / (p41 + p42) is preferably 0.1 to 1, more preferably 0.5 to 1, and still more preferably 0.7 to 1.

Q is a cross-linking group having a C—O—C group, typically a cross-linking group represented by the above formula (2a) or (2b), in particular, a formula (2a ′), (2b ′) or (2a ′) '), (2
b "), preferably (2a""),(2b"")
Is a cross-linking group. In this case, when the cross-linking group is trivalent or more, in the above formula (3a), Q is bonded to three or more of the following units.

[0057]

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The high molecular weight silicone compound of the above formula (3a) of the present invention has a carboxyl group in which some hydrogen atoms are substituted by an acid-decomposable group and a crosslinking group having a C—O—C group. More preferably, the total of the acid-decomposable group and the cross-linking group is more than 0 mol% on average and not more than 80 mol%, particularly 2 to 40 mol%, based on the total carboxyl groups in the formula (3a). Is preferred.

In this case, the proportion of the crosslinking group having a C—O—C group to the entire carboxyl group in the formula (3a) is more than 0 mol% on average and 80 mol% or less, preferably 1 to 20 mol%. When the content is 0 mol%, the contrast of the alkali dissolution rate becomes small, and the advantage of the cross-linking group cannot be brought out, resulting in poor resolution. On the other hand, if it exceeds 80 mol%, it crosslinks too much and gels, loses its solubility in alkali, causes a change in film thickness, the generation of stress in the film or the generation of bubbles during alkali development, and the reduction of hydrophilic groups. Therefore, the adhesion to the substrate may be poor.

The ratio of the acid-decomposable group to the total carboxyl group in the formula (3a) is more than 0 mol% on average and 80%.
It is preferably at most mol%, particularly preferably from 10 to 40 mol%. At 0 mol%, the contrast of the alkali dissolution rate becomes small, and the resolution becomes poor. On the other hand, if it exceeds 80 mol%, the solubility in alkali may be lost, or the affinity with a developing solution may be reduced during alkali development, resulting in poor resolution.

The size of the pattern and the shape of the pattern can be arbitrarily controlled by appropriately selecting the values of the crosslinking group and the acid-decomposable group having a C—O—C group within the above ranges. In the polymer silicone compound of the present invention, the content of the crosslinking group having a C—O—C group and the acid-decomposable group affects the contrast of the dissolution rate of the resist film, and controls the resist dimensions such as pattern dimension control and pattern shape. It is related to the characteristics of

Here, the high molecular silicone compound may have two or more acid-decomposable groups in the molecule, or two or more polymers having different acid-decomposable groups may be blended.

The polymer silicone compound of the present invention has a weight average molecular weight of 1,000 to 500,000, preferably 1,500 to 300,000. When the weight average molecular weight is less than 1,000, the resist material has poor heat resistance, and when it exceeds 500,000, the resist material cannot be uniformly applied when spin-coated.

Next, the method for producing the high molecular silicone compound of the above formula (1) of the present invention will be described. The high molecular silicone compound has a divalent to hexavalent carbon number of 5 to 6 having a carboxylic acid alkyl ester group bonded thereto. Hydrolyzing a trichlorosilane compound having 12 monocyclic or polycyclic hydrocarbon groups or a bridged cyclic hydrocarbon group and, if necessary, a linear, branched or cyclic alkyl group, After further thermal condensation of the hydrolyzed condensate, the alkyl ester group is hydrolyzed (KOH, N
aOH or the like) to obtain a high molecular silicone compound of the following formula (1 ′). Note that trimethylsilylation is preferable in order to protect the silanol group at the main chain terminal in consideration of storage stability. By introducing an acid-decomposable group into the carboxyl group of the obtained high molecular silicone compound, the desired high molecular silicone compound can be obtained.

[0065]

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(In the formula, R ¹ , p ¹ , p 2, Z, q, and x have the same meanings as described above, and in this case, x = m + n.) Here, the acid-decomposable group is introduced by a known method. Can be done by Examples of the method of crosslinking with a crosslinking group having a C—O—C group include a method using an alkenyl ether compound or a halogenated alkyl ether compound.

That is, as a method for producing the polymer silicone compound of the present invention having a crosslinkable group having a C—O—C group, for example, the polymer silicone compound (1 ′) obtained by the above polymerization method may be used. General formula (4) for carboxyl group
Is introduced, and after isolation, is reacted with an alkenyl ether compound or a halogenated alkyl ether compound to form C—O—C within the molecule and / or between the molecules.
A method of cross-linking by a cross-linking group having a group, or a reaction with an alkenyl ether compound or a halogenated alkyl ether compound to cause intramolecular and / or intermolecular C-
After crosslinking with a group represented by OC and isolation, a method of introducing an acid-decomposable group represented by the general formula (4), or a reaction with an alkenyl ether compound or a halogenated alkyl ether compound and the general formula (4) )), The reaction with an alkenyl ether compound or a halogenated alkyl ether compound and the introduction of the acid-decomposable group represented by the general formula (4) are collectively performed. The preferred method is to do so. Further, if necessary, an acid-decomposable group represented by the general formula (5), a tertiary alkyl group, a trialkylsilyl group, an oxoalkyl group, or the like may be introduced into the obtained polymer silicone compound. It is possible.

Specifically, as a first method, a high molecular silicone compound having a repeating unit represented by the above formula (1 ′), an alkenyl ether compound represented by the following general formula (I) or (II): As a second method using a compound represented by the following general formula (4a), a polymer silicone compound having a repeating unit represented by the above formula (1 ′) and a polymer silicone compound represented by the following general formula (VI) or (VII) Using a halogenated alkyl ether compound and a compound represented by the following general formula (4b).

[0069]

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Here, R ¹ , Z, R ⁴ , R ⁵ , R ⁷ , R ⁸ ,
p1, p2, q and x have the same meanings as described above,
R ^3a and R ^{6a each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms.

Further, in the vinyl ether compound represented by the formula (I) or (II), A is a c-valent (c is 2 to 8) aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms. Represents an aromatic hydrocarbon group or a heterocyclic group,
Is -CO-O-, -NHCOO- or -NHCONH-
R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, and d represents 0 or an integer of 1 to 10.

Specifically, an aliphatic or fat having a c value of A
Preferred as cyclic saturated hydrocarbon groups and aromatic hydrocarbon groups are
Or O, NH, N having 1 to 50, especially 1 to 40 carbon atoms
(CH _Three), S, SO_TwoHeteroatoms such as
Unsubstituted or hydroxyl group, carboxyl group, acyl group or fluoro group
A substituted alkylene group, preferably having 6 to 5 carbon atoms
0, especially 6 to 40 arylene groups, these alkylene groups
And an arylene group are bonded to each other,
The c ″ value (c ″ is 3 to 8) from which the bonded hydrogen atom is eliminated.
And an integer c), and further a c-valent heterocyclic group,
Examples include a group in which a heterocyclic group is bonded to the above hydrocarbon group.
Can be The “heteroatom-intervening” group in A above;
Represents an alicyclic saturated hydrocarbon group, an aromatic hydrocarbon group or
(C ′ +)
1) It means a valence group.

Specifically, the following can be mentioned as A.

[0074]

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[0075]

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[0076]

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[0077]

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The compound represented by the general formula (I) is described, for example, in Stephen. C. Lapin, Polymer
s Paint Color Journal. 179
(4237), 321 (1988), that is, by a reaction between a polyhydric alcohol or a polyhydric phenol and acetylene, or a reaction between a polyhydric alcohol or a polyhydric phenol and a halogenated alkyl vinyl ether. it can.

Specific examples of the compound of the formula (I) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, and 1,3-butanediol divinyl ether. Vinyl ether, 1,4
-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, and the following formulas (I-1) to (I-31) However, the present invention is not limited thereto.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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On the other hand, when B is -CO-O-, the compound represented by the general formula (II) can be produced by reacting a polyvalent carboxylic acid with a halogenated alkyl vinyl ether. Specific examples of the compound represented by the formula (II) when B is -CO-O- include diethylene vinyl ether terephthalate, diethylene vinyl ether phthalate, diethylene vinyl ether isophthalate, dipropylene vinyl ether phthalate, and dipropylene vinyl ether terephthalate. Diethylene vinyl ether isophthalate, diethylene vinyl ether maleate, diethylene vinyl ether fumarate, diethylene vinyl ether itaconate, and the like, but are not limited thereto.

The alkenyl ether group-containing compound preferably used in the present invention includes an alkenyl ether compound having an active hydrogen represented by the following general formula (III), (IV) or (V) and an isocyanate group. Alkenyl ether group-containing compounds synthesized by a reaction with a compound having the alkenyl ether group.

[0087]

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(R ^3a , R ⁴ and R ⁵ have the same meanings as described above.)

B is -NHCOO- or -NHCONH-
In the above case, as the compound having an isocyanate group represented by the general formula (II), for example, a compound described in Handbook of Crosslinking Agent (published by Taiseisha, 1981) can be used. Specifically, triphenylmethane triisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-tolylene diisocyanate Polyisocyanate type such as nate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylolpropane, adduct of hexamethylene diisocyanate and water, xylene diisocyanate Examples thereof include polyisocyanate adducts such as adducts with trimethylolpropane. By reacting the above-mentioned isocyanate group-containing compound with an active hydrogen-containing alkenyl ether compound, various compounds having an alkenyl ether group at a terminal can be obtained. Such compounds are represented by the following formulas (II-1) to (II-1)
Examples shown in 1) can be cited, but are not limited thereto.

[0090]

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[0091]

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In the first method, for example, the formula (3)
When the high molecular silicone compound of a) is obtained, the weight average molecular weight is 1,000 to 50,000, and preferably p31 with respect to 1 mol of the carboxyl group of the high molecular compound represented by the following general formula (3 ′). Moles of the general formulas (I), (I
An alkenyl ether compound represented by I) and p41 +
By reacting p42 mol of the compound represented by the general formula (4a), for example, the following general formulas (3a'-1) and (3a'-
The polymer compound represented by 2) can be obtained.

[0093]

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Here, R ¹ , x, p31, p41, p4
2, p32 and q have the same meaning as described above, and p31 + p
41 + p42 + p32 + q = 1.

[0095]

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[0096]

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In the above formula, Q, m ', n' and other symbols are the same as above. In the first method, the reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran, or ethyl acetate, and may be used alone or as a mixture of two or more.

As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, pyridinium p-toluenesulfonate and the like are preferable. It is preferable that the content is 0.1 to 10 mol% with respect to 1 mol of the carboxyl group of the polymer compound represented by the formula (1 ′).

The reaction temperature is -20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 1
00 hours, preferably 0.5 to 20 hours.

When the above reactions are carried out collectively without isolation,
The order of adding the alkenyl ether compound represented by the general formula (I) or (II) and the compound represented by the general formula (4a) is not particularly limited, but first, the compound represented by the general formula (4a) is added, After the reaction has sufficiently proceeded, it is preferable to add the alkenyl ether compound represented by the general formula (I) or (II). For example, the alkenyl ether compound represented by the general formula (I) or (II) and the compound represented by the general formula (4a) are added simultaneously, or the alkenyl ether compound represented by the general formula (I) or (II) is added first. When added, the compound represented by the general formula (I) or (II)
In some cases, a part of the reaction points of the alkenyl ether compound represented by the formula (1) is hydrolyzed by water in the reaction system, the structure of the produced polymer compound becomes complicated, and the control of physical properties may be difficult.

[0101]

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(Wherein R ¹ , R ³ -R ⁵ , R ^6a , R ⁷ ,
R ⁸ , Z, p1, p2, q, x, A, B, c, and d each have the same meaning as described above, and Z ₁ is a halogen atom (C
1, Br or I). )

The compounds of the above formulas (VI) and (VII) and the compound of the formula (4b) are obtained by adding hydrogen chloride and hydrogen bromide to the compounds of the above formulas (I) and (II) and the compound of the formula (4a). Alternatively, it can be obtained by reacting hydrogen iodide.

In the second method, for example, when obtaining a high molecular silicone compound of the formula (3a), the weight average molecular weight is 1,
P31 + p4 with respect to 1 mol of the phenolic hydroxyl group and the carboxyl group of the polymer compound having a repeating unit represented by the general formula (3 ′) of 000 to 500,000.
1 mol of the halogenated alkyl ether compound represented by the general formula (VI) or (VII) and p41 mol of the compound represented by the general formula (4b) are reacted, and for example, the above-mentioned formula (3a′-1), (3a The polymer compound represented by '-2) can be obtained.

The above production method is preferably carried out in a solvent in the presence of a base. As the reaction solvent, aprotic polar solvents such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran and dimethylsulfoxide are preferable.
A mixture of more than one species may be used.

As the base, triethylamine, pyridine, diisopropylamine, potassium carbonate and the like are preferable. The amount of the base to be used is 1 mole times 1 mole of the carboxyl group of the polymer compound represented by the general formula (1 ′) to be reacted. More preferably, it is preferably at least 5 mol times.

The reaction temperature is -50 to 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.5 to 1
00 hours, preferably 1 to 20 hours.

As described above, the acid obtained by reacting the compound of the formula (4a) or (4b) with the polymer having a repeating unit of the formula (1 ′) or (3 ′) is obtained. Compound having a decomposable group, for example, the following formula (3d)
After obtaining the compound represented by the formula (I), the compound may be isolated and then subjected to crosslinking using the compound represented by the formula (I), (II) or (VI) or (VII).

[0109]

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The polymer compound represented by the formula (3a′-1) or (3a′-2) obtained by the above first or second method may be added to the original formula (3 ′) if necessary. A) reacting a dialkyl dicarbonate compound, an alkoxycarbonylalkyl halide or the like with p42 mol with respect to 1 mol of the carboxyl group of the polymer compound represented by the formula (1) to introduce an acid-decomposable group represented by the general formula (5); By reacting a tertiary alkyl halide, a trialkylsilyl halide, an oxoalkyl compound, or the like, for example, a compound represented by the general formula (3b′-1) or (3
A polymer compound represented by b′-2) can be obtained.

[0111]

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[0112]

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In the above formula, Q, m ', n' and other symbols are the same as above.

The method for introducing the acid-decomposable group of the above formula (5) is as follows.
It is preferable to carry out the reaction in a solvent in the presence of a base.

Examples of the reaction solvent include acetonitrile, acetone, dimethylformamide, dimethylacetamide,
Aprotic polar solvents such as tetrahydrofuran and dimethylsulfoxide are preferred, and they may be used alone or as a mixture of two or more.

As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable. The amount of the base is 1 to 1 mol of the carboxyl group of the polymer compound represented by the general formula (1 '). The molar ratio is preferably at least 5 times, especially at least 5 times.

The reaction temperature is 0-100 ° C., preferably 0-60 ° C. The reaction time is 0.2 to 100
Hours, preferably 1 to 10 hours.

Examples of the dialkyl dicarbonate compound include di-tert-butyl dicarbonate and di-tert-amyl dicarbonate. Examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonyl methyl chloride and
tert-amyloxycarbonylmethyl chloride, t
tert-butoxycarbonylmethyl bromide, ter
Examples of t-butoxycarbonylethyl chloride include trialkylsilyl halides such as trimethylsilyl chloride, triethylsilyl chloride, and dimethyl-tert-butylsilyl chloride.

The polymer compound represented by the general formula (3a'-1) or (3a'-2) obtained by the first or second method may be added to the original compound represented by the general formula (3 The tertiary alkylation or oxoalkylation can be performed by reacting p42 mol of a tertiary alkylating agent and an oxoalkyl compound with respect to 1 mol of the carboxyl group of the polymer compound represented by ').

The above method is preferably carried out in a solvent in the presence of an acid. As the reaction solvent, dimethylformamide, dimethylacetamide, tetrahydrofuran, aprotic polar solvents such as ethyl acetate are preferred,
They may be used alone or in combination of two or more.

As the acid for the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, pyridinium p-toluenesulfonate and the like are preferably used. )), Relative to 1 mol of the carboxyl group of the polymer compound represented by the formula (1).
Preferably it is 1 to 10 mol%.

The reaction temperature is -20 to 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.2 to 1
00 hours, preferably 0.5 to 20 hours.

As the tertiary alkylating agent, isobutene, 2
-Methyl-1-butene, 2-methyl-2-butene and the like, and the oxoalkyl compound is α-angelicalactone, 2-cyclohexen-1-one, 5,6-
And dihydro-2H-pyran-2-one.

The formulas (3a'-1) and (3a'-
The polymer compound having a repeating unit represented by the following general formula (3c'-1) or (3c'-2) directly without passing through the polymer compound represented by the formula (2) Decomposable group, tertiary alkyl group, trialkylsilyl group,
After the introduction of an oxoalkyl group or the like, an acid-decomposable group represented by the general formula (4) can be introduced as necessary.

[0125]

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[0126]

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In the polymer compound of the present invention, the acid-decomposable group of R ² is not limited to one type, and two or more types can be introduced. In this case, after introducing p41 mol of the acid-decomposable group per 1 mol of all the hydroxyl groups of the polymer compound of the formula (1 ′) as described above, a different acid-decomposable group is introduced in the same manner as described above. By introducing p42 mol of the above, a polymer compound in which two or more of such acid-decomposable groups are introduced or such an acid-decomposable group is repeatedly introduced can be obtained.

The radiation-sensitive resin composition of the present invention is a radiation-sensitive resin composition containing the following components. (A) As the resin, the above-mentioned high molecular silicone compound (B) Photo-acid generator (C) Solvent dissolving the above-mentioned components (A) and (B) Further, the following components can be contained as required. (D) Dissolution controlling agent (E) Basic compound (F) Compound having a group represented by ≡C-COOH in the molecule (G) Acetylene alcohol derivative

Here, the solvent of the component (C) used in the present invention is an organic solvent in which additives such as the resin (A), (B) a photoacid generator, and a dissolution controlling agent can be dissolved. Any may be used. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-methoxybutanol.
Alcohols such as ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether,
Ethers such as propylene glycol dimethyl ether and diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-acetate -Butyl, tert-butyl propionate,
Esters such as propylene glycol-mono-tert-butyl ether acetate are mentioned, and one of these can be used alone or in combination of two or more, but is not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the highest solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate as a safe solvent and a mixture thereof Solvents are preferably used. The amount of the organic solvent used is from 200 to 1,000 parts, especially from 400 to 100 parts (parts by weight, hereinafter the same) of the resin (A).
800 parts are preferred.

As the photoacid generator (B), a compound capable of generating an acid upon irradiation with actinic rays or radiation can be appropriately selected and used. Specific examples of the photoacid generator include the following. The following general formula (6a-
1), an onium salt of (6a-2) or (6b), a diazomethane derivative of the following general formula (7), a glyoxime derivative of the following general formula (8), a bissulfone derivative of the following general formula (9), 10) N-hydroxyimide compound sulfonic acid ester, β-ketosulfonic acid derivative, disulfone derivative, nitrobenzylsulfonate derivative, sulfonic acid ester derivative and the like.

[0131]

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(Wherein R ^30a , R ^30b and R ^30c each represent a linear, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl group having 1 to 12 carbon atoms, 6 to 12 carbon atoms) 20 aryl groups or 7-1 carbon atoms
2 represents an aralkyl group or an aryloxoalkyl group, and a part or all of the hydrogen atoms of these groups may be substituted by an alkoxy group or the like. Also, R ^30b and R ^30c
May form a ring, and when forming a ring, R
^30b and R ^30c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion. )

The above R ^30a , R ^30b and R ^30c may be the same or different from each other. Specifically, as the alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group,
An adamantyl group and the like can be mentioned. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group,
Examples include a hexenyl group and a cyclohexenyl group. Examples of the oxoalkyl group and the oxoalkenyl group include a 2-oxocyclopentyl group and a 2-oxocycloheptyl group, and a 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, and a 2-cyclohexyl-2.
-Oxoethyl group, 2- (4-methylcyclohexyl)
And 2-alkyl-2-oxoethyl groups such as -2-oxoethyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group,
alkoxyphenyl groups such as m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4 -Methylphenyl group, ethylphenyl group, 4-
tert-butylphenyl group, 4-butylphenyl group,
Alkyl phenyl group such as dimethyl phenyl group, methyl naphthyl group, alkyl naphthyl group such as ethyl naphthyl group,
Methoxynaphthyl group, alkoxynaphthyl group such as ethoxynaphthyl group, dimethylnaphthyl group, dialkylnaphthyl group such as diethylnaphthyl group, dimethoxynaphthyl group,
And a dialkoxynaphthyl group such as a diethoxynaphthyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenethyl group and the like. Examples of the aryloxoalkyl group include 2- (phenyl) -2-oxoethyl, 2- (1-naphthyl) -2-oxoethyl, 2- (2-naphthyl) -2-oxoethyl and the like.
-Aryl-2-oxoethyl group and the like. K ^-
Non-nucleophilic counter ions include halide ions such as chloride ions and bromide ions, triflate, 1,1,1-
Fluoroalkylsulfonates such as trifluoroethanesulfonate and nonafluorobutanesulfonate, arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, 1,2,3,4,5-pentafluorobenzenesulfonate, mesylate, butanesulfonate and the like Alkylsulfonate.

[0134]

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(Wherein R ^31a and R ^31b each have 1 carbon atom)
8 linear, branched or cyclic alkyl group, R ³² represents a linear 1 to 10 carbon atoms, branched or cyclic alkylene group, R ^{33 a,} R ^33b is 3 to 7 carbon atoms, respectively Represents a 2-oxoalkyl group, and K ⁻ represents a non-nucleophilic counter ion. )

Specific examples of R ^31a and R ^31b include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. Octyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl and the like. R ³² includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a 1,4-cyclohexylene group, and a 1,2-cyclohexylene A 1,3-cyclopentylene group, a 1,4-cyclooctylene group, a 1,4-cyclohexanedimethylene group, and the like. ^{Examples of} R ^33a and R ^33b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is can be exemplified the same as the equation (6a).

[0137]

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(Wherein R ³⁴ and R ³⁵ are a linear, branched or cyclic alkyl or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or a halogenated aryl group having 6 to 20 carbon atoms or Represents an aralkyl group having 7 to 12 carbon atoms)

Examples of the alkyl group of R ³⁴ and R ³⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. Group, amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, and a 1,1,1-
Examples thereof include a trichloroethyl group and a nonafluorobutyl group. Examples of the aryl group include an alkoxyphenyl group such as a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and a m-tert-butoxyphenyl group. Examples thereof include an alkylphenyl group such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorobenzene group, a chlorobenzene group, a 1,2,3,4,5-pentafluorobenzene group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0140]

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(Wherein R ³⁶ , R ³⁷ and R ^{38 each} have 1 to 1 carbon atoms)
2 represents a linear, branched or cyclic alkyl group or a halogenated alkyl group, an aryl group having 6 to 20 carbon atoms or an aryl halide group, or an aralkyl group having 7 to 12 carbon atoms. R ³⁷ and R ³⁸ may be bonded to each other to form a cyclic structure. In the case of forming a cyclic structure, R ³⁷ and R ³⁸ are each a linear or branched alkylene group having 1 to 6 carbon atoms. Represents )

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group represented by R ³⁶ , R ³⁷ and R ³⁸ include the same groups as those described for R ³⁴ and R ³⁵ . The alkylene group for R ³⁷ and R ³⁸ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

[0143]

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(In the formula, R ^30a and R ^30b have the same meanings as described above.)

[0145]

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(Wherein, R ³⁹ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and part or all of the hydrogen atoms of these groups is Furthermore a linear or branched alkyl or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group or .R ⁴⁰ optionally substituted by phenyl group, C 1 to C 8
Represents a linear, branched or substituted alkyl group, alkenyl group or alkoxyalkyl group, phenyl group, or naphthyl group, and some or all of the hydrogen atoms of these groups further have an alkyl group having 1 to 4 carbon atoms. Or an alkoxy group; having 1 carbon atom
Or a phenyl group which may be substituted with an alkyl group, an alkoxy group, a nitro group or an acetyl group;
A heteroaromatic group; or a chlorine atom. )

Here, the arylene group for R ³⁹ includes:
1,2-phenylene group, 1,8-naphthylene group and the like, alkylene groups include methylene group, 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, 1-
Phenyl-1,2-ethylene group, norbornane-2,3
Examples of the -diyl group and the alkenylene group include a 1,2-vinylene group, a 1-phenyl-1,2-vinylene group, and a 5-norbornene-2,3-diyl group. The alkyl group for R ⁴⁰ is the same as R ^{30a to} R ^30c, and the alkenyl group is a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-
Hexenyl group, 5-hexenyl group, 1-heptenyl group,
A 3-heptenyl group, a 6-heptenyl group, a 7-octenyl group and the like include, as an alkoxyalkyl group, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pentoxymethyl group, a hexyloxymethyl group, Butyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group,
Pentoxyethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group,
Examples include an ethoxypentyl group, a methoxyhexyl group, and a methoxyheptyl group.

It is to be noted that carbon atoms having 1 carbon atom which may be further substituted
Examples of the linear or branched alkyl group of to 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group, and the alkoxy group includes a methoxy group, An ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like, and a monocyclic aromatic group include a phenyl group, a pyridyl group and a furyl group.

As the photoacid generator, specifically, for example, diphenyliodonium trifluoromethanesulfonate,
Trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfone Acid (p-te
rt-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p- Toluenesulfonic acid (p-ter
t-butoxyphenyl) diphenylsulfonium, p-
Bis (p-tert-butoxyphenyl) phenylsulfonium toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate,
Trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate,
Cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, trifluoromethanesulfonate Dicyclohexylphenylsulfonium, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, (2-norbonyl) methyl trifluoromethanesulfonate (2-oxocyclohexyl) ) Sulfonium, ethylenebis [meth (2-oxo-cyclopentyl) sulfonium trifluoromethanesulfonate],
Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate,

Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (Isobutylsulfonyl)
Diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) Diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-
Diazomethane derivatives such as amylsulfonyl) diazomethane and 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane;

Bis-o- (p-toluenesulfonyl)-
α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o
-(P-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl)
-2,3-pentanedione glyoxime, bis-o-
(P-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o-
(N-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedione glyoxime, Bis-o- (n-butanesulfonyl) -2-methyl-3,4
-Pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o-
(Trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o
-(Tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (Benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (pt
tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-
Glyoxime derivatives such as dimethylglyoxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime,

Bissulfone derivatives such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane , 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p
Β-ketosulfone derivatives such as -toluenesulfonyl) propane; disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; nitrobenzylsulfonates such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate Derivatives, sulfonic acids such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene Ester derivatives,

N-hydroxysuccinimide methyl sulfonate, N-hydroxysuccinimide trifluoromethyl sulfonate, N-hydroxysuccinimide ethyl sulfonate, N-hydroxysuccinimide propyl sulfonate, N-hydroxysuccinimide isopropyl sulfonate, N-hydroxysuccinimide pentylsulfonic acid ester, N-hydroxysuccinimideoctylsulfonic acid ester, N-hydroxysuccinimide-p-
Toluenesulfonic acid ester, N-hydroxysuccinimide-p-anisylsulfonic acid ester, N-hydroxysuccinimide-2-chloroethylsulfonic acid ester, N-hydroxysuccinimidebenzenesulfonic acid ester, N-hydroxysuccinimide-2,4
6-trimethylphenylsulfonic acid ester, N-hydroxysuccinimidonaphthylsulfonic acid ester, N
-Hydroxy-2-phenylsuccinimide methyl sulfonate, N-hydroxymaleimidomethyl sulfonate, N-hydroxymaleimidoethyl sulfonate, N-hydroxy-2-phenylmaleimidomethyl sulfonate, N-hydroxyglutarimide methyl sulfone Acid ester, N-hydroxyglutarimidophenylsulfonic acid ester, N-hydroxyphthalimidomethylsulfonic acid ester, N-hydroxyphthalimidophenylsulfonic acid ester, N-
Hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide-p-toluenesulfonic acid ester, N-hydroxy-1,8-naphthalimidomethylsulfonic acid ester, N-hydroxy-
1,8-naphthalimidophenylsulfonic acid ester,
N-hydroxy-5-norbornene-2,3-dicarboximide methylsulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonic acid ester, N-hydroxy-
5-norbornene-2,3-dicarboximide-p-
And sulfonic acid ester derivatives of N-hydroxyimide compounds such as toluenesulfonic acid ester.

Among them, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate,
triphenylsulfonium p-toluenesulfonate, p
-(P-tert-butoxyphenyl) diphenylsulfonium toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) ) Sulfonium, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 1,2 ′
-Onium salts such as naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl)
Diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n
Diazomethane derivatives such as -propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, and bis (tert-butylsulfonyl) diazomethane;
Bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl)-
glyoxime derivatives such as α-dimethylglyoxime, bissulfone derivatives such as bisnaphthylsulfonylmethane,
N-hydroxysuccinimide methyl sulfonate, N-hydroxysuccinimide trifluoromethyl sulfonate, N-hydroxysuccinimide propyl sulfonate, N-hydroxysuccinimide isopropyl sulfonate, N-hydroxysuccinimide pentyl sulfonate, N-hydroxy Sulfonate derivatives of N-hydroxyimide compounds such as succinimide-p-toluenesulfonic acid ester, N-hydroxy-1,8-naphthalimidomethylsulfonic acid ester and N-hydroxy-1,8-naphthalimidophenylsulfonic acid ester Is preferably used.

The photoacid generators may be used alone or in combination of two or more. The onium salt is excellent in the effect of improving the rectangularity, and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect. However, by combining the two, fine adjustment of the profile can be performed.

The amount of the photoacid generator to be added was as follows:
The amount is preferably 0.1 to 15 parts, more preferably 0.5 to 8 parts with respect to 0 parts. If the amount is less than 0.1 part, the sensitivity may be poor, and if the amount is more than 15 parts, the resolution of the resist material may decrease due to a decrease in the alkali dissolution rate. Performance may be reduced.

The radiation-sensitive composition of the present invention may further contain a dissolution controlling agent as the component (D).
The dissolution controlling agent has an average molecular weight of 100 to 1,000.
0, preferably 150 to 800, and the compound having two or more phenolic hydroxyl groups in the molecule has a hydrogen atom of the phenolic hydroxyl group of an average of 0 by the acid-decomposable group.
A compound in which the hydrogen atom of the carboxyl group of the compound having a carboxyl group in the molecule is substituted with an acid-decomposable group at a rate of 80 to 100 mol% as a whole is added.

The substitution rate of the hydrogen atom of the phenolic hydroxyl group or carboxyl group by the acid-decomposable group is 0 mol% or more, preferably 30 mol% or more, of the total phenolic hydroxyl group or carboxyl group. The upper limit is 100 mol%, more preferably 80 mol%.

In this case, the phenolic hydroxyl group is 2
As the compound having one or more compounds or the compound having a carboxyl group, compounds represented by the following formulas (i) to (xiv) are preferable.

[0160]

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[0161]

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[0162]

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[0163]

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(Wherein R ¹⁵ and R ¹⁶ are each a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, and R ¹⁷ is a hydrogen atom or 1 to 8 carbon atoms)
8, a linear or branched alkyl or alkenyl group,
Or - (R ²¹⁾ is h-COOH, R ¹⁸ is - (C
H ₂ ) i- (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ¹⁹ is an alkylene group having 1 to 10 carbon atoms, and 6 carbon atoms
-10 arylene groups, carbonyl groups, sulfonyl groups,
An oxygen atom or a sulfur atom, R ²⁰ is a hydrogen atom or a carbon number 1 to
8 is a linear or branched alkyl or alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group, and R ²¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, R ²² Is a hydrogen atom or a hydroxyl group. Also, j
Is an integer of 0 to 5, and u and h are 0 or 1. s,
t, s ′, t ′, s ″, and t ″ are respectively s + t = 8,
It is a number satisfying s ′ + t ′ = 5, s ″ + t ″ = 4, and having at least one hydroxyl group in each phenyl skeleton. α is the molecular weight of the compounds of formulas (viii) and (ix)
It is a number to be set to 00 to 1,000. )

In the above formula, R ¹⁵ and R ¹⁶ are, for example, hydrogen, methyl, ethyl, butyl, propyl, ethynyl, cyclohexyl, and R ¹⁷ are, for example, R
¹⁵ or the same as R ¹⁶ , or -COOH, -CH ₂
COOH and R ¹⁸ include, for example, an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom and a sulfur atom, and R ¹⁹ includes, for example, a methylene group or R ¹⁸
Examples of R ²⁰ include a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, a phenyl group substituted with a hydroxyl group, a naphthyl group, and the like.

Here, the acid-decomposable group of the dissolution controlling agent includes a group represented by the above general formula (4) and a group represented by the above general formula (5)
And a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, and an oxoalkyl group having 4 to 20 carbon atoms.

The compounding amount of the above-mentioned dissolution controlling agent is as follows:
It is 0 to 50 parts, preferably 5 to 50 parts, more preferably 10 to 30 parts with respect to 00 parts, and can be used alone or in combination of two or more. If the amount is less than 5 parts, the resolution may not be improved. If the amount is more than 50 parts, the pattern may be reduced in film thickness and the resolution may be reduced.

[0168] The dissolution controlling agent as described above can be used for the compound having a phenolic hydroxyl group or a carboxyl group as (A)
It can be synthesized by chemically reacting an acid-decomposable group similarly to the resin.

The radiation-sensitive composition of the present invention may be a compound having a weight average molecular weight of less than 1,000 and having a carboxyl group in the molecule as another dissolution controlling agent instead of or in addition to the dissolution controlling agent. On average, the hydrogen atom of the carboxyl group is at least 0% to 100% by the acid-decomposable group.
Compounds partially substituted at the following ratios can be blended.

In this case, the compound in which the hydrogen atom of the carboxyl group is partially substituted with such an acid-decomposable group has a repeating unit represented by the following general formula (11) and has a weight average molecular weight of less than 1,000. 1 selected from a certain compound
Species or two or more compounds are preferred.

[0171]

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(Wherein R ¹ , R ² , Z, n, m, x, p
2, q is the same as above, but p11 is 0 ≦ p11 / (p11
+ P2 + q) ≦ 0 or a positive number in the range of 1. )

Here, the acid-decomposable group of the dissolution controlling agent includes a group represented by the general formula (4), a group represented by the general formula (5), and a tertiary alkyl group having 4 to 20 carbon atoms. And a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, and an oxoalkyl group having 4 to 20 carbon atoms.

[0174] The blending amount of the above-mentioned another dissolution controlling agent is as follows.
0 to 50 parts, especially 0 to 30 parts, preferably 0
It is preferable that the content be in the range of 5 to 5 parts.

The other dissolution controlling agent as described above can be synthesized by chemically reacting a compound having a carboxyl group with an acid-decomposable group in the same manner as the base resin.

As the dissolution controlling agent (D), a silicone compound can be preferably used in order not to impair the oxygen plasma etching resistance. As the dissolution controlling agent for the silicone compound, a carboxyl group or a hydroxyl group of the silicone compound represented by the following general formulas (12) to (14) is te
It is preferable to use one protected with an rt-butyl group or a tert-butoxycarbonylmethyl group.

[0177]

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(In the formula, R ¹⁰ represents a methyl group or a phenyl group, and R ¹¹ represents a carboxyethyl group or a p-hydroxyphenylalkyl group (provided that the alkyl group is a straight-chain, branched or X is a trimethylsilyl group, a triphenylsilyl group or -SiR
¹⁰ R ¹¹ (R ¹⁰ and R ¹¹ have the same meanings as described above). γ is an integer of 0 to 50, δ is an integer of 1 to 50, ε is 3
And an integer of 10 to 10. )

The silicone compounds of the formulas (12) to (14) in which the carboxyl group or hydroxyl group is protected with an alkali-soluble group (tert-butyl group or tert-butoxycarbonylmethyl group) include The compounds of the following groups A to C are exemplified. Here, Me represents a methyl group, and t-Bu represents a tert-butyl group.

[0180]

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[0181]

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[0182]

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The content of the dissolution controlling agent was (A) 4% of the whole resin.
The content is preferably 0% by weight or less, particularly preferably 10 to 30% by weight. If the content is more than 40% by weight, the oxygen plasma etching resistance of the resist film is significantly reduced, so that there is a possibility that the resist film cannot be used as a two-layer resist.

The radiation-sensitive composition of the present invention further comprises
A basic compound can be blended as the component (E).

As the basic compound to be added as the (E) additive, a compound capable of suppressing the rate of diffusion of the acid generated from the acid generator into the resist film is suitable. Incorporation of a basic compound suppresses the diffusion rate of acid in the resist film to improve resolution, suppresses sensitivity changes after exposure, reduces substrate and environment dependency, reduces exposure margin and pattern Profiles and the like can be improved.

Examples of such a basic compound include:
Primary, secondary, tertiary aliphatic amines, mixed amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples include a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

Specifically, examples of primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tertiary aliphatic amines.
t-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
Nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified. As secondary aliphatic amines, dimethylamine, diethylamine, di-n
-Propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine,
Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N
-Dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, and the like. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, and triisopropylamine. , Tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine,
Triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetra Examples include methylethylenediamine, N, N, N ', N'-tetramethyltetraethylenepentamine and the like.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline,
N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline , 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyl toluidine, etc.), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, Pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methyl) Pyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridyl , 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl- 4-phenylpyridine, 2- (1-ethylpropyl) pyridine,
Aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (Eg, quinoline, 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,1
Examples thereof include 0-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and 3-pyridinesulfonic acid as a nitrogen-containing compound having a sulfonyl group; Pyridinium p-toluenesulfonate and the like are exemplified. Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, and 2,4-quinolinediol. , 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-imino Diethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1
-Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2
-Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol,
Examples thereof include 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, and N- (2-hydroxyethyl) isonicotinamide. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
N-dimethylacetamide, propionamide, benzamide and the like are exemplified. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, basic compounds represented by the following general formulas (15) and (16) can be blended.

[0191]

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(Wherein R⁴¹, R⁴², R⁴³, R⁴⁷, R⁴⁸Is
Each independently represents a linear, branched or cyclic carbon number of 1
~ 20 alkylene groups, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁹, R⁵⁰
Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group
And R⁴⁴And R⁴⁵, R⁴⁵And R ⁴⁶, R⁴⁴And R⁴⁶, R⁴⁴When
R⁴⁵And R⁴⁶, R⁴⁹And R⁵⁰Each combine to form a ring
You may. S, T and U each represent an integer of 0 to 20
You. However, when S, T, U = 0, R⁴⁴, R⁴⁵, R⁴⁶,
R⁴⁹, R⁵⁰Does not contain a hydrogen atom. )

The alkylene group represented by R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ has 1 to 20 carbon atoms, preferably 1 carbon atom.
-10, more preferably 1-8, and specifically, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-
Examples include a pentylene group, an isopentylene group, a hexylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group.

The alkyl group of R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
8, more preferably 1 to 6, which may be linear, branched, or cyclic. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, nonyl, decyl, dodecyl Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like.

Further, R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ^46
46, if R ⁴⁴ and R ⁴⁵ and R ^46, R ⁴⁹ and R ⁵⁰ form rings, the number of carbon atoms in the ring is 1 to 20, more preferably 1 to
8, more preferably 1 to 6, and in these rings, an alkyl group having 1 to 6, particularly 1 to 4 carbon atoms may be branched.

S, T and U are each an integer of 0 to 20, more preferably 1 to 10, further preferably 1 to 8.

Specific examples of the compounds of the above (15) and (16) include tris {2- (methoxymethoxy) ethyl}
Amine, tris {2- (methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methoxy} ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- ( 1-methoxyethoxy) ethyl @ amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2-{(2-
Hydroxyethoxy) ethoxydiethyl] amine, 4,
7,13,16,21,24-hexaoxa-1,10
-Diazabicyclo [8.8.8] hexacosan, 4,
7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,10,13-
Tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-
Crown-5, 1-aza-18-crown-6 and the like. As the component (E), tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds Amide derivative, imide derivative, tris {2- (methoxymethoxy) ethyl} amine, tris {(2- (2-methoxyethoxy) ethyl} amine, tris [2-} (2-methoxyethoxy)
Methyl {ethyl] amine, 1-aza-15-crown-
5 and the like are preferable.

The compounding amount of the above basic compound is 0.001 to 10 parts, preferably 0.01 to 1 part with respect to 1 part of the photoacid generator.
~ 1 part. If the amount is less than 0.001 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 10 parts, the resolution and sensitivity may be reduced.

Further, the radiation-sensitive composition of the present invention comprises
As the component (F), a compound having a group represented by ≡C-COOH in the molecule can be blended.

As the compound having a group represented by ≡C-COOH in the molecule blended as the component (F), for example, one or more compounds selected from the following groups I and II may be used. However, the present invention is not limited to these. By mixing the component (F), the PE of the resist
D stability can be improved, and edge roughness on a nitride film substrate can be improved.

[Group I] A part or all of the hydrogen atoms of the phenolic hydroxyl group of the compounds represented by the following formulas (17) to (26) may be replaced by -R ⁵¹ -COOH (R ⁵¹ is a straight-chain having 1 to 10 carbon atoms). A phenolic hydroxyl group (C) in the molecule and a ≡C-C
The molar ratio with the group (D) represented by OOH is C / (C +
D) = 0.1 to 1.0. [Group II] Compounds represented by the following general formulas (27) to (31).

[0202]

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[0203]

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(Wherein R ¹ is a hydrogen atom or a methyl group, and R ⁵² and R ⁵³ are each a hydrogen atom or a C 1 -C 1
8 is a linear or branched alkyl or alkenyl group, and R ⁵⁴ is a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or — (R ⁵⁹ )
h-COOR 'group (R' is a hydrogen atom or an -R ⁵⁹ -COO
H), and R ⁵⁵ is — (CH ₂ ) i — (i = 2 to 10);
An arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ⁵⁶ has 1 to 10 carbon atoms
Alkylene group, arylene group having 6 to 10 carbon atoms, carbonyl group, sulfonyl group, oxygen atom or sulfur atom, R ⁵⁷
Is a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, a phenyl group or a naphthyl group each substituted with a hydroxyl group, and R ⁵⁸ is a hydrogen atom or a straight chain having 1 to 8 carbon atoms. It is a chain or branched alkyl group or alkenyl group or —R ⁵⁹ —COOH group. R ⁵⁹ has 1 carbon atom
And 10 to 10 linear or branched alkylene groups. j is an integer of 0 to 5, and u and h are 0 or 1. s1,
t1, s2, t2, s3, t3, s4, and t4 are s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, and s, respectively.
It is a number that satisfies 4 + t4 = 6 and has at least one hydroxyl group in each phenyl skeleton. κ is given by the equation (2)
The compound of 3) was used for weight average molecular weight of 1,000 to 5,000.
And λ is a number such that the compound of the formula (24) has a weight average molecular weight of 1,000 to 10,000. )

[0205]

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(R ⁵² , R ⁵³ and R ⁵⁹ have the same meaning as described above. S5 and t5 are s5 ≧ 0, t5 ≧ 0 and s5 + t
5 = 5 is a number that satisfies 5. R ⁶⁰ is a hydrogen atom or a hydroxyl group, and h ′ is 0 or 1. )

Specific examples of the component (F) include, but are not limited to, compounds represented by the following formulas VIII-1 to IX-14 and IX-1-10.

[0208]

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[0209]

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[0210]

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(Where R ″ is a hydrogen atom or CH ₂ COO
H group, and in each compound, 10 to 100 mol% of R ″ is a CH ₂ COOH group. Α and κ have the same meanings as described above.)

[0212]

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[0213]

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The compounds having a group represented by ≡C—COOH in the molecule can be used alone or in combination of two or more.

The amount of the compound having a group represented by ≡C-COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0 to 5 parts with respect to 100 parts of the resin (A). 0.1 to 3 parts, more preferably 0.1 to 2 parts. 5
When the amount is more than the parts, the resolution of the radiation-sensitive composition may decrease. The radiation-sensitive composition of the present invention further comprises (G)
An acetylene alcohol derivative can be blended as a component, which can improve the storage stability. As the acetylene alcohol derivative, those represented by the following general formulas (32) and (33) can be suitably used.

[0216]

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(Wherein, R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms; Represents 0 or a positive number and satisfies the following values: 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30,
0 ≦ X + Y ≦ 40. )

As acetylene alcohol derivatives, Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol TG, Surfynol PC, Surfynol 44 are preferred.
0, Surfynol 465, Surfynol 485 (A
ir Products and Chemicals I
nc. And Surfynol E1004 (manufactured by Nissin Chemical Industry Co., Ltd.).

The acetylene alcohol derivative may be added in an amount of 0.01 to 2 in 100% by weight of the radiation-sensitive resin composition.
%, More preferably 0.02 to 1% by weight.
If the amount is less than 0.01% by weight, the effect of improving applicability and storage stability may not be sufficiently obtained. If the amount is more than 2% by weight, the resolution of the radiation-sensitive composition may decrease.

The radiation-sensitive composition of the present invention may contain, as an optional component, a surfactant which is commonly used for improving coating properties, in addition to the above components. In addition, the addition amount of the optional component can be a normal amount as long as the effect of the present invention is not impaired.

The surfactant is preferably a nonionic surfactant, and is preferably a perfluoroalkylpolyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkyl EO adduct, or a fluorine-containing organosiloxane-based surfactant. And the like. For example, Florard "FC-430",
"FC-431" (all are Sumitomo 3M Limited)
), Surflon "S-141", "S-145" (all manufactured by Asahi Glass Co., Ltd.), Unidyne "DS-40"
1 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-815 "
1 "(manufactured by Dainippon Ink Industries, Ltd.)," X-70-09 "
2 "," X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florado “FC-430” (manufactured by Sumitomo 3M Limited),
"X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) and Troysol S-366 (manufactured by Troy Chemical Co., Ltd.).

In the present invention, the radiation-sensitive resin composition having the above-mentioned components has a viscosity at 25 ° C. of not more than 6.0 mPa · sec, preferably from 0.9 to 5.0.
mPa · sec, more preferably 1.5 to 4.5 mPa
・ It is good to be within the range of sec. The viscosity is 6.0mPa.
If the time exceeds sec, the resolution performance deteriorates, which is not preferable. The viscosity at 25 ° C. is, for example, 25 ° C.
, And then can be measured with an E-type viscometer or the like.

The viscosity can be adjusted mainly by the use ratio of the solvent (C) to the component (A). Usually, 4 parts by weight of the solvent (C) is added to 100 parts by weight of the component (A).
It is used in an amount of from 00 to 5,000 parts by weight, preferably from 700 to 2,000 parts by weight. As a specific method of adjusting the viscosity, for example, first, the component (A) 100
Using 400 parts by weight of the solvent (C) with respect to parts by weight, the solid content is dissolved, and the component (B) is added and dissolved therein. Other additives can be added as needed. The viscosity of the obtained composition is measured. If the viscosity is higher than desired, the composition is sequentially diluted with the same solvent in which the solid content is dissolved as described above, and the viscosity is measured. The viscosity of the composition depends on the type of the repeating unit of the component (A), the copolymerization ratio, the molecular weight and the degree of dispersion,
Also, it greatly changes depending on the combination with other additive components.
For this reason, it is extremely difficult to predict in advance the optimum amount of solvent used and the amount of change in viscosity due to dilution, so the above specific method is effective.

The solution composition of the present invention is applied on a substrate, and the solvent is removed by subsequent drying to form a resist coating film. The thickness of this coating film is 0.1 to 1.2 μm
And more preferably 0.2 to 0.35 μm. In the present invention, the formed resist coating film is 40 to 70% / 200 μm with respect to light having a wavelength of 193 nm,
In particular, it is preferable to have a transmittance of 45 to 65% / 200 μm. When the resist coating film has the transmittance in the above range, it is possible to obtain a rectangular profile in which only a standing wave is not generated, and a preferable result is obtained. As a method of adjusting the transmittance, for example, the transmittance of the composition for light having a wavelength of 193 nm can be adjusted by the type, copolymerization ratio, and molecular weight of each repeating unit in the component (A). Furthermore, (B) which has absorption at that wavelength
This is achieved by appropriately adjusting the amounts of the components, the acid-decomposable dissolution inhibiting compound, the dye, the plasticizer, the surfactant, the photosensitizer, the organic base compound, and the compound that promotes the solubility of the exposed area in the developing solution. You.

A pattern can be formed by using the radiation-sensitive resin composition of the present invention by using a known lithography technique. For example, a pattern such as spin coating is applied to a substrate such as a silicon wafer. Film thickness 0.05
２．０2.0 μm, and apply it on a hot plate at 60-150 ° C. for 1-10 minutes, preferably 80
Pre-bake at ~ 120 ° C for 1-5 minutes. Next, a mask for forming a target pattern is held over the above resist film, and a high energy ray such as far ultraviolet rays having a wavelength of 300 nm or less, excimer laser, X-ray, EUV or the like or an electron beam is exposed at 1 to 200 mJ / cm ^2. (1 to 200 μC /
cm ² ), preferably 10 to 100 mJ / cm ² (1
１００100 μC / cm ² )
Post exposure bake (PEB) on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes. Further, using a developer of an aqueous alkali solution such as 0.1 to 5%, preferably 2 to 3% tetramethylammonium hydroxide (TMAH),
Dipping for 0.1 to 3 minutes, preferably 0.5 to 2 minutes (d
ip) method, paddle method, spray method (sp
(ray) method to form a target pattern on the substrate by performing development. The material of the present invention is particularly suitable for fine patterning using 254 to 193 nm far ultraviolet rays or excimer lasers, X-rays and electron beams among high energy rays. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

Further, the radiation-sensitive composition of the present invention is useful as a two-layer resist material because it is excellent in oxygen plasma etching resistance by using the polymer silicone compound (A) as a resin. That is, after forming a thick organic polymer layer as a lower resist on a substrate according to a conventional method, the resist solution of the present invention is spin-coated thereon. The upper resist layer (film thickness: 0.1 to 0.5 μm) of the present invention is formed by patterning in the same manner as described above, and then by etching, the lower resist is selectively etched. Can be formed in the lower layer.

As the lower resist, a novolak resin-based positive resist can be used. After coating on the substrate, hard baking is performed at 200 ° C. for 1 hour to prevent intermixing with the silicone-based resist. be able to.

[0228]

EXAMPLES <Synthesis Example> [Synthesis Example 1] Synthesis of poly (3-carboxycyclohexylsilsesquioxane) 150.0 g (0.544 mol) of 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester in 150 g of toluene It was dissolved and added dropwise to 300 g of water at room temperature with stirring. After completion of the dropwise addition, an acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice after the aqueous layer became neutral. The solvent was distilled off from the organic layer using an evaporator. 200 ℃
And polymerized for 2 hours. A solution obtained by adding 800 g of tetrahydrofuran to the polymer and dissolving the solution was dropped into 1,000 g of a 10% sodium hydroxide solution, and heated at 40 ° C. for 3 hours to hydrolyze a methyl ester group. The polymer was crystallized by acidification with hydrochloric acid, filtered and dried to obtain poly (3-carboxycyclohexylsilsesquioxane) in a yield of 8%.
Obtained in 3.4 g. The weight average molecular weight of the obtained polymer was 3,000.

[Synthesis Example 2] Synthesis of poly [(3-carboxycyclohexylsilsesquioxane)-(cyclohexylsilsesquioxane)] 3-Trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester 75.0 g (0.272 mol) ) And 59.2 g (0.272 m) of cyclohexyltrichlorosilane
ol) was dissolved in 150 g of toluene and added dropwise to 300 g of water with stirring at room temperature. After completion of the dropwise addition, an acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice after the aqueous layer became neutral. The solvent was distilled off from the organic layer using an evaporator. The concentrate was heated at 200 ° C. for 2 hours to polymerize. The polymer was dissolved by adding 800 g of tetrahydrofuran to 10%
The solution was dropped into 1,000 g of a sodium hydroxide solution and heated at 40 ° C. for 3 hours to hydrolyze a methyl ester group. The polymer was crystallized by acidification with hydrochloric acid, filtered and dried to obtain 82.0 g of poly [(3-carboxycyclohexylsilsesquioxane)-(cyclohexylsilsesquioxane)]. The weight average molecular weight of the obtained polymer was 3,500. In 1 H-NMR analysis, the composition ratio of 3-carboxycyclohexylsilsesquioxane / cyclohexylsilsesquioxane was 50%.
/ 50 (molar ratio).

[Synthesis Examples 3 to 8] Silicone polymers shown in Table 1 were obtained in the same manner as in Synthesis Examples 1 and 2. Table 1 shows the weight average molecular weight and composition ratio of the obtained polymer.

[0231]

[Table 1]

[0232]

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[Synthesis Example 9] 50 g of the polymer obtained in Synthesis Example 1 was dissolved in 180 ml of tetrahydrofuran, a catalytic amount of p-toluenesulfonic acid was added, and 23.0 g of ethyl vinyl ether was added while stirring at 20 ° C. .
After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 5 L of water, whereby a white solid was obtained. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried in vacuo. The obtained polymer had a structure represented by the following formula (Polym. 1), and it was confirmed by 1 H-NMR analysis that 80% of the hydrogen atoms of the carboxyl groups of the polymer compound were ethoxyethylated. Was.

[Synthesis Examples 10 to 19]
Using any of the polymers of Synthesis Examples 1 to 8, instead of ethyl vinyl ether, Polym. Silicone polymers represented by the following formulas (Polyms. 2 to 11) were obtained in the same manner except that compounds capable of introducing acid-decomposable groups 2 to 11 were used.

[Synthesis Example 20] 20 g of the polymer obtained in Synthesis Example 1 was dissolved in 200 ml of dimethylformamide, potassium carbonate was added as a solid, and 1.0 g of chloroacetic acid-tert-butyl ester was added with stirring. After reaction at 60 ° C. for 6 hours, solid potassium carbonate was filtered off from the reaction solution, and 10 L of water was added dropwise to obtain a white solid. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has the following formula (Poly
m. 1H-NMR analysis revealed that 75% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxyethylated, and the tert-butylcarbonylation rate was 5%. Was.

[Synthesis Example 21] 20 g of the polymer obtained in Synthesis Example 1 was dissolved in 200 ml of dimethylformamide, potassium carbonate was added as a solid, and 13.0 g of chloroacetic acid-tert-butyl ester was added with stirring. After reaction at 60 ° C. for 6 hours, solid potassium carbonate was filtered off from the reaction solution, and 10 L of water was added dropwise to obtain a white solid. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has the following formula (Poly
m. It has the structure represented by 13), and it was confirmed by analysis by 1 H-NMR that 65% of the hydrogen atoms of the carboxyl groups of the polymer compound were ethoxyethylated.

[Synthesis Example 22] 50 g of the polymer obtained in Synthesis Example 1 was dissolved in 180 ml of tetrahydrofuran.
After adding trifluoroacetic anhydride, 18.2 g of t-butyl alcohol was added while stirring at 5 ° C. or lower. After reacting for 2 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 5 L of water, whereby a white solid was obtained. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried in vacuo. The resulting polymer is
It has a structure represented by the following formula (Polym. 14), and ¹
In the analysis by H-NMR, it was confirmed that 80% of the hydrogen atoms of the carboxyl group of the polymer compound were tert-butylated.

[Synthesis Example 23] A synthesis was performed in the same manner as in Synthesis Example 22 except that the polymer of Synthesis Example 5 was used.
lym. 15) A silicone polymer was obtained.

[0239]

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[0240]

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[0241]

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[0242]

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[0243]

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[Synthesis Example 24] Synthesis of poly (3-carboxycyclohexylsilsesquioxane) 150.0 g (0.544 mol) of 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester was dissolved in 150 g of toluene, and 300 g of water was dissolved. It was added dropwise with stirring at room temperature. After completion of the dropwise addition, an acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice after the aqueous layer became neutral. The solvent was distilled off from the organic layer using an evaporator. 200 ℃
And polymerized for 2 hours. A solution obtained by adding 800 g of tetrahydrofuran to the polymer and dissolving it was dropped into 1,000 g of a 10% sodium hydroxide solution, and heated at 40 ° C. for 3 hours to hydrolyze the methyl ester. The polymer was crystallized by acidification with hydrochloric acid, filtered and dried to give poly (3-carboxycyclohexylsilsesquioxane) in a yield of 83.
Obtained in 4 g. The weight average molecular weight of the obtained polymer is 3,
000.

Synthesis Example 25 Synthesis of Poly [(3-carboxycyclohexylsilsesquioxane)-(cyclohexylsilsesquioxane)] 3-Trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester 75.0 g (0.272 mol) ) And 59.2 g (0.272 m) of cyclohexyltrichlorosilane
ol) was dissolved in 150 g of toluene and added dropwise to 300 g of water with stirring at room temperature. After completion of the dropwise addition, an acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice after the aqueous layer became neutral. The solvent was distilled off from the organic layer using an evaporator. The concentrate was heated at 200 ° C. for 2 hours to polymerize. The polymer was dissolved by adding 800 g of tetrahydrofuran to 10%
The solution was dropped into 1,000 g of a sodium hydroxide solution and heated at 40 ° C. for 3 hours to hydrolyze the methyl ester. The polymer was crystallized by acidification with hydrochloric acid, filtered and dried to obtain 82.0 g of poly [(3-carboxycyclohexylsilsesquioxane)-(cyclohexylsilsesquioxane)]. The weight average molecular weight of the obtained polymer was 3,500. In 1 H-NMR analysis, the composition ratio of 3-carboxycyclohexylsilsesquioxane / cyclohexylsilsesquioxane was 50%.
/ 50 (molar ratio).

[Synthesis Examples 26 to 31] Silicone polymers were obtained in the same manner as in Synthesis Example 25 except that the cyclohexyltrichlorosilane compound was changed as shown in Table 1. Table 2 shows the composition ratio and the weight average molecular weight.

Synthesis Example 32 50 g of the polymer obtained in Synthesis Example 24 was dissolved in 180 ml of tetrahydrofuran, and a catalytic amount of p-toluenesulfonic acid was added.
While stirring with 13.7 g of ethyl vinyl ether, 4-
2.5 g of butanediol divinyl ether were added.
After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 5 L of water, whereby a white solid was obtained. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried in vacuo. The obtained polymer has a structure represented by the following formula (Polym. 16). In 1 H-NMR analysis, 53% of the hydrogen atoms of the carboxyl group of the polymer compound are ethoxyethylated, and the hydrogen of the carboxyl group is hydrogenated. It was confirmed that 5% of the atoms were crosslinked.

[Synthesis Examples 33 to 39] In Synthesis Example 32, Polym. 3 was used instead of ethyl vinyl ether and 4-butanediol divinyl ether. The following formula (Polym. 17 to 23) is prepared in the same manner except that a compound capable of introducing an acid-decomposable group and a crosslinking group shown in 17 to 23 is used.
Was obtained.

[Synthesis Example 40] 20 g of the polymer obtained in Synthesis Example 32 was dissolved in 200 ml of dimethylformamide, potassium carbonate was added as a solid, and 1.0 g of chloroacetic acid-tert-butyl ester was added with stirring. After reaction at 60 ° C. for 6 hours, solid potassium carbonate was filtered off from the reaction solution, and 10 L of water was added dropwise to obtain a white solid. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has the following formula (Poly
m. In the analysis by 1 H-NMR, 53% of the hydrogen atoms of the carboxyl group of the polymer compound are ethoxyethylated, 5% of the hydrogen atoms of the carboxyl group are crosslinked, and tert-butyl The carbonylation rate was confirmed to be 5%.

[Synthesis Examples 41 to 47] Silicone polymers represented by the following formula (Polyms. 25 to 31) were obtained in the same manner as in Synthesis Example 32 except that the base polymer was changed to Synthesis Examples 25 to 31.

The structure of the obtained polymer was as shown in the following formula, and the respective substitution rates were as shown in Table 3. In the following formula, R represents a group which crosslinks the following units between molecules or intramolecularly, and (R) shows a state where a crosslinking group R is bonded.

[0252]

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[0253]

[Table 2]

[0254]

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[0255]

[Table 3]

[0256]

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[0257]

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[0258]

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[0259]

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[Examples 1-31 and Comparative Examples 1-2] <Adjustment and Evaluation of Positive-Type Radiation-Sensitive Resin Composition> 1.37 g of the resin (polym.) Shown in Table 4 below in the above Synthesis Example, 30 mg of a photoacid generator, 1.5 mg of an organic basic compound (amine), and, if necessary, a surfactant (30 mg) were blended and dissolved with 6.0 g of propylene glycol monoethyl ether acetate (PGMEA). The viscosity of the obtained composition is measured. If the viscosity is higher than the desired viscosity (Table 4), the viscosity is measured by successively diluting with the same solvent (PGMEA) in which the solid content is dissolved as described above. This was repeated to obtain the desired viscosity. The obtained solution was filtered through a 0.1 μm microfilter to obtain radiation-sensitive resin compositions of Examples 1 to 31. As Comparative Examples 1-2 and 2a, the respective viscosities were within the range of the present invention (2
The composition deviated from 6 mPa · sec or less at 5 ° C.) was similarly prepared. In Table 4, PAG. 1 to 7 are represented by the following formulas.

[0261]

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(Evaluation Test) [Viscosity] The adjusted composition was placed in a precision high-temperature bath at 25 ° C for 3 hours.
After holding for 0 minutes, the viscosity of the composition was measured with an E-type viscometer, and the value was indicated as a viscosity at 25 ° C. [In-plane uniformity] For Examples 1 to 31, the obtained positive resist solution was applied to a DUV manufactured by Prewer using a spin coater.
30 (1600 °) was applied to the substrate at a film thickness of 3500 ° or less, and then dried at 140 ° C. for 90 seconds to obtain a resist film. Film thickness gauge (Prometrics, Spectrum
ra Map SM3000), the film thickness was measured at 49 points in the wafer, and based on the measured data, the <Ran
ge> (difference between the maximum value and the minimum value: Angstroms) and <standard deviation> based on the sample were used as indices of in-plane uniformity. Further, when the same composition as in Comparative Example 2 was applied to a thick film satisfying the in-plane uniformity, the film thickness at that time was 500 nm, which was designated as Comparative Example 2a.

[Resolution] First, the sensitivity (Eth) was determined.
The sensitivity was measured by exposing the substrate coated as described above with 9300 (exposure wavelength: 193 nm) manufactured by ISI Co.
The minimum exposure that reproduced a 0 μm line and space (1: 1) was taken as the sensitivity. Next, an exposure amount for resolving a 0.20 μm line and space (1: 1) is defined as an optimum exposure amount (Eopt), and a minimum line width of a separated line and space at this exposure amount is evaluated. Resolution. The pattern collapse was measured by a scanning electron microscope (S4000, manufactured by Hitachi, Ltd.) for the repetitive pattern near the limit resolution at that time. At this time, the collapse and disappearance of the end pattern were observed (× in the table), and the collapse and disappearance of the end pattern were not defined (○ in the table).

[0264]

[Table 4]

In Table 4, DBN: 1,5-diazabicyclo [4.3.0] -5-nonene TPI: triphenylimidazole As apparent from the results in Table 4, Comparative Examples 1 and 2 showed in-plane uniformity. (Range large, standard deviation large). In Comparative Example 2a, the same composition as in Comparative Example 2 was used to obtain a thick film (ET = 5000 °) so as to obtain in-plane uniformity.
And subjected to an evaluation test. Here, although the problem of in-plane uniformity becomes smaller, problems such as degradation of resolution and collapse of the pattern arise. On the other hand, the radiation-sensitive composition of the present invention has excellent in-plane uniformity even during a thin film process, can exhibit sufficiently satisfactory resolution performance, and does not cause the problem of pattern collapse. That is, it is possible to cope with thinning of lithography such as far ultraviolet light, particularly ArF excimer laser light (wavelength 193 nm).

[0266]

According to the radiation-sensitive composition of the present invention, sufficient in-plane uniformity is maintained even in a thin film process, and a fine pattern can be reproduced without a problem such as collapse of the pattern.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shoichiro Yasunami 4000F, Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. CC03

Claims (4)

[Claims] 1. A resin having a property of increasing the dissolution rate in an alkali developing solution by the action of an acid, and further comprising a resin containing a Si element, a photoacid generator, and a solvent.
A radiation-sensitive resin composition having a viscosity of not more than 6.0 mPa · sec. 2. A viscosity at 25 ° C. of 0.9 to 5.0 mPa.
The radiation-sensitive resin composition according to claim 1, wherein the composition is within the range of sec. 3. A viscosity at 25 ° C. of 1.5 to 4.5 mPa.
The radiation-sensitive resin composition according to claim 1, wherein the composition is within the range of sec. 4. The resin containing a Si element is a polymer containing a repeating unit represented by the following general formula (1) and having a group decomposed by the action of an acid.
4. The radiation-sensitive resin composition according to any one of items 1 to 3. Embedded image [In the formula, Z is a divalent or hexavalent monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms, or a bridged cyclic hydrocarbon group;
¹ represents a linear, branched or cyclic unsubstituted or substituted alkyl group or alkenyl group having 1 to 8 carbon atoms. R ² represents an acid-decomposable group. m is 0 or a positive integer, n is a positive integer, and is a number satisfying m + n ≦ 5. x is a positive integer. p1 and p2 are positive numbers, q is 0 or a positive number, and 0 <
p1 / (p1 + p2 + q) ≦ 0.9, 0 <p2 / (p1
+ P2 + q) ≦ 0.9, 0 ≦ q / (p1 + p2 + q) ≦
0.7, which satisfies p1 + p2 + q = 1. In the carboxyl group in the repeating unit, 90% or less of the hydrogen atom of the carboxyl group is represented by the following general formula (2)
It may be substituted by a crosslinking group having a C—O—C group represented by a) or (2b), and may be crosslinked intra- and / or intermolecularly. Embedded image (Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ³ and R ⁴ are bonded to each other to form a ring when forming a good. ring optionally, R ^3, R both combined number of carbon atoms of ⁴ to 8, the .R ⁵ showing the in both integral linear or branched alkylene group,
A linear or branched alkylene group having 1 to 10 carbon atoms, d
Is 0 or an integer of 1 to 10. A is (c '+ 1)
A saturated or unsaturated aliphatic or alicyclic hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a hetero atom interposed; A part of the bonding hydrogen atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O- or -NH
CONH- is shown. c ′ is an integer of 1 to 7. )]