JPH11236416A - Polystyrene-based polymer compound, chemical amplification positive type resist material and pattern formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer compound comprising a modified end containing an acid unstable group, providing a resist material having excellent high sensitivity, high resolution, etc., by using the compound as a base resin, capable of a resist pattern having heat resistance. SOLUTION: This high molecular weight compound is a polymer compound of the formula (R is hydroxyl group or an OR<3> ; R<1> is H or methyl; R<2> is a 1-30C alkyl; R<3> is an acid unstable group; (x) is 0 or a positive integer; (y) is a positive integer; x+y<=5; (k) and (m) are each 0 or a positive number; (n) is a positive number; k+m+n<=5; (p) and (q) are each a positive number; 0<q<=0.8 and p+1=1; Δ is a number to make a weight-average molecular weight 1,000-500,000; P is H, a 1-30C alkyl or the like). The polymer compound may be intermolecularly or intramolecularly cross-linked. The polymer compound is used as a base resin and mixed with an organic solvent and an acid generator to give the chemical amplification positive type resist material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polymer having a terminal-modified compound having one or more acid labile groups, or a polymer having a C-terminal or an intramolecular and / or intermolecular compound.
A polymer compound cross-linked by a cross-linking group having a -OC group, and by blending this polymer compound as a base resin, alkali dissolution contrast before and after exposure is significantly high, and high sensitivity and high resolution And especially super LS
The present invention relates to a chemically amplified positive resist material having excellent reproducibility as a fine pattern forming material for manufacturing I and a pattern forming method.

[0002]

2. Description of the Related Art In recent years,
As the integration and speed of LSIs have been increasing and the pattern rules have been required to be finer, far-ultraviolet lithography is expected as a next-generation fine processing technology. The deep ultraviolet lithography can process 0.5 μm or less, and when a resist material having low light absorption is used, a pattern having a side wall nearly perpendicular to the substrate can be formed.

A recently developed acid-catalyzed chemically amplified positive resist material (Japanese Patent Publication No. 2-27660,
U.S. Pat. No. 3,278,829) uses a high-intensity KrF excimer laser as a light source of far ultraviolet light, and is particularly promising for far ultraviolet lithography having high sensitivity, high resolution, high dry etching resistance, and excellent characteristics. It is expected as a resist material.

As such a chemically amplified positive resist material, there are known a two-component system comprising a base resin and an acid generator, and a three-component system comprising a base resin, an acid generator and a dissolution controller having an acid labile group. Have been.

For example, Japanese Patent Application Laid-Open No. Sho 62-115440 discloses a resist material comprising poly-4-tert-butoxystyrene and an acid generator. Is a two-component resist material comprising a resin having a tert-butoxy group in the molecule and an acid generator.
No. 8 proposes a two-component resist material comprising a polyhydroxystyrene containing a methyl group, an isopropyl group, a tert-butyl group, a tetrahydropyranyl group and a trimethylsilyl group, and an acid generator.

Further, JP-A-6-100488 discloses poly [3,4-bis (2-tetrahydropyranyloxy) styrene], poly [3,4-bis (tert-butoxycarbonyloxy) styrene], Poly [3,5-
A resist material comprising a polydihydroxystyrene derivative such as bis (2-tetrahydropyranyloxy) styrene] and an acid generator has been proposed.

However, the base resin of these resist materials has an acid labile group in a side chain, and the acid labile group is decomposed by a strong acid such as a tert-butyl group and a tert-butoxycarbonyl group. As a result, it reacts with the basic compound in the air to deactivate, so that the decomposition of the acid labile group hardly occurs, and the pattern shape of the resist material tends to be a T-top shape. On the other hand, since alkoxyalkyl groups such as ethoxyethyl groups are decomposed by weak acids, the effect of basic compounds in the air is small, but the pattern shape becomes extremely thin with the passage of time from exposure to heat treatment. Or has a bulky group in the side chain, so that heat resistance is lowered, sensitivity and resolution are not satisfactory, and both have problems and have not yet been put to practical use At present, it is desirable to improve these problems.

The polymer compound described in Japanese Patent Application Laid-Open No. Hei 8-305025 is intended to improve the above-mentioned problem. It is difficult, and Japanese Unexamined Patent Application Publication No.
However, it has the disadvantage of inducing by-products of the cross-linking groups described in Japanese Unexamined Patent Application Publication No. H11-157,086. That is, in designing a resist composition, a polymer compound having various alkali dissolution rates is required by selecting an acid generator and an additive and setting the amount of addition, and further, reproducibility of the production of the polymer compound is required. However, the production method described in the above publication has a drawback that the selection of the acid labile group and the crosslinking group and the ratio of the substituents must be restricted.

The present invention has been made in view of the above circumstances,
Especially when used as a base resin for chemically amplified positive resist material, it has higher sensitivity and resolution, exposure latitude, process adaptability and reproducibility than conventional resist materials, excellent plasma etching resistance, and resist pattern It is an object of the present invention to provide a polymer compound that provides a chemically amplified positive resist material having excellent heat resistance, a chemically amplified positive resist material using the polymer compound as a base resin, and a pattern forming method.

[0010]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies in order to achieve the above object, and as a result, have found that one or more acid labile groups obtained by the method described below can be used. Having a terminal-modified high molecular compound or the high molecular compound further having C-
A polymer compound cross-linked by a cross-linking group having an OC group is used as a base resin, and has an acid generator, further a basic compound, and a group represented by ≡C-COOH in the molecule. A chemically amplified positive resist material containing an aromatic compound enhances the dissolution contrast of the resist film, in particular increases the dissolution rate after exposure, and further improves the PED stability of the resist. By improving edge roughness and blending acetylene alcohol derivatives, coating properties and storage stability are improved, and high resolution, exposure latitude, process adaptability, high practicality, and precise fine processing are achieved. It was found to be advantageous and very effective as a resist material for VLSI.

That is, the present invention provides the following polymer compound, a chemically amplified positive resist material, and a pattern forming method.

Claim 1: A terminal represented by the following general formula (1) having the following P is a weight average molecular weight of 1,000 to 500,
000 high molecular compounds.

[0013]

Embedded image [Wherein, R represents a hydroxyl group or an OR ³ group, at least one of which is a hydroxyl group. R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear, branched, or R ³ represents an acid labile group, and represents a cyclic alkyl group.
Is 0 or a positive integer, y is a positive integer, a number satisfying x + y ≦ 5, k is 0 or a positive integer, m is 0 or a positive integer, n is a positive integer, and k + m + n It is a number that satisfies ≦ 5. p and q are positive numbers, 0 <q ≦ 0.8, p
It is a number that satisfies + q = 1. When n is 2 or more, R ³ may be the same or different.
Δ is a number that makes the weight average molecular weight 1,000 to 500,000. P is a hydrogen atom, a straight chain having 1 to 30 carbon atoms,
A branched or cyclic alkyl or alkenyl group, an aromatic hydrocarbon group having 6 to 50 carbon atoms, a carboxyl group, a hydroxyl group, or a group represented by the following general formula (2), (3) or (4) And all of the terminals cannot be hydrogen atoms at the same time. )

[0014]

Embedded image (Wherein, R ⁴ is an (r + 1) -valent aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic saturated hydrocarbon group or 6 to 50 carbon atoms.
R ⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 50 carbon atoms, an alkoxy group having 1 to 30 carbon atoms Or a hydroxyl group, and R ^5a represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 50 carbon atoms. H is 0 or 1, and r is 1 to
Indicates a positive integer of 3. In addition, any one or two of the phenolic hydroxyl group represented by R of the polymer compound represented by the general formula (1), the hydroxyl group represented by R ⁵ in the general formula (2), and the hydroxyl group represented by the general formula (3) The above hydroxyl group may be cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a C—O—C group obtained by reaction with an alkenyl ether compound or a halogenated alkyl ether compound. The total amount of the phenolic hydroxyl group of the formula (1), the hydroxyl group of R ⁵ in the general formula (2) and the total hydrogen atom of the hydroxyl group in the general formula (3) is more than 0 mol%. The ratio is not more than mol%. Claim 2: The polymer compound according to claim 1, represented by the following general formula (5).

[0015]

Embedded image [Wherein, R represents a hydroxyl group or an OR ³ group, at least one of which is a hydroxyl group. R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear, branched, or R ³ represents an acid labile group, and R ⁹ and R ¹⁰ represent a cyclic alkyl group.
Represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ¹¹ represents a monovalent hydrocarbon group which may have a heteroatom having 1 to 18 carbon atoms. , R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , R ¹⁰ and R ¹¹ may form a ring, and when forming a ring, R ⁹ , R ¹⁰ , and R ¹¹ each have 1 to 18 carbon atoms. Represents a linear or branched alkylene group. R ¹² is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms,
An oxoalkyl group having 4 to 20 carbon atoms or —CR ⁹ R ¹⁰ O
It represents a group represented by R ^11. a is an integer of 0 to 6. Also, p1 and p2 are positive numbers, q1 and q2 are 0 or positive numbers, and 0 <p1 / (p1 + q1 + q2 + p2) ≦ 0.8,
0 ≦ q1 / (p1 + q1 + q2 + p2) ≦ 0.8, 0 ≦
q2 / (p1 + q1 + q2 + p2) ≦ 0.8, p1 + q
1 + q2 + p2 = 1, but q1 and q2
Do not become 0 at the same time. x, y, k, m, n,
Δ and P have the same meanings as above. In addition, any one or two of the phenolic hydroxyl group represented by R of the polymer compound represented by the general formula (5), the hydroxyl group represented by R ⁵ in the general formula (2), and the hydroxyl group represented by the general formula (3) Even if a hydrogen atom of the above hydroxyl group is removed and its oxygen atom is cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a C—O—C group represented by the following general formula (6a) or (6b) The total amount of the acid labile group and the crosslinking group is preferably the phenolic hydroxyl group represented by R in the polymer compound of the formula (5), the hydroxyl group of R ⁵ in the above formula (2) and the above formula (3) The ratio is more than 0 mol% and not more than 80 mol% of the average of all the hydrogen atoms of the hydroxyl group in the above.

[0016]

Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ⁷ each represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear alkylene group having 1 to 10 carbon atoms;
Represents a branched or cyclic alkylene group, d is 0 or 1
It is an integer of 10. A represents a c-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; A part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. B is -CO-O
—, —NHCO—O— or —NHCONH—. c
Is an integer of 2 to 8, and c 'is an integer of 1 to 7. )] Claim 3: In the polymer compound represented by the general formula (1) or (5), R ³ is represented by the following general formula (7) or (8)
A tertiary alkyl group having 4 to 20 carbon atoms, wherein each alkyl group is selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.
The polymer compound according to claim 1, wherein the polymer compound is a kind or two or more kinds.

[0017]

Embedded image (Wherein R ⁹ and R ¹⁰ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ¹¹ may have a heteroatom having 1 to 18 carbon atoms. R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , R ¹⁰ and R ¹¹ may form a ring, and when forming a ring, R ⁹ and R ¹⁰ ,
R ¹¹ represents a linear or branched alkylene group having 1 to 18 carbon atoms. R ¹² is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above general formula (7). Is shown. a is an integer of 0 to 6. Claim 4: C- represented by the general formula (6a) or (6b)
The polymer compound according to claim 2, wherein the crosslinking group having an OC group is represented by the following general formula (6a ') or (6b').

[0018]

Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ^{7 each} represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, d is 0 or an integer of 1 to 5. A is a c ''-valent linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, Represents an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed, and a part of the hydrogen atoms bonded to the carbon atom is substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c '' is 2 to 4,
c ″ ′ is an integer of 1 to 3. Claim 5: (A): Organic solvent (B): Any one of claims 1 to 4 as a base resin
4. A chemically amplified positive resist composition comprising the polymer compound (C): an acid generator.

Claim 6: In addition, as a base resin different from the components (D) and (B), one type of hydrogen atom of a phenolic hydroxyl group of a polymer compound having a repeating unit represented by the following general formula (9) is used. Alternatively, a polymer compound having a weight average molecular weight of 3,000 to 300,000 partially substituted by two or more acid labile groups at a ratio of 0 to 80 mol% on average as a whole is blended. Item 6. The polymer compound according to Item 5,

[0020]

Embedded image [Wherein, R ¹ , R ² , R ⁹ , R ¹⁰ , and R ¹¹ have the same meanings as described above, and R ¹² is an acid labile group different from —CR ⁹ R ¹⁰ OR ¹¹ ; f is 0 or a positive number, g is a positive number, and e +
f + g = 1, 0 ≦ e / (e + f + g) ≦ 0.5,
0.4 ≦ g / (e + f + g) ≦ 0.9. In addition, the phenolic hydroxyl group of the polymer compound represented by the above general formula (9) is obtained by reacting a phenolic hydroxyl group with an alkenyl ether compound or a halogenated alkyl ether.
It may be cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a -OC group. In the formula (9), the total amount of the acid labile group and the cross-linking group is e = 0, f = 0, g = 1
In this case, the ratio is more than 0 mol% and not more than 80 mol% on the average of all hydrogen atoms of the phenolic hydroxyl group. Claim 7: The chemically amplified positive resist material according to claim 5 or 6, further comprising (E) a dissolution controlling agent.

In a preferred embodiment, the composition further comprises (F) a basic compound as an additive.
5. The chemically amplified positive resist material according to claim 1.

(9) The method according to any one of (5) to (8), further comprising (G): an aromatic compound having a group represented by ≡C-COOH in the molecule as an additive. The positive resist composition according to any one of the preceding claims.

(10) The chemically amplified positive resist material according to any one of (5) to (9), further comprising (H) an ultraviolet absorber.

(11) The chemically amplified positive resist material according to any one of (5) to (10), further comprising (I): an acetylene alcohol derivative.

Claim 12: (i) a step of applying the chemically amplified positive resist material according to any one of claims 5 to 11 onto a substrate;
i) Next, after the heat treatment, a wavelength of 30
A pattern forming method, comprising: a step of exposing to a high-energy ray or an electron beam of 0 nm or less; and (iii) a step of performing a heat treatment as necessary and then developing with a developer.

The polymer compound of the present invention is characterized in that the polymer terminal of the polyhydroxystyrene derivative is modified. When incorporated into a chemically amplified positive resist material as a base resin, the performance is improved over conventional base resins due to the effect of the terminal groups of the polymer. For example, environmental stability is improved by making the terminal a carboxylic acid.
Further, by using alcohol, hydrophilicity can be imparted, and the adhesion to the substrate can be improved. Further, the dissolution rate of the overexposed portion is improved as compared with the conventional base resin, and the alkali dissolution rate contrast before and after exposure is significantly increased.

Further, the polymer terminal group has a C-
It can be cross-linked by a cross-linking group having an OC group. In this case, when the terminal of polyhydroxystyrene is cross-linked, the cross-linking occurs linearly. Is further improved, and the alkali dissolution rate contrast before and after exposure is significantly increased.

Further, in the case of a polymer in which an alkoxyalkyl group is independently added to the side chain of a phenolic hydroxyl group, the elimination reaction proceeds with a weak acid, so that it is difficult to form a T-top shape. And the pattern shape becomes extremely thin with the lapse of time from exposure to heat treatment. Furthermore, since the dissolution inhibiting effect on alkali is low, a high substitution rate compound must be used in order to obtain a dissolution contrast, which has a disadvantage of lacking heat resistance. On the other hand, in the case of a polymer in which the side chain of a phenolic hydroxyl group is protected with a tert-butoxycarbonyl group, when this is blended with a resist material, the alkali dissolution inhibiting property is improved, and a dissolution contrast can be obtained with a low substitution rate, and heat resistance can be obtained. Although it has the advantage of being good, it is necessary to use an acid generator that generates a strong acid such as trifluoromethanesulfonic acid in order to make it soluble in alkali by elimination. Thus, it has a drawback that it tends to have a T-top shape.

For such a polymer, a polymer compound having a terminal modified as described above, or a phenolic hydroxyl group of the polymer compound, and R in the general formula (2)
^A molecule having a C—O—C group as a cross-linkable group obtained by reacting a hydroxyl group of ⁵ and any one or more of the hydroxyl groups in formula (3) with an alkenyl ether compound or a halogenated alkyl ether compound; A resist material using a polymer compound crosslinked inside and / or between molecules has a disadvantage that the heat resistance of a polymer in which a side chain is protected by an acetal group is low, and that a T-top in a polymer protected by a tert-butoxycarbonyl group is low. An object of the present invention is to eliminate the disadvantage that the shape is easily formed.

On the other hand, as an effect of the polymer compound used in the chemically amplified positive resist composition of the present invention, the polymer compound is cross-linked by a cross-linking group having an acid-labile C—O—C group and protected by an acid-labile group. In the case of a high molecular compound, the weight average molecular weight of the unexposed portion of the resist film and the solubility in an alkali developing solution do not change, but the weight average molecular weight of the exposed portion of the resist film is degraded by the generated acid. After that, since the weight-average molecular weight of the alkali-soluble base resin before being protected by the crosslinking group and the acid-labile group is accompanied by elimination of the acid-labile group, the alkali dissolution rate is greatly increased as compared with the unexposed part. Accordingly, the dissolution contrast can be increased, and as a result, a higher resolution can be achieved. In particular, the cross-linking of the polymer terminals further improves the dissolution rate of the overexposed portion as described above, and significantly increases the alkali dissolution rate before and after exposure.

When a crosslinking group having a C—O—C group is decomposed by an acid, an alcohol compound (diol, triol, polyol compound, etc.) is formed. And the resolution can be increased as a result.

Further, in designing the resist composition, the selection of the acid generator and the additives and the setting of the amount of the addition include:
Polymer compounds with various alkali dissolution rates are required, and reproducibility of the production of the polymer compounds is required. However, by using the above-mentioned polymer compounds, the selection and substitution of acid labile groups and crosslinking groups are restricted. It is possible to design without being restricted by the base ratio.

That is, a chemically amplified positive resist material using the above-mentioned polymer compound as a base resin has much less problems than conventional ones, such as a tendency to form a T-top shape, a narrow pattern shape, and a lack of heat resistance. It is possible to increase the dissolution contrast of the resist film, and as a result, it has high sensitivity and high resolution, and it is possible to arbitrarily control the pattern dimension and the pattern shape by the composition. It becomes a chemically amplified positive resist material having excellent adaptability and reproducibility.

Now, the present invention will be described in further detail. The novel polymer compound of the present invention is a polymer compound having one or more acid labile groups and a terminal-modified polymer compound, Furthermore, intramolecular and / or intermolecular C-
It is a polymer compound having a weight average molecular weight of 1,000 to 500,000 crosslinked by a crosslinking group having an OC group.

The polymer compound is represented by the following general formula (1-
i) having a repeating unit represented by i) and having a terminal represented by the following P
And represented by the following general formula (1).

[0036]

Embedded image [Wherein, R represents a hydroxyl group or an OR ³ group, at least one of which is a hydroxyl group. R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear, branched, or R ³ represents an acid labile group, and represents a cyclic alkyl group.
Is 0 or a positive integer, y is a positive integer, a number satisfying x + y ≦ 5, k is 0 or a positive integer, m is 0 or a positive integer, n is a positive integer, and k + m + n It is a number that satisfies ≦ 5. p and q are positive numbers, 0 <q ≦ 0.8, p
It is a number that satisfies + q = 1. When n is 2 or more, R ³ may be the same or different.
Δ is a number that makes the weight average molecular weight 1,000 to 500,000. P is a hydrogen atom, a straight chain having 1 to 30 carbon atoms,
A branched or cyclic alkyl or alkenyl group, an aromatic hydrocarbon group having 6 to 50 carbon atoms, a carboxyl group, a hydroxyl group, or a group represented by the following general formula (2), (3) or (4) And all of the terminals cannot be hydrogen atoms at the same time. )

[0037]

Embedded image (Wherein, R ⁴ is an (r + 1) -valent aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic saturated hydrocarbon group or 6 to 50 carbon atoms.
R ⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 50 carbon atoms, an alkoxy group having 1 to 30 carbon atoms Or a hydroxyl group, and R ^5a represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 50 carbon atoms. H is 0 or 1, and r is 1 to
Indicates a positive integer of 3. In addition, any one or two of the phenolic hydroxyl group represented by R of the polymer compound represented by the general formula (1), the hydroxyl group represented by R ⁵ in the general formula (2), and the hydroxyl group represented by the general formula (3) The above-mentioned hydroxyl group may be cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a C—O—C group obtained by a reaction with an alkenyl ether compound or a halogenated alkyl ether. The total amount of the phenolic hydroxyl group of the formula (1), the hydroxyl group of R ⁵ in the above general formula (2) and the total hydrogen atom of the hydroxyl group in the above general formula (3) is more than 80 mol%. % Or less. ]

Here, R represents a hydroxyl group or OR ³ ,
At least one of R is a hydroxyl group. R ¹ represents a hydrogen atom or a methyl group; R ² represents a linear, branched or cyclic alkyl group having 1 to 30, preferably 1 to 15, more preferably 1 to 8 carbon atoms; As a branched or cyclic alkyl group, a methyl group, an ethyl group, a propyl group,
Isopropyl group, n-butyl group, isobutyl group, ter
Examples thereof include a t-butyl group, a cyclohexyl group, and a cyclopentyl group. R ³ is an acid labile group. X is 0
Alternatively, y is a positive integer, and satisfies x + y ≦ 5. However, y is preferably 1 to 3, particularly preferably 1 or 2. k is 0 or a positive integer, m is 0 or a positive integer, n is a positive integer and satisfies k + m + n ≦ 5, where n is 1-2, and m is 0-1. preferable. When n is 2 or more, R ³ may be the same or different. p and q are positive numbers, and 0 <
q ≦ 0.8, p + q = 1.

P is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30, preferably 1 to 15, more preferably 1 to 8, carbon atoms, 6 to 50, preferably 6 to 6 carbon atoms.
30, more preferably 6 to 20 aromatic hydrocarbon groups, carboxyl groups, hydroxyl groups or groups represented by the above general formula (2), (3) or (4), but all of the terminal groups P are simultaneously hydrogen. It cannot be an atom.

Here, the linear, branched or cyclic alkyl or alkenyl group includes a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonanyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Pentadecyl group, heptadecyl group, nonadecyl group, docosanyl group, heptacosanyl group, 2,2-dimethylbutyl group,
2,3-dimethylbutyl group, 2,2,3-trimethylbutyl group, hexamethylethyl group, decahydronaphthyl group, cyclohexyl group, dicyclohexyl group, norbornyl group, norpinyl group, adamantyl group, 1,3-dimethyladamantyl group , A cyclopentyl group, a vinyl group, an allyl group, a butenyl group, a hexenyl group, a cyclohexenyl group and the like.

As the aromatic hydrocarbon group, a phenyl group,
Benzyl group, tert-butylbenzyl group, diphenyl group, triphenyl group, naphthyl group, anthranyl group,
Examples thereof include a 1,2,3-tripentylbenzyl group and a hexapentylbenzyl group.

As the (r + 1) -valent aliphatic hydrocarbon group or alicyclic saturated hydrocarbon group for R ⁴ , methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene group, ter
t-butylene group, pentylene group, hexylene group, octylene group, nonanylene group, decylene group, undecylene group,
Dodecylene group, tridecylene group, pentadecylene group, heptadecylene group, nonadecylene group, docosanylene group, heptacosanylene group, 2,2-dimethylbutylene group, 2,
3-dimethylbutylene group, 2,2,3-trimethylbutylene group, hexamethylethylene group, decahydronaphthalene group, cyclohexavinylene group, cyclohexylene group, cyclohexenylene group, dicyclohexylene group, norbornylene group, adamantylene Groups, 1,3-dimethyladamantylene groups, cyclopentylene groups, and trivalent groups formed by further losing one or two hydrogen atoms from these groups;
Examples thereof include a tetravalent group.

Examples of the (r + 1) -valent aromatic hydrocarbon group for R ⁴ include a phenylene group, a benzylene group, a tert-butylbenzylene group, a diphenylene group, a triphenylene group,
A naphthylene group, an anthranylene group, a 1,2,3-tripentylbenzylene group, a hexapentylbenzylene group, and a trivalent or tetravalent group formed by losing one or two hydrogen atoms from these groups. No.

Examples of the linear, branched or cyclic alkyl group and aromatic hydrocarbon group for R ⁵ include the same groups as described above. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and an iso-group. Propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-
Butoxy group, pentyloxy group, hexyloxy group, octyloxy group, nonanyloxy group, decyloxy group,
Undecyloxy group, dodecyloxy group, tridecyloxy group, pentadecyloxy group, heptadecyloxy group, nonadecyloxy group, docosanyloxy group, heptacosanyloxy group, 2,2-dimethylbutoxy group, 2,
3-dimethylbutoxy group, 2,2,3-trimethylbutoxy group, hexamethylethoxy group, cyclohexyloxy group, decahydronaphthyloxy group, dicyclohexyloxy group, norbornyloxy group, norpinyloxy group, adamantyloxy group, Examples include a 3-dimethyladamantyloxy group and a cyclopentyloxy group.

As the acid labile group for R ³ , various types are selected. In particular, groups represented by the following formulas (7) and (8), tertiary alkyl groups having 4 to 20 carbon atoms, and each alkyl group include Trialkylsilyl group having 1 to 6 carbon atoms, 4 to 2 carbon atoms
It is preferably an oxoalkyl group of 0 or the like.

[0046]

Embedded image

In the formula, R ⁹ and R ¹⁰ represent a hydrogen atom or a carbon atom
Represents a linear, branched or cyclic alkyl group of from 1 to 8, preferably 1 to 6, more preferably 1 to 5, and R ¹¹ has 1 to 18, preferably 1 to 10, more preferably 1 to 1 carbon atoms. 8
Represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom, wherein R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , and R ¹⁰ and R ¹¹ may form a ring, When a ring is formed, R ⁹ , R
¹⁰ and R ¹¹ each have 1 to 18 carbon atoms, preferably 1 to 1 carbon atoms.
0, more preferably 1 to 8 linear or branched alkylene groups. R ¹² has 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms.
15, more preferably a tertiary alkyl group having 4 to 10 carbon atoms, each alkyl group being a trialkylsilyl group having 1 to 6 carbon atoms, and an oxo group having 4 to 20 carbon atoms, preferably 4 to 15, more preferably 4 to 10 carbon atoms. Alkyl group or the above general formula (6)
Represents a group represented by A is an integer of 0 to 6.

Examples of the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms for R ⁹ and R ¹⁰ include the same groups as described for R ² .

R ¹¹ represents a linear, branched or cyclic alkyl group, phenyl group, p-methylphenyl group, p-
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.

[0050]

Embedded image

The tertiary alkyl group for R ¹² includes t
tert-butyl group, 1-methylcyclohexyl group, 2-
Examples thereof include a (2-methyl) adamantyl group and a tert-amyl group.

The trialkylsilyl group for R ¹² includes trimethylsilyl, triethylsilyl, dimethyl-t
The carbon number of each alkyl group such as tert-butylsilyl group is 1
To 6 are mentioned.

Examples of the oxoalkyl group for R ¹² include a 3-oxocyclohexyl group and a group represented by the following formula.

[0054]

Embedded image

As the acid labile group represented by the above formula (7), specifically, 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 labile group of the above formula (8), for example, a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a tert-amyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group , 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

In the present invention, the high molecular compound represented by the above general formula (1) having the above-mentioned terminal P is a phenolic hydroxyl group represented by R, a hydroxyl group represented by R ⁵ in the above general formula (2) and the above general formula (1). Any one or more of the hydroxyl groups in (3) may be intramolecular and / or molecular by a crosslinking group having a C—O—C group obtained by reaction with an alkenyl ether compound or a halogenated alkyl ether compound described below. It may be crosslinked between.

The total amount of the acid labile group and the crosslinking group is determined by the formula (1), the phenolic hydroxyl group and the general formula (2)
The ratio is more than 0 mol% and not more than 80 mol% of the average of all hydrogen atoms of the hydroxyl group of R ^{5 in} the formula (3) and the hydroxyl group in the general formula (3).

The crosslinking group having a CO—C group is a group represented by the following general formula (6a) or (6b), preferably a group represented by the following general formula (6a ′) or (6b ′) Can be mentioned.

[0059]

Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ⁷ each represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear alkylene group having 1 to 10 carbon atoms;
Represents a branched or cyclic alkylene group, d is 0 or 1
It is an integer of 10. A represents a c-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; A part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. B is -CO-O
—, —NHCO—O— or —NHCONH—. c
Is an integer of 2 to 8, and c 'is an integer of 1 to 7. )

[0060]

Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ^{7 each} represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, d is 0 or an integer of 1 to 5. A is a c ''-valent linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, Represents an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed, and a part of the hydrogen atoms bonded to the carbon atom is substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c '' is 2 to 4,
c ″ ′ is an integer of 1 to 3. )

Here, as the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, the same as those described above can be exemplified.

The linear, branched or cyclic alkylene group having 1 to 10 carbon atoms for R ⁸ includes methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, cyclohexylene. And cyclopentylene groups.

Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

A specific example of A will be described later. The crosslinking groups (6a) and (6b) are derived from alkenyl ether compounds and halogenated alkyl ether compounds described below.

As is apparent from the value of c ′ in the above formulas (6a) and (6b), the crosslinkable group is not limited to divalent but trivalent to trivalent.
It may be an octavalent group. For example, divalent crosslinking groups are represented by the following formulas (6a ″) and (6b ″), and trivalent crosslinking groups are represented by the following formulas (6a ′ ″) and (6b ′ ″) Things.

[0066]

Embedded image

As a specific example, the crosslinked polymer compound according to the present invention has a repeating unit represented by the following general formula (5-i) and the terminal represented by the following general formula (P) 5) The phenolic hydroxyl group represented by R of the polymer compound of the polymer compound and / or the hydrogen atom of R ⁵ in the general formula (2) and / or the hydrogen atom of the hydroxyl group in the general formula (3) are removed. A high molecular compound in which the oxygen atom is crosslinked inside and / or between molecules by a crosslinking group having a C—O—C group represented by the above general formula (6a) or (6b) can be given.

[0068]

Embedded image (Wherein, R represents a hydroxyl group or an OR ³ group, and at least 1
The individual is a hydroxyl group. R ¹ represents a hydrogen atom or a methyl group; R ² represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms; and R ³ represents an acid labile group. R ⁹ , R ¹⁰
Represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ¹¹ represents a monovalent hydrocarbon group which may have a heteroatom having 1 to 18 carbon atoms. , R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , R ¹⁰ and R ¹¹ may form a ring, and when forming a ring, R ⁹ , R ¹⁰ , and R ¹¹ each have 1 to 18 carbon atoms. Represents a linear or branched alkylene group. R ¹² is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms,
An oxoalkyl group having 4 to 20 carbon atoms or —CR ⁹ R ¹⁰ O
It represents a group represented by R ^11. a is an integer of 0 to 6. Also, p1 and p2 are positive numbers, q1 and q2 are 0 or positive numbers, and 0 <p1 / (p1 + q1 + q2 + p2) ≦ 0.8,
0 ≦ q1 / (p1 + q1 + q2 + p2) ≦ 0.8, 0 ≦
q2 / (p1 + q1 + q2 + p2) ≦ 0.8, p1 + q
1 + q2 + p2 = 1, but q1 and q2
Do not become 0 at the same time. x, y, k, m, n,
Δ and P have the same meanings as above. Note that p1
+ P2 = p and q1 + q2 = q. )

Here, R, R ^{1 to} R ³ , R ^{9 to} R ¹² , x,
Specific examples and suitable ranges of y, k, m, n, a, and P are as described above. P1 and p2 are positive numbers, q1 and q2 are 0 or positive numbers, and 0 <p1 / (p1 + q1 + q2 + p2)
≦ 0.8, 0 ≦ q1 / (p1 + q1 + q2 + p2) ≦
0.8, 0 ≦ q2 / (p1 + q1 + q2 + p2) ≦ 0.
8, which is a number that satisfies p1 + q1 + q2 + p2 = 1, but q1 and q2 never become 0 at the same time.

More preferably, p1, p2, q1, q2
Are as follows.

[0071]

(Equation 1) Further, it is desirable that q1 / (q1 + q2) is 0 to 1, more preferably 0.5 to 1, and still more preferably 0.7 to 1.

Also in this polymer compound, the total amount of the acid labile group and the crosslinking group is determined by the phenolic hydroxyl group of the formula (5), the hydroxyl group of R ⁵ in the general formula (2) and the general formula (3) The ratio is more than 0 mol% and not more than 80 mol% of the average of all the hydrogen atoms of the hydroxyl group in ()).

Examples of the polymer compound include those having a repeating unit represented by the following formulas (5′-1) to (5′-7) and having a terminal P.

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded imageHowever, in the above formula, h is 0 or 1, and y is an integer of 1 to 3.
A number, U₁, U _Two, U_ThreeRepresents the following units.

[0079]

Embedded image

P is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 50 carbon atoms, a carboxyl group, a hydroxyl group or a compound represented by the general formula (2) , (3) or (4),
Not all of the terminal groups P are simultaneously hydrogen atoms. Q
Is a crosslinking group having a C—O—C group, typically represented by the above formula (6)
a) or a crosslinking group represented by (6b), in particular, a compound represented by the formula (6)
a ''), (6b ''), (6a '''), (6
b '' ′), preferably a crosslinking group represented by (6a ′) or (6b ′). In addition, when a crosslinking group is trivalent or more,
In the above formula (5), Q is bonded to three or more of the following units.

[0081]

Embedded image

The above formulas (5'-2) and (5'-5)
Indicates a state of intramolecular bonding, and the other indicates a state of intermolecular bonding, which may be used alone or in combination.

The crosslinked polymer compound of the present invention may have a phenolic hydroxyl group and / or a compound of the formula (2)
And / or the intramolecular and / or intramolecular compound obtained by reacting the hydroxyl group of R ⁵ and / or the hydroxyl group in the general formula (3) with an alkenyl ether compound or a halogenated alkyl ether.
Alternatively, it is cross-linked by a cross-linking group having a C—O—C group between molecules. In this case, as described above, the total amount of the acid labile group and the cross-linking group is a phenolic compound of the formula (1). More than 0 mol% and more than 80 mol%, especially 2 to 50 mol%, of the average of all the hydrogen atoms of the hydroxyl group and / or the hydroxyl group of R ⁵ in the general formula (2) and / or the hydroxyl group in the general formula (3).
It is preferred that

In this case, the proportion of the crosslinking group having a C—O—C group is more than 0 mol% on average and 80 mol% or less, preferably 0.2 to 20 mol%. When it is 0 mol%, the advantages of the cross-linking group cannot be brought out, the contrast of the alkali dissolution rate becomes small, and the resolution may be deteriorated. On the other hand, if it exceeds 80 mol%, it crosslinks too much and gels and loses solubility in alkali,
In the case of alkali development, a change in film thickness, stress in the film or generation of air bubbles may be caused, or adhesion to the substrate may be poor due to a decrease in the number of hydrophilic groups.

The ratio of acid labile groups is 0 mol% on average.
And more preferably 80 mol% or less, particularly preferably 10 to 50 mol%. At 0 mol%, the contrast of the alkali dissolution rate becomes small, and the resolution becomes poor. On the other hand, 80 mol%
If it exceeds, the solubility in alkali may be lost, or the affinity with a developing solution may be lowered during alkali development, resulting in poor resolution.

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

The polymer compound according to the present invention must have a weight average molecular weight of 1,000 to 500,000, preferably 3,000 to 50,000. If the weight average molecular weight is less than 1,000, the resist material will have poor heat resistance, and if it exceeds 500,000, the alkali solubility will be reduced and the resolution will be degraded.

Further, in the polymer compound according to the present invention, the molecular weight distribution (Mw / M
When n) is wide, it is difficult to design the number of crosslinks due to the presence of a polymer having a low molecular weight or a high molecular weight, and it may be difficult to produce a resist material having the same performance. Therefore, the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer,
In order to obtain a resist material suitably used for fine pattern dimensions, the molecular weight distribution should be 1.0 to 1.5, particularly 1.0 to 1.5.
Preferably, the dispersion is as narrow as 1.3. However, it is not limited to these, and it is of course possible to use those having a molecular weight distribution of more than 1.5.

The method for producing the crosslinked polymer compound according to the present invention includes, for example, the general formula (1-
An acid labile group represented by the general formula (7) is introduced into a phenolic hydroxyl group of a polymer compound having a repeating unit represented by i), and after isolation, is reacted with an alkenyl ether compound or a halogenated alkyl ether compound. A method of crosslinking with a crosslinking group having a C—O—C group in the molecule and / or between the molecules, or a method of reacting with an alkenyl ether compound or a halogenated alkyl ether compound to form a C—O—C—C in the molecule and / or between the molecules. And isolating and then introducing an acid labile group represented by the general formula (7), or a reaction with an alkenyl ether compound or a halogenated alkyl ether compound and the reaction represented by the general formula (7). There is a method in which acid labile groups are introduced at once, but alkenyl ether compounds or halogenated How the introduction of acid labile groups represented by reacting the general formula with ether compound (7) in the batch it is preferable. In addition, the polymer compound obtained as described above may optionally contain an acid labile group represented by the general formula (8),
It is also possible to introduce a tertiary alkyl group, a trialkylsilyl group, an oxoalkyl group or the like.

The terminal of the polymer compound having a repeating unit represented by the general formula (1-i) is a hydrogen atom, a linear, branched or cyclic alkyl or alkenyl group having 1 to 30 carbon atoms, In order to modify with an aromatic hydrocarbon group, a carboxyl group, a hydroxyl group or a group represented by the general formula (2), (3) or (4), a general terminating agent for living anion polymerization can be variously modified. It can be synthesized by changing to a terminator. For example, when the terminal of the polymer compound is a hydrogen atom, water or alcohol is used as a terminator, and when it is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, methyl iodide is used as a terminator. , Ethyl bromide, alkyl halides such as butyl bromide can be used, and when an aromatic hydrocarbon group is used, 4-chlorobenzene, chlorobenzyl, 4-naphthalene bromide,
Halogenated aromatic hydrocarbon groups such as 4-chlorobiphenyl and anthracene bromide can be used. When the terminal of the polymer compound is a carboxyl group, carbonic acid or the like is used as a terminator, and when the terminal is a hydroxyl group, a combination of trimethoxyborane and hydrogen peroxide can be used as the terminator.

When the terminal of the polymer compound is a group represented by the general formula (2), methyl carbonyl chloride, methoxy carbonyl chloride, ethoxy carbonyl chloride, butoxy carbonyl chloride,
Cyclopropanecarbonyl chloride, 1-adamantanecarbonyl chloride, cyclohexanecarbonyl chloride, benzyloxycarbonyl chloride, methylcarbonylmethyl chloride, methoxycarbonylethyl chloride, tert-butoxycarbonylmethyl chloride, butoxycarbonylbenzyl chloride,
Cyclohexyloxycarbonyl chloride, cyclopentanecarbonyl chloride, cyclopentanecarbonylmethyl chloride, 1-adamantanecarbonylhexyl chloride, cyclohexanecarbonylmethyl chloride, benzyloxycarbonyl chloride and the like can be used.

When a group represented by the general formula (3) is used,
As a terminator, ethylene oxide, propylene oxide, styrene oxide, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 2-bromoethyl vinyl ether, methyl ethyl ketone, cyclohexanone, pentanone, 3-acetylnoradamantane, formaldehyde, acetaldehyde, trimethylaldehyde, methyl formate , Methyl acetate and the like can be used.

When a group represented by the general formula (4) is used,
As a terminator, chloromethyl methyl ether, 2-bromoethyl methyl ether, chloromethyl octyl ether, chloromethyl cyclohexyl ether, chloromethyl benzyl ether and the like can be used.

In this case, the amount of the terminator added is preferably at least equimolar to the initiator.

Next, the method for producing the above-mentioned crosslinked polymer compound will be specifically described. As a first method, a polymer having a repeating unit represented by the formula (1 ′) and having a terminal P is used. A compound, an alkenyl ether compound represented by the following general formula (I) or (II), and a compound represented by the following general formula (7)
A method using the compound represented by a), as a second method,
A polymer compound having a repeating unit represented by the formula (1 ′) and having a terminal P, and a compound represented by the following general formula (VII) or (VI)
A method using a halogenated alkyl ether compound represented by II) and a compound represented by the following general formula (7b) is exemplified.

[0096]

Embedded image

Here, R ¹ , R ² , R ⁸ , R ⁹ , x, y and p 1, p 2, q 1, q 2 have the same meaning as described above.
1 + p2 + q1 + q2 = 1. R ⁵ and R ⁶ have the same meaning as above, and R ^9a 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 represents 2 to 8) 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, and a part of the hydrogen atom bonded to the carbon atom is a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. May be replaced by B represents -CO-O-, -NHCO-O- or -NHCONH-, and d represents 0 or an integer of 1 to 10.

Specifically, the C-valent hydrocarbon group of A preferably has 1 to 50 carbon atoms, particularly 1 to 40 carbon atoms such as O, NH,
N (CH _3), S, unsubstituted or hydroxyl or may be heteroatoms interposed such SO _2, a carboxyl group, an acyl group or a fluorine atom-substituted alkylene group, preferably having a carbon number of 6-5
0, especially 6 to 40 arylene groups, groups in which these alkylene groups and arylene groups are bonded, and c ″ valence (c ”is an integer of 3 to 8) from which a hydrogen atom bonded to a carbon atom of each of the above groups is eliminated. And a c-valent heterocyclic group, and a group in which the heterocyclic group is bonded to the above-mentioned hydrocarbon group.

Specific examples include the following as A.

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

The compound represented by the formula (I) is described, for example, in Stephen. C. Lapin, Polymer
s Paint Color Journal. 17
9 (4237) and 321 (1988), that is, by a reaction between a polyhydric alcohol or polyhydric phenol and acetylene, or a reaction between a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether. Can be.

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, 1,4- Divinyloxymethylcyclohexane, 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 Propylene 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.

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

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 suitably 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.

[0114]

Embedded image (R ^6a , R ⁷ and R ⁸ have the same meaning as described above.)

B is -NHCO-O- or -NHCONH
Examples of a method for obtaining the compound represented by the general formula (II) in the case of-include a crosslinking agent handbook (published by Taisei Corporation,
Compounds having an isocyanate group described in 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 Nate, polymethylene polyphenyl isocyanate, polyisocyanate type such as hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylolpropane,
Examples thereof include adducts of hexamethylene diisocyanate and water, and adducts of xylene diisocyanate and trimethylolpropane, and polyisocyanate adducts. 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
Examples represented by (II-11) can be given, but the invention is not limited thereto.

[0116]

Embedded image

[0117]

Embedded image

In the first method, the weight average molecular weight is 1,000 to 500,000, and preferably has a repeating unit represented by the general formula (1 ′) having a molecular weight distribution of 1.0 to 1.5. And the hydrogen atom of the phenolic hydroxyl group of the polymer compound having a terminal P is defined as p1 mole of the alkenyl ether compound represented by the general formula (I) or (II) relative to 1 mole of the total hydroxyl group and q1 mole of the alkenyl ether compound. By reacting the compound represented by the formula (7a), for example, the following general formula (5)
A polymer compound having a repeating unit represented by a′-1) or (5a′-7) and having a terminal P can be obtained. In addition, the terminal P of the polymer compound and the compound represented by the general formula (7a) can be further reacted. In the following formula, m + n = y, and h, k, m, n,
x, y, p1, p2, q1, q2, R 1, R 2, R 9, R
¹⁰ , R ¹¹ and Q each have the same meaning as described above.

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image In the above formula, U ₁ and U ₃ ′ represent the following units.

[0124]

Embedded image

The reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran, ethyl acetate and the like, 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 preferably used. It is preferable that the hydrogen atom of the phenolic hydroxyl group of the polymer compound represented by the formula (1 ′) is 0.1 to 10 mol% based on 1 mol of all the hydroxyl groups.

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 (7a) is not particularly limited, but first, the compound represented by the general formula (7a) 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 (7a) 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.

[0129]

Embedded image [Wherein, R ¹ , R ² , x, y, p1, p2, q1, q2,
R ^9a , R ¹⁰ , R ¹¹ and R ⁶ , R ⁷ , R ⁸ , A, B, c, d
Has the same meaning as above, and Z is a halogen atom (Cl, Br or I). ]

The compounds of the above formulas (VI) and (VII) and the compound of the formula (7b) are the same as the compounds of the above formulas (I) and (II) and the compound of the formula (7a) except for hydrogen chloride and hydrogen bromide. Alternatively, it can be obtained by reacting hydrogen iodide.

In the second method, the weight average molecular weight is preferably 1,0.
The phenolic hydroxyl group of the high molecular compound having a repeating unit represented by the general formula (1 ′) having a molecular weight distribution of 1.0 to 1.5 and having a terminal of P; The reaction is carried out by reacting p1 mol of the halogenated alkyl ether compound represented by the general formula (VI) or (VII) with q1 mol of the compound represented by the general formula (7b). ) To (5a'-)
A polymer compound having a repeating unit represented by 7) and having a terminal at P can be obtained. In addition, the terminal P of the polymer compound and the compound represented by the general formula (7b) can be further reacted.

The above production method is preferably carried out in a solvent in the presence of a base.

As the reaction solvent, 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.

The base is preferably triethylamine, pyridine, diisopropylamine, potassium carbonate or the like. The amount of the base used is (p) per mole of the phenolic hydroxyl group of the polymer compound represented by the general formula (1 ′) to be reacted.
It is preferably at least 1 + q1) mol.

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, a polymer having a repeating unit represented by the formula (1 ′) and having a terminal P is reacted with a compound of the formula (7a) or (7b) to obtain a compound represented by the following formula: After obtaining a polymer compound having a repeating unit represented by (10) and having a terminal at P, this is isolated and then represented by the formula (I), (II) or (VI), (VII) Crosslinking may be performed using a compound.

[0137]

Embedded image

The polymer obtained by the above first or second method and having, for example, a repeating unit represented by formulas (5a′-1) to (5a′-7) and having a terminal P is
If necessary, q2 mol of dialkyl dicarbonate compound or alkoxycarbonylalkyl with respect to 1 mol of phenolic hydroxyl group of a polymer compound having a repeating unit represented by the general formula (1 ′) and terminating at P By reacting a halide or the like to introduce an acid labile group represented by the general formula (8), or reacting a tertiary alkyl halide, a trialkylsilyl halide, an oxoalkyl compound or the like, for example, the above-mentioned general formula (5 ′) A polymer compound having a repeating unit represented by -1) to (5′-7) and having a terminal P can be obtained.

The method for introducing the acid labile group of the above formula (8) is as follows.
It is preferable to carry out the reaction in a solvent in the presence of a base.

As the reaction solvent, 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, and the amount of the base is based on 1 mol of the phenolic hydroxyl group of the original polymer compound represented by the general formula (1 ′). It is preferably q2 mol.

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-butoxycarbonylmethyl chloride,
tert-amyloxycarbonylmethyl chloride, t
tert-butoxycarbonylmethyl bromide, ter
t-butoxycarbonylethyl chloride, ethoxyethoxycarbonylmethyl chloride, ethoxyethoxycarbonylmethyl bromide, tetrahydropyranyloxycarbonylmethyl chloride, tetrahydropyranyloxycarbonylmethyl bromide, tetrahydrofuranyloxycarbonylmethyl chloride, tetrahydrofuranyloxycarbonylmethyl bromide, etc. Examples of the trialkylsilyl halide include trimethylsilyl chloride, triethylsilyl chloride, and dimethyl-tert-butylsilyl chloride.

Further, a polymer having repeating units represented by formulas (5a′-1) to (5a′-7) and having a terminal P is obtained by the first or second method. ,
If necessary, a tertiary alkylating agent having q2 mol per 1 mol of the phenolic hydroxyl group of the polymer compound having a repeating unit represented by the general formula (1 ′) and having a terminal P;
The oxoalkyl compound can be reacted for tertiary alkylation or oxoalkylation.

The above method is preferably carried out in a solvent in the presence of an acid.

The reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran, ethyl acetate, etc., and may be used alone or as a mixture of two or more.

As the acid for the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, pyridinium p-toluenesulfonate and the like are preferable. Having a repeating unit represented by the formula (1 ′),
A phenolic hydroxyl group of a polymer compound having the general formula (2)
Is preferably 0.1 to 10 mol% with respect to 1 mol of the hydroxyl group of R ⁵ in formula (1) and the hydroxyl group in formula (3).

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 a 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.

Incidentally, the general formulas (5a'-1) to (5a'-
7) The polymer compound having a repeating unit represented by the following general formulas (5b′-1) to (5b′-7) represented by the following general formula (5b′-1) without passing through the polymer compound represented by the general formula (8) ), A tertiary alkyl group, a trialkylsilyl group, an oxoalkyl group, or the like, and then, if necessary, an acid labile group represented by the general formula (7).

[0151]

Embedded image

[0152]

Embedded image

[0153]

Embedded image

[0154]

Embedded image

[0155]

Embedded image Where R ¹ , R ² , Q, p1, p2, q1, q2,
h, x, and y each have the same meaning as described above. Also,
U ₃ ″ represents the following units.

[0156]

Embedded image

In the polymer compound according to the present invention, R ³
The acid labile group is not limited to one type, and two or more types can be introduced. In this case, q1 mol of an acid labile group is introduced as described above with respect to 1 mol of all hydroxyl groups of a polymer compound having a repeating unit of the formula (1 ′) and terminating at P, and then, By introducing q2 moles of different acid labile groups in the same manner as described above, a polymer compound in which two or more such acid labile groups are introduced as appropriate or more can be obtained.

The chemically amplified positive resist composition of the present invention comprises:
The polymer compound is used as a base polymer and contains the following components. (A): an organic solvent; (B): a polymer compound of the above formula (1), preferably formula (5) as a base resin; and (C): an acid generator.

In this case, the resist composition of the present invention may further contain one or more of the following components (D) to (I) in addition to the above components (A) to (C).

(D): As a base resin different from the component (B), one or more acid (s) containing one or more hydrogen atoms of the phenolic hydroxyl group of a polymer compound having a repeating unit represented by the following general formula (9): 0 mol% on average due to unstable groups
A polymer compound having a weight average molecular weight of 3,000 to 300,000 partially substituted at a ratio of at least 80 mol%.

[0161]

Embedded image [Wherein, R ¹ , R ² , R ⁹ , R ¹⁰ , and R ¹¹ have the same meanings as described above, and R ¹² is an acid labile group different from —CR ⁹ R ¹⁰ OR ¹¹ ; f is 0 or a positive number, g is a positive number, and e +
f + g = 1, 0 ≦ e / (e + f + g) ≦ 0.5,
0.4 ≦ g / (e + f + g) ≦ 0.9. In addition, the phenolic hydroxyl group of the polymer compound represented by the above general formula (9) is obtained by reacting a phenolic hydroxyl group with an alkenyl ether compound or a halogenated alkyl ether.
It may be cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a -OC group. In the formula (9), the total amount of the acid labile group and the cross-linking group is e = 0, f = 0, g = 1
In this case, the ratio is more than 0 mol% and not more than 80 mol% on the average of all hydrogen atoms of the phenolic hydroxyl group. (E): dissolution controlling agent. (F): Basic compound. (G): an aromatic compound having a group represented by ≡C-COOH in the molecule. (H): UV absorber. (I): acetylene alcohol derivative.

Here, the organic solvent of the component (A) used in the present invention may be any organic solvent which can dissolve the acid generator, the base resin, the dissolution controlling agent and the like. Examples of such an organic solvent include ketones such as cyclohexanone, methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol,
Alcohols such as -methoxy-2-propanol and 1-ethoxy-2-propanol, and ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, 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, 3
Esters such as ethyl ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; one of these being used alone or as a mixture of two or more; However, the present invention is not limited to these. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and ethyl lactate, which have the highest solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate, which is a safe solvent, is used. And a mixed solvent thereof are preferably used.

The amount of the organic solvent used is 100 base resin (total amount of the above components (B) and (D), the same applies hereinafter).
Parts (weight parts, the same applies hereinafter)
Parts, especially 400 to 800 parts, are suitable.

Examples of the acid generator of the component (C) include an onium salt of the following general formula (11), a diazomethane derivative of the formula (12), a glyoxime derivative of the formula (13), a β-ketosulfone derivative, a disulfone derivative, and nitrobenzyl. Sulfonate derivatives, sulfonic acid ester derivatives, imido-yl sulfonate derivatives, and the like.

[0165] _{^{(R 30) b M + K}} - (11) ( where, R ³⁰ is a straight-chain having 1 to 12 carbon atoms, branched or cyclic alkyl group, an aryl group or a carbon number of 6 to 12 carbon atoms Represents 7 to 12 aralkyl groups, M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and b is 2 or 3.)

As the alkyl group for R ^30, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group,
An oxocyclohexyl group, a norbornyl group, an adamantyl group and the like can be mentioned. As the aryl group, a phenyl group,
p-methoxyphenyl group, m-methoxyphenyl group, o
-Methoxyphenyl group, ethoxyphenyl group, p-te
an alkoxyphenyl group such as an rt-butoxyphenyl group, an m-tert-butoxyphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group,
Ethylphenyl group, 4-tert-butylphenyl group,
Examples thereof include an alkylphenyl group such as a 4-butylphenyl group and a dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate , 4-fluorobenzenesulfonate, arylsulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0167]

Embedded image (However, R ³¹ and R ³² are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms, or a C ⁷ to C 12 12 represents an aralkyl group)

Examples of the alkyl group for R ³¹ and R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. Examples of the aryl group include phenyl, p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert.
An alkoxyphenyl group such as -butoxyphenyl group, 2-
Examples thereof include an alkylphenyl group such as a 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.

[0169]

Embedded image (However, R ³³ , R ³⁴ , and R ³⁵ are linear having 1 to 12 carbon atoms;
It represents a branched or cyclic alkyl group or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms, an aryl halide group or an aralkyl group having 7 to 12 carbon atoms. Also,
R ³⁴ and R ³⁵ may combine with each other to form a cyclic structure, and when forming a cyclic structure, R ³⁴ and R ³⁵ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. . )

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ³³ , R ³⁴ , and R ³⁵ include the same groups as those described for R ³¹ and R ³² . The alkylene group for R ³⁴ and R ³⁵ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

More specifically, for example, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-
(Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris trifluoromethanesulfonate (P-tert-butoxyphenyl) sulfonium,
triphenylsulfonium p-toluenesulfonate, p
-(P-tert-butoxyphenyl) diphenylsulfonium toluenesulfonate, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-toluenesulfonate)
(t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate Onium salts such as bis (benze) Sulfonyl) diazomethane, bis (p- toluenesulfonyl) diazomethane, bis (xylene sulfonyl) diazomethane, bis (cyclohexyl sulfonyl) diazomethane, bis (cyclopentyl sulfonyl) diazomethane, bis (n- butylsulfonyl)
Diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (t
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-
Diazomethane derivatives such as cyclohexylsulfonyl-1- (tert-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- (p-tert-butylbenzenesulfonyl) -α
Glyoxime derivatives such as -dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime, 2-cyclohexylcarbonyl-2
Β-ketosulfone derivatives such as-(p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane; disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; 2,6-dinitrop-toluenesulfonate Nitrobenzylsulfonate derivatives such as benzyl and 2,4-dinitrobenzyl p-toluenesulfonate;
Tris (methanesulfonyloxy) benzene, 1,2,2
Sulfonate derivatives such as 3-tris (trifluoromethanesulfonyloxy) benzene and 1,2,3-tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-triflate, phthalimido-yl-
Tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,
Imido-yl-sulfonate derivatives such as 3-dicarboximido-yl-tosylate and 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate; and triphenylsulfonium trifluoromethanesulfonate; Triphenylmethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-
Onium such as tert-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), and tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate Salt, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, Bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl)
Diazomethane derivatives such as diazomethane and bis (tert-butylsulfonyl) diazomethane; bis-o- (p-
Glyoxime derivatives such as toluenesulfonyl) -α-dimethylglyoxime and bis-o- (n-butanesulfonyl) -α-dimethylglyoxime are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. 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 compounding amount of the acid generator is based on 100 parts of the base resin.
The amount is preferably from 0.2 to 15 parts, more preferably from 0.5 to 8 parts with respect to the part. If the amount exceeds 15 parts, the transmittance of the resist decreases, and the resolution may be poor.

The base resin other than the polymer compound relating to the component (B) of the component (D) is represented by the following general formula (9)
Weight average molecular weight having a repeating unit represented by 3,
000-300,000 high molecular compounds are used.
By blending the component (D), it is advantageous to control the dimension of the pattern and the shape of the pattern as desired.

[0174]

Embedded image [Wherein, R ¹ , R ² , R ⁹ , R ¹⁰ , and R ¹¹ have the same meanings as described above, and R ¹² is an acid labile group different from —CR ⁹ R ¹⁰ OR ¹¹ ; f is 0 or a positive number, g is a positive number, and e +
f + g = 1, 0 ≦ e / (e + f + g) ≦ 0.5,
0.4 ≦ g / (e + f + g) ≦ 0.9. In addition, the phenolic hydroxyl group of the polymer compound represented by the above general formula (9) is obtained by reacting a phenolic hydroxyl group with an alkenyl ether compound or a halogenated alkyl ether.
It may be cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a -OC group. In the formula (9), the total amount of the acid labile group and the cross-linking group is e = 0, f = 0, g = 1
In this case, the ratio is more than 0 mol% and not more than 80 mol% on the average of all hydrogen atoms of the phenolic hydroxyl group. ]

Such a high molecular compound has a weight average molecular weight of 3,000 to 300,000, preferably 5,000.
It must be between 0 and 30,000. If the weight average molecular weight is less than 3,000, the resist material will have poor heat resistance. If it exceeds 300,000, the alkali solubility will be reduced and the resolution will be poor.

Further, even in the base resin of the component (D), when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer is present, and when a large amount of low molecular weight polymer is present, heat resistance is low. In some cases, when a high-molecular-weight polymer is present in a large amount, it may be difficult to dissolve in alkali, and may cause tailing after pattern formation. Therefore, as the pattern rule becomes finer, the influence of such molecular weight and molecular weight distribution tends to increase. Therefore, in order to obtain a resist material suitably used for fine pattern dimensions, the molecular weight distribution of the base resin must be as follows. 0
It is preferably a narrow dispersion of 2.5 to 2.5, particularly 1.0 to 1.5.

The blending ratio of the base resin (D) to the base resin (crosslinked polymer compound) of the component (B) is preferably 0: 100 to 90:10 by weight. In particular, 0: 100 to 50:50 is preferable. If the amount of the base resin (D) is greater than the above weight ratio, the desired effect of the base resin (crosslinked polymer compound) of the component (B) may not be obtained.

In the resist composition of the present invention, a dissolution controlling agent can be further added as a component (E), whereby the contrast can be improved. As the dissolution controlling agent, the hydrogen atom of the phenolic hydroxyl group of a compound having an average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule is entirely formed by an acid labile group. 0-100 mol% on average
The substituted compound is blended at the ratio of

Incidentally, the substitution rate of the hydrogen atom of the phenolic hydroxyl group by the acid labile group is 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group on average.
The upper limit is 100 mol%, more preferably 80 mol%.

In this case, such a phenolic hydroxyl group is 2
Compounds having one or more of the following formulas (i) to (xi)
Are preferred.

[0181]

Embedded image

[0182]

Embedded image

[0183]

Embedded image (Wherein, R ²¹ and R ²² each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ²³ represents a hydrogen atom or a linear chain having 1 to 8 carbon atoms. Or branched alkyl or alkenyl group, or-
(R ²⁷ ) _h —COOH, and R ²⁴ 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, R
²⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ²⁶ is a hydrogen atom or a linear or branched chain having 1 to 8 carbon atoms. An alkyl group, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group,
²⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms. J is an integer of 0 to 5, and h and u are 0 or 1. s, t, s ′, t ′, s ″, and t ″ satisfy s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and have at least one hydroxyl group in each phenyl skeleton. Such a number. α is the equation (viii), (ix)
Is a number with a molecular weight of 100 to 1,000. )

In the above formula, R ²¹ and R ²² include, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group, ethynyl group, cyclohexyl group, and R ²³ include, for example, R
²¹ and R ²² , or -COOH, -CH ₂
COOH and R ²⁴ include, for example, an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom and a sulfur atom, and R ²⁵ includes, for example, a methylene group or R ²⁴
Materials similar to those in, for example hydrogen atom R ^26, a methyl group, an ethyl group, butyl group, propyl group, an ethynyl group, a cyclohexyl group, each phenyl group substituted with a hydroxyl group, a naphthyl group and the like.

Here, as the acid labile group of the dissolution controlling agent, groups represented by the above general formulas (7) and (8), tertiary alkyl groups having 4 to 20 carbon atoms, and each alkyl group can be used. Trialkylsilyl group having 1 to 6 carbon atoms, 4 to 2 carbon atoms
And an oxoalkyl group of 0.

The compound (dissolution controlling agent) in which the phenolic hydroxyl group is partially substituted with an acid labile group is 0 to 50 parts, preferably 5 to 50 parts, per 100 parts of the base resin.
Parts, more preferably 10 to 30 parts, and they 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.

The above-mentioned dissolution controlling agent can be synthesized by chemically reacting a compound having a phenolic hydroxyl group with an acid labile group in the same manner as in the base resin.

The resist composition of the present invention may have a weight average molecular weight of more than 1,000 and not more than 3,000 as another dissolution controlling agent instead of or in addition to the above dissolution controlling agent, and a phenolic hydroxyl group in the molecule. And a compound in which the hydrogen atom of the phenolic hydroxyl group is partially substituted by an acid labile group at an average rate of 0% or more and 60% or less as a whole.

In this case, as the compound in which the hydrogen atom of the phenolic hydroxyl group is partially substituted with such an acid labile group,
One or more compounds selected from compounds having a repeating unit represented by the following general formula (14) and having a weight average molecular weight of more than 1,000 and not more than 3,000 are preferred.

[0190]

Embedded image (In the formula, R ³ represents an acid labile group, and v and w are numbers satisfying 0 ≦ v / (v + w) ≦ 0.6, respectively.)

Here, the acid labile group of the dissolution controlling agent includes a group represented by the general formula (7), a group represented by the general formula (8), and a tertiary alkyl group having 4 to 20 carbon atoms. And each alkyl group includes a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

The compounding amount of the above-mentioned another dissolution controlling agent is based on the total amount of the dissolution controlling agent and the dissolution controlling agent as a whole.
0 to 50 parts, especially 0 to 30 parts, preferably 1 to 0 parts
It is preferable that the amount be in a range such that at least one part is used.

The other dissolution controlling agent as described above can be synthesized by chemically reacting a compound having a phenolic hydroxyl group with an acid labile group as in the case of the base resin.

As the basic compound as the component (F), a compound capable of suppressing the rate of diffusion of the acid generated from the acid generator into the resist film is suitable. By the compounding, the diffusion rate of the acid in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, and the exposure margin and the pattern profile are improved. be able to.

Such basic compounds include primary, secondary and tertiary aliphatic amines, hybrid amines, and the like.
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples of the compound 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, and an aliphatic amine is particularly preferably used.

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 (For example, quinoline, 3-quinolinecarbonitrile, etc.), 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 amide derivatives 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 formulas (15) and (16) can be blended.

[0200]

Embedded image (Wherein, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ are each independently a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, R ⁴⁴ , R ⁴⁵ and R ⁴⁶⁾ , R ⁴⁹ and R ⁵⁰ are hydrogen atoms,
An alkyl group or an amino group having 1 to 20 carbon atoms, R ⁴⁴
And R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ ,
R ⁴⁹ and R ⁵⁰ may be combined with each other to form a ring.
S, T, and U each represent an integer of 0 to 20. However,
When S, T, U = 0, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ , R ⁵⁰
Does not contain a hydrogen atom. )

Here, the alkylene group of 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 groups of R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ have 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, 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, and further preferably an integer of 1 to 8.

Specific examples of the compounds of the above formulas (15) and (16) include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, and 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) ethoxy} ethyl] 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, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6
And the like. Especially 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 derivatives, imide derivatives, 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 preferred.

The above-mentioned basic compounds can be used alone or in combination of two or more. The compounding amount is 0.01 to 2 parts, especially 0.01 to 2 parts, based on 100 parts of the total base resin. ~ 1 part is preferred. If the amount is less than 0.01 part, the effect is not obtained, and if it exceeds 2 parts, the sensitivity may be too low.

Further, the resist composition of the present invention may further comprise (G)
≡C-COOH in the molecule blended as
Is -R⁵⁷ -COOH (R⁵⁷ Is a straight-chain having 1 to 10 carbon atoms or
Is a branched alkylene group)
The compound is, for example, one selected from the following groups I and II
Or two or more compounds can be used,
It is not limited to them. (G) By the composition of the component
Improves the PED stability of the resist,
Edge roughness can be improved. [Group I] Compounds represented by the following formulas (17) to (26)
Part or all of the hydrogen atoms of the phenolic hydroxyl group of the product
R⁵⁷ -COOH (R⁵⁷ Is linear or branched having 1 to 10 carbon atoms.
Substituted by a branched alkylene group)
Phenolic hydroxyl group (C) and ≡C-COOH
Molar ratio with the group (D) is C / (C + D) = 0.1 to
A compound that is 1.0. [Group II] A compound represented by the following general formulas (27) and (28)
Compound.

[0208]

Embedded image

[0209]

Embedded image (Where R ¹ is a hydrogen atom or a methyl group,
R ⁵¹ and R ⁵² each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms;
⁵³ is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or — (R ⁵⁷ ) _h —CO
An OR ′ group (R ′ is a hydrogen atom or —R ⁵⁷ —COOH); R ⁵⁴ is — (CH ₂ ) _i — (i = 2 to 10);
-10 arylene groups, carbonyl groups, sulfonyl groups,
An oxygen atom or a sulfur atom, R ⁵⁵ is an alkylene group having 1 to 10 carbon atoms, 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 is a hydrogen atom or a carbon atom having 1 to 8 carbon atoms. A linear or branched alkyl group, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group, R ⁵⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms, and R ⁵⁸ is is a hydrogen atom or a linear or branched alkyl or alkenyl group, or -R ⁵⁷ -COOH group having 1 to 8 carbon atoms. j is an integer of 0 to 5, and u and h are 0 or 1. s1, t1, s
2, t2, s3, t3, s4, and t4 are respectively s1 + t
1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4
= 6 and has at least one hydroxyl group in each phenyl skeleton. β is a number which makes the compound of the formula (22) a weight average molecular weight of 1,000 to 5,000, and γ is a number which makes the compound of the formula (23) a weight average molecular weight of 1,000.
This is a number from 0 to 10,000. )

[0210]

Embedded image (R ⁵¹ , R ⁵² and R ⁵⁷ have the same meanings as above.
t5 is a number that s5 ≧ 0 and t5 ≧ 0, and s5 + t5 = 5. )

Specific examples of the component (G) include, but are not limited to, compounds represented by the following general formulas III-1 to IV-14 and IV-1 to IV-6.

[0212]

Embedded image

[0213]

Embedded image

[0214]

Embedded image (However, R ″ represents a hydrogen atom or a CH ₂ COOH group,
In each compound, 10 to 100 mol% of R ″ is CH ₂ C
OOH group. α and β have the same meaning as described above. )

[0215]

Embedded image

The aromatic compound 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 aromatic compound having a group represented by ≡C-COOH in the molecule is 0.1 to 5 parts, more preferably 1 to 3 parts, per 100 parts of the base resin. If the amount is less than 0.1 part, the footing on the nitride film substrate and the effect of improving the PED may not be sufficiently obtained, and if the amount is more than 5 parts, the resolution of the resist material may decrease.

The resist composition of the present invention further comprises (H)
A compound having a molar absorbance at a wavelength of 248 nm of 10,000 or less can be blended as a component ultraviolet absorber. This makes it possible to design and control a resist having an appropriate transmittance for substrates having different reflectivities.

More specifically, pentalene, indene, naphthalene, azulene, peptalene, biphenylene, indacene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene,
Naphthalene, preiaden, picene, perylene, pentaphen, pentacene, benzophenanthrene, anthraquinone, anthrone benzantrone, 2,7-dimethoxynaphthalene, 2-ethyl-9,10-dimethoxyanthoselan, 9,10-dimethylanthracene, 9- Ethoxyanthracene, 1,2-naphthoquinone, 9-fluorene, condensed polycyclic hydrocarbon derivatives such as the following general formulas (29) and (30), condensed heterocyclic derivatives such as thioxanthen-9-one, thianthrene and dibenzothiophene; 2,
3,4-tribitroxybenzophenone, 2,3,4
4′-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone,
Benzophenone derivatives such as 4,4'-bis (dimethylamino) benzophenone; squaric acid derivatives such as squaric acid and dimethyl squarate;

[0220]

Embedded image (Wherein, R ^{61 to} R ⁶³ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, a linear R ⁶⁴ is a substituted or unsubstituted divalent aliphatic hydrocarbon group which may contain an oxygen atom, or a substituted or unsubstituted group which may contain an oxygen atom. A divalent alicyclic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom or an oxygen atom,
⁶⁵ is an acid labile group. J is 0 or 1. E, F,
G is 0 or an integer of 1 to 9, H is a positive integer of 1 to 10, and satisfies E + F + G + H ≦ 10. )

More specifically, the above formulas (29) and (30)
Wherein R ^{61 to} R ⁶³ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, a linear or branched Linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, ter
Those having 1 to 10 carbon atoms such as a t-butyl group, a hexyl group, a cyclohexyl group and an adamantyl group are preferred, and among them, a methyl group, an ethyl group, an isopropyl group and a tert-butyl group are more preferably used. Examples of the linear or branched alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hexyloxy, and cyclohexyloxy. Those having formulas 1 to 8 are preferred, and among them, methoxy, ethoxy, isopropoxy and tert-butoxy groups are more preferably used. As the linear or branched alkoxyalkyl group, for example, those having 2 to 10 carbon atoms such as methoxymethyl group, 1-ethoxypropyl group, 1-propoxyethyl group and tert-butoxyethyl group are preferable, and among them, Preferred are a methoxymethyl group, a 1-ethoxyethyl group, a 1-ethoxypropyl group, a 1-propoxyethyl group and the like. As the linear or branched alkenyl group, those having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group and a butenyl group are preferred. As the aryl group, those having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, and a cumenyl group are preferable.

R ⁶⁴ is a substituted or unsubstituted divalent aliphatic hydrocarbon group which may contain an oxygen atom, or a substituted or unsubstituted divalent alicyclic hydrocarbon group which may contain an oxygen atom. A substituted or unsubstituted divalent aromatic hydrocarbon group or an oxygen atom which may contain an oxygen atom. In the formula, J is 0 or 1, and when J is 0, -R ⁶⁴
The bond is a single bond;

Examples of the substituted or unsubstituted divalent aliphatic hydrocarbon group which may contain an oxygen atom include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec- Butylene group, -CH ₂
O- group, -CH ₂ CH ₂ O- group, -CH ₂ OCH ₂ - is preferred has 1 to 10 carbon atoms, such as radicals, among them methylene group, an ethylene group, -CH ₂ O- group, - CH ₂ CH ₂ O-
Groups are more preferably used.

Examples of the substituted or unsubstituted divalent alicyclic hydrocarbon group which may contain an oxygen atom include, for example,
4-cyclohexylene group, 2-oxacyclohexane-
1,4-ylene group, 2-thiacyclohexane-1,4-
Examples thereof include those having 5 to 10 carbon atoms such as an ylene group.

Examples of the substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom include, for example, o-
Phenylene group, p-phenylene group, 1,2-xylene-
3,6-ylene group, toluene-2,5-ylene group, 1-
Those having 6 to 14 carbon atoms, such as cumene-2,5-ylene group, or -CH ₂ Ph- group, -CH ₂ PhCH ₂ -
Groups, -OCH ₂ Ph- group, -OCH ₂ PhCH ₂ O- group (Ph is a phenylene group) allyl alkylene group having 6 to 14 carbon atoms such as.

Further, R ⁶⁵ is an acid labile group, and the acid labile group as referred to herein means a group obtained by substituting a carboxyl group with one or more functional groups capable of decomposing in the presence of an acid. It is not particularly limited as long as it decomposes in the presence of an acid to release a functional group exhibiting alkali solubility. In particular, groups represented by the following general formulas (31a), (31b), and (31c) are preferred. preferable.

[0227]

Embedded image (Wherein, R ^{66 to} R ⁶⁹ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, Alternatively, it is a branched alkenyl group or an aryl group, and these groups may contain a carbonyl group in the chain, but all of R ^{66 to} R ⁶⁹ must not be hydrogen atoms. ⁶⁶ and R ⁶⁷ may be bonded to each other to form a ring, and R ⁶⁹ is a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl A group or an aryl group, and these groups may contain a carbonyl group in the chain, and R ⁶⁹ may combine with R ⁶⁶ to form a ring.)

In this case, the above-mentioned linear or branched alkyl group, linear or branched alkoxy group, linear or branched alkoxyalkyl group, linear or branched alkenyl group, aryl group Examples thereof include the same as those described above for R ^{61 to} R ⁶³ .

In the formula (31a), the ring formed by combining R ⁶⁶ and R ⁶⁷ with each other includes, for example, cyclohexylidene, cyclopentylidene, 3-oxocyclohexylidene, 3-oxo- Examples thereof include those having 4 to 10 carbon atoms such as a 4-oxacyclohexylidene group and a 4-methylcyclohexylidene group.

In the formula (31b), the ring formed by bonding R ⁶⁶ and R ⁶⁷ to each other includes, for example, 1-silacyclohexylidene group, 1-silacyclopentylidene group, 3-oxo-1- Silacyclopentylidene group, 4-
C3-C3 such as methyl-1-silacyclopentylidene group
9 are mentioned.

Further, in the formula (31c), as the ring formed by bonding R ⁶⁹ and R ⁶⁶ to each other, for example, a 2-oxacyclohexylidene group, a 2-oxacyclopentylidene group, a 2-oxa-4- Those having 4 to 10 carbon atoms such as a methylcyclohexylidene group are exemplified.

Here, the group represented by the above formula (31a) includes, for example, tert-amyl group, 1,1-dimethylethyl group, 1,1-dimethylbutyl group, 1-ethyl-
In addition to tertiary alkyl groups having 4 to 10 carbon atoms such as 1-methylpropyl group and 1,1-diethylpropyl group, 1,1-dimethyl-3-oxobutyl group, 3-oxocyclohexyl group, 1-methyl-3 A 3-oxoalkyl group such as -oxo-4-oxacyclohexyl group is preferred.

Examples of the group represented by the above formula (31b) include a trialkylsilyl group having 3 to 10 carbon atoms such as a trimethylsilyl group, an ethyldimethylsilyl group, a dimethylpropylsilyl group, a diethylmethylsilyl group and a triethylsilyl group. It is suitable.

Examples of the group represented by the above formula (31c) include 1-methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-ethoxypropyl group,
1-ethoxyisobutyl group, 1-n-propoxyethyl group, 1-tert-butoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert
-Pentoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2′-n-butoxyethoxy) ethyl group,
1- (2′-ethylhexyl) oxyethyl group, 1-
(4′-acetoxymethylcyclohexylmethyloxy) ethyl group, 1- {4 ′-(tert-butoxycarbonyloxymethyl) cyclohexylmethyloxy} ethyl group, 2-methoxy-2-propyl group, 1-ethoxypropyl group, dimethoxy Those having 2 to 8 carbon atoms such as a methyl group, a diethoxymethyl group, a tetrahydrofuranyl group and a tetrahydropyranyl group are preferred.

In the above formulas (29) and (30), E, F and G are each 0 or a positive integer of 1 to 9;
Is a positive integer of 1 to 10 and satisfies E + F + G + H ≦ 10.

Preferred specific examples of the compounds of the above formulas (29) and (30) include the compounds represented by the following (32a) to (32j).

[0237]

Embedded image (In the formula, R ⁷⁰ is an acid labile group.)

As the ultraviolet absorbent, bis (4-
Hydroxyphenyl) sulfoxide, bis (4-ter
t-butoxyphenyl) sulfoxide, bis (4-te
diarylsulfoxide derivatives such as rt-butoxycarbonyloxyphenyl) sulfoxide, bis [4- (1-ethoxyethoxy) phenyl] sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-te
rt-butoxyphenyl) sulfone, bis (4-ter
t-butoxycarbonyloxyphenyl) sulfone, bis [4- (1-ethoxyethoxy) phenyl] sulfone, bis [4- (1-ethoxypropoxy) phenyl]
Diarylsulfone derivatives such as sulfone, benzoquinonediazide, naphthoquinonediazide, anthraquinonediazide, diazo compounds such as diazofluorene, diazotetralone and diazophenanthrone, naphthoquinone-1,2
-Complete or partial ester compound of diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone, naphthoquinone-1,2-diazide-4-sulfonic acid chloride and 2,4,4'-trihydroxybenzophenone And quinonediazide group-containing compounds such as complete or partial ester compounds.

As the ultraviolet absorber, tert-butyl 9-anthracenecarboxylate, tert-amyl 9-anthracenecarboxylate, tert-methoxymethyl 9-anthracenecarboxylate, tert-ethoxyethyl 9-anthracenecarboxylate, Tert-tetrahydropyranyl anthracenecarboxylate, tert-tetrahydrofuranyl 9-anthracenecarboxylate,
A partial ester compound of naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone can be exemplified.

The compounding amount of the ultraviolet absorbent (H) is preferably 0 to 10 parts, more preferably 0.5 to 10 parts, and still more preferably 1 to 5 parts with respect to 100 parts of the base resin. preferable.

The resist composition of the present invention further comprises (I)
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 formulas (33) and (34) can be preferably used.

[0243]

Embedded image (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, and X and Y are 0 or Indicates 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
Inc. Olfin E1004 (manufactured by Nissin Chemical Industry Co., Ltd.).

The acetylene alcohol derivative is added in an amount of 0.01 to 2% by weight, more preferably 0.02 to 1% by weight, based on 100% by weight of the resist composition. 0.0
If the amount is less than 1% by weight, the effect of improving coating properties and storage stability may not be sufficiently obtained, and if the amount is more than 2% by weight, the resolution of the resist material may decrease.

The resist composition of the present invention may contain, as an optional component, other than the above components, a surfactant which is commonly used to improve coating properties. 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 examples thereof include perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. For example, Florard "F
C-430 "," FC-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-1 "
45 (all manufactured by Asahi Glass Co., Ltd.), Unidyne “DS
-401 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-8 "
151 "(manufactured by Dainippon Ink and Chemicals, Inc.)," X-70-
092 "and" X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florad “FC-430” (Sumitomo 3M Limited)
X-70-093 "(Shin-Etsu Chemical Co., Ltd.)
Is mentioned.

A pattern can be formed using the chemically amplified positive resist material of the present invention by employing a known lithography technique. For example, a pattern such as spin coating is applied onto a substrate such as a silicon wafer. The film is applied so as to have a thickness of 0.5 to 2.0 μm, and is prebaked on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably at 80 to 120 ° C. for 1 to 5 minutes. Next, a mask for forming a target pattern is held over the resist film, and a deep ultraviolet ray having a wavelength of 300 nm or less, an excimer laser, a high energy ray such as an X-ray or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² . Preferably 10
After irradiating to about 100 mJ / cm ² , post-exposure bake (PEB) is performed 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. In addition, the material of the present invention is most suitable for fine patterning with far ultraviolet rays of 254 to 193 nm or excimer laser, X-rays and electron beams among high energy rays. If the above range is outside the upper and lower limits, the desired pattern may not be obtained.

[0249]

When the polymer compound of the present invention is used as a base resin for a chemically amplified positive resist material, it is sensitive to high energy rays, excellent in sensitivity, resolution, plasma etching resistance, and resist pattern. Excellent heat resistance and reproducibility. Further, the pattern is unlikely to be overhanging, and has excellent dimensional controllability. Further, the storage stability is improved by blending the acetylene alcohol derivative. Therefore, when the polymer compound of the present invention is used as a base resin of a chemically amplified positive resist material, it can be a resist material having a small absorption at the exposure wavelength of a KrF excimer laser due to these characteristics. Moreover, a pattern perpendicular to the substrate can be easily formed.
For this reason, it is suitable as a fine pattern forming material and a pattern forming method for VLSI manufacturing.

[0250]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

[Synthesis Example 1] Carboxylic acid-terminated poly (p-1)
-Ethoxyethoxystyrene-p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene)
Synthesis of tetrahydrofuran 700 as a solvent in a 2 L flask
ml, sec-butyllithium 7 × 10 ^-3 as an initiator
mol. P-te at −78 ° C.
100 g of rt-butoxystyrene was added and polymerized while stirring for 1 hour. The reaction solution turned red. Further, in order to make the carboxylic acid terminal, the polymerization termination reaction is carried out by adding tert-butyl chloroacetate to 1.4 × 10 ^-2 mo.
1 was added.

Next, the reaction mixture was poured into methanol,
The resulting polymer was precipitated, separated and dried to obtain 99 g of a white polymer (tert-butyl carboxylate-terminated poly p-tert-butoxystyrene). The weight average molecular weight of this polymer was determined by a light scattering method to be 1.
4 × 10 ⁴ g / mol, very monodisperse in terms of molecular weight distribution from the GPC elution curve (Mw / Mn = 1.07)
It was confirmed that the polymer had a high molecular weight.

The above tert-butyl carboxylate-terminated poly p-tert-butoxystyrene (90 g) was mixed with acetone 90
After dissolving in 0 ml, adding a small amount of concentrated hydrochloric acid at 60 ° C. and stirring for 7 hours, the mixture was poured into water to precipitate a polymer, and the polymer was washed and dried to obtain 60 g of a polymer. The weight average molecular weight of the obtained polymer was 1.0 × 10 ⁴ g / mol. Moreover, a peak attributable to tert- butyl group ¹ H-NMR is not observed, 170 ¹³ C-NMR
It was confirmed that the polymer obtained by the presence of C = O in ppm was a carboxylic acid-terminated polyhydroxystyrene having a narrow molecular weight distribution.

The obtained carboxylic acid-terminated polyhydroxystyrene (1,000 g) was mixed with tetrahydrofuran (1,000 m).
After addition of a catalytic amount of p-toluenesulfonic acid, the mixture was stirred at 30 ° C. with ethyl vinyl ether 3
0 g was added. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia and the neutralized reaction solution was added dropwise to 10 L of water to obtain a white solid. After filtering this, acetone 50
It was dissolved in 0 ml, added dropwise to 10 L of water, filtered, and dried under vacuum. From the ¹ H-NMR of the obtained polymer, it was confirmed that the hydrogen atom of the hydroxyl group of the carboxylic acid-terminated polyhydroxystyrene was 27% ethoxyethylated.

Furthermore, 50 g of the obtained partially ethoxyethoxylated carboxylic acid-terminated polyhydroxystyrene was dissolved in 500 ml of pyridine, and 7 g of di-tert-butyl dicarbonate was added with stirring at 45 ° C. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid. After filtration, this was dissolved in 50 ml of acetone, dropped into 2 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer was represented by the following formula Polym. Has a structure represented by 1, ^{1-ethoxyethyl} ratio of the hydrogen atoms of the hydroxyl groups of the H-NMR from carboxylic acid terminated polyhydroxystyrene 27% t-BOC rate is 8%, the weight-average molecular weight (Mw ) And molecular weight distribution (Mw / Mn) were as shown in Table 1.

[Synthesis Example 2] Carboxylic acid-terminated poly (p-1)
Synthesis of -ethoxypropoxystyrene-p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene) The carboxylic acid terminal obtained in the same manner as in Synthesis Example 1 except that the termination reaction in Synthesis Example 1 was changed to CO _2. After dissolving 50 g of polyhydroxystyrene in 500 ml of tetrahydrofuran and adding a catalytic amount of p-toluenesulfonic acid, 27 g of ethoxypropenyl ether was added while stirring at 40 ° C. After reacting for 12 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 10 L of water, whereby a white solid was obtained. After filtration, this was dissolved in 500 ml of acetone, dropped into 10 L of water, filtered, and dried in vacuo. From the ¹ H-NMR of the obtained polymer, it was confirmed that the hydrogen atom of the hydroxyl group of the carboxylic acid-terminated polyhydroxystyrene was ethoxypropylated by 24%.

Further, 50 g of the obtained partially ethoxypropoxylated carboxylic acid-terminated polyhydroxystyrene was dissolved in 500 ml of pyridine, and 8 g of di-tert-butyl dicarbonate was added with stirring at 45 ° C. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid. This is filtered and dissolved in 50 ml of acetone,
The solution was dropped into 2 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer was represented by the following formula Polym. Having a structure represented by 2, the ethoxypropylation rate of the hydrogen atom of the hydroxyl group of the carboxylic acid-terminated polyhydroxystyrene is 24%, and the t-BOC conversion rate is 11% from ¹ H-NMR;
Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Was as shown in Table 1.

[Synthesis Example 3] Alcohol-terminated poly (p-1)
-Ethoxyethoxystyrene-p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene)
Synthesis of tetrahydrofuran 700 as a solvent in a 2 L flask
ml, sec-butyllithium 7 × 10 ^-3 as an initiator
mol. P-te at −78 ° C.
100 g of rt-butoxystyrene was added and polymerized while stirring for 1 hour. The reaction solution turned red. Further, 1.4 × 10 ⁻² mol of ethylene oxide was added to the polymerization solution in order to make an alcohol terminal.

Next, the reaction mixture was poured into methanol,
The resulting polymer was precipitated, separated and dried to obtain 99 g of a white polymer (alcohol-terminated polypt).
tert-butoxystyrene) was obtained. This polymer had a weight average molecular weight of 1.4 × 10 ⁴ g / m by a light scattering method.
ol, and it was confirmed from the GPC elution curve that the polymer was very monodisperse (Mw / Mn = 1.07) in terms of molecular weight distribution.

90 g of the above alcohol-terminated poly p-tert-butoxystyrene was dissolved in 900 ml of acetone.
After adding a small amount of concentrated hydrochloric acid at 60 ° C. and stirring for 7 hours, the mixture was poured into water to precipitate a polymer, which was washed and dried.
g of polymer were obtained. The weight average molecular weight of the obtained polymer was 1.0 × 10 ⁴ g / mol. In addition, ¹ H
That no peak derived from a tert-butyl group was observed in ¹ -NMR, and 4.17 to 4.28 pp in ¹ H-NMR.
m, ¹³ C-NMR confirmed that the polymer obtained due to the presence of 58 ppm of CH ₂ —OH was an alcohol-terminated polyhydroxystyrene having a narrow molecular weight distribution.

100 g of the obtained alcohol-terminated polyhydroxystyrene was added to 1,000 ml of dimethylformamide.
And a catalytic amount of pyridinium p-toluenesulfonate was added, and then 30 g of ethyl vinyl ether was added while stirring at 30 ° C. After reacting for 16 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 10 L of water to obtain a white solid. After filtration, this was dissolved in 500 ml of acetone, dropped into 10 L of water, filtered, and dried in vacuo. The resulting polymer has ¹ H
From -NMR, it was confirmed that the hydrogen atom of the hydroxyl group of the alcohol-terminated polyhydroxystyrene was ethoxyethylated by 27%.

Further, 50 g of the obtained partially ethoxyethoxylated alcohol-terminated polyhydroxystyrene was dissolved in 500 ml of pyridine, and 7 g of di-tert-butyl dicarbonate was added with stirring at 45 ° C. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid. After filtration, this was dissolved in 50 ml of acetone, dropped into 2 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer was represented by the following formula Polym. Has a structure represented by 3, ethoxyethyl rate of the hydrogen atom of the hydroxyl group of alcohol-terminated polyhydroxystyrene from ¹ H-NMR is 27% t-BOC rate is 8%, weight average molecular weight (Mw) And the molecular weight distribution (Mw / Mn) was as shown in Table 1.

[Synthesis Example 4] Triphenyl-terminated poly (p-
Synthesis of 1-ethoxypropoxystyrene-p-hydroxystyrene) In a 2 L flask, tetrahydrofuran 1,0
00 ml, sec-butyllithium 2.4 as initiator
× 10 ^-2 mol was charged. 300 g of p-tert-butoxystyrene was added to this mixed solution at -78 ° C, and 1
The polymerization was carried out with stirring for an hour. The reaction solution turned red. Furthermore, in order to make the terminal triphenyl, a polymerization termination reaction is performed by adding triphenylmethyl chloride 3.0 to the reaction solution.
× 10 ^-2 mol was added.

Next, the reaction mixture was poured into methanol,
The resulting polymer was precipitated, separated and dried to give 298 g of a white polymer (triphenyl-terminated polyp).
-Tert-butoxystyrene) was obtained. This polymer had a weight average molecular weight of 1.4 × 10 ⁴ g by a light scattering method.
/ Mol, and it was confirmed from a GPC elution curve that the polymer was very high in monodispersity (Mw / Mn = 1.10) in terms of molecular weight distribution.

The above triphenyl-terminated poly p-tert-
Dissolve 190 g of butoxystyrene in 1,000 ml of acetone, add a small amount of concentrated hydrochloric acid at 60 ° C and stir for 7 hours.
Poured into water to precipitate the polymer, washed and dried to obtain 125 g of polymer. The weight average molecular weight of the obtained polymer was 9,500 g / mol. Further, ¹ H-NMR with tert- not observed a peak derived from a butyl group, confirmed that the polymer obtained by the presence of triphenyl at ¹ H-NMR is narrow triphenyl-terminated polyhydroxystyrene having a molecular weight distribution Was done.

100 g of triphenyl-terminated polyhydroxystyrene obtained in a 2 L flask was dissolved in 700 ml of tetrahydrofuran, a catalytic amount of methanesulfonic acid was added, and then 25 g of ethoxypropenyl ether was added with stirring at 20 ° C. After reacting for 2 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 10 L of water to obtain a white solid. After filtration, this was dissolved in 500 ml of acetone, dropped into 10 L of water, filtered, and dried in vacuo. The resulting polymer has the following chemical formula P
olym. ¹ H-NMR confirmed that 26% of the hydrogen atoms of the hydroxyl groups of the triphenyl-terminated polyhydroxystyrene were ethoxypropylated. Weight average molecular weight (Mw) and molecular weight distribution (Mw /
Mn) was as shown in Table 1.

[Synthesis Example 5] Synthesis of poly (p-1-ethoxypropoxystyrene-p-hydroxystyrene) terminated with alcohol carboxylic acid In a 2 L flask, tetrahydrofuran 2,0 was used as a solvent.
00 ml, sodium naphthalene 1.3 × as initiator
10 ^-2 mol was charged. The mixed solution is added at -78 ° C with p.
200 g of -tert-butoxystyrene was added and polymerized while stirring for 1 hour. The reaction solution turned red. Further, in order to terminate the carboxylic acid, the polymerization termination reaction was performed by adding 1.5 × 10 ⁻² mol of carbon dioxide dissolved in tetrahydrofuran to the reaction solution. On the other hand, in order to make the terminal of the hydroxyl group, the polymerization termination reaction is performed by adding 1 × 10 ⁻² m of trimethoxyborane dissolved in tetrahydrofuran to the reaction solution.
After adding and reacting, acetic acid 1 × 10 ^-2 mol,
1.5 × 10 ⁻² mol of aqueous hydrogen peroxide was added.

Next, the reaction mixture was poured into methanol,
The resulting polymer was precipitated, separated and dried to obtain 198 g of a white polymer (alcohol-carboxylic acid-terminated poly p-tert-butoxystyrene).
This polymer had a weight average molecular weight of 1.6 × by light scattering.
It was 10 ⁴ g / mol, and it was confirmed from the GPC elution curve that the polymer was very high in monodispersity (Mw / Mn = 1.05) in terms of molecular weight distribution.

The alcohol carboxylic acid-terminated polypt
ert-butoxystyrene 190 g in acetone 1,00
After dissolving in 0 ml, adding a small amount of concentrated hydrochloric acid at 60 ° C. and stirring for 7 hours, the mixture was poured into water to precipitate a polymer, and the polymer was washed and dried to obtain 125 g of a polymer. The weight average molecular weight of the obtained polymer was 9,500 g / mol. Further, ¹ peak attributable to tert- butyl group H-NMR is not observed, the presence of C = O of 170ppm at ¹³ C-NMR, also 4.17～ in ¹ H-NMR
4.28 ppm, 58 ppm of CH ₂ -by ¹³ C-NMR
It was confirmed that the polymer obtained by the presence of OH was an alcohol carboxylic acid-terminated polyhydroxystyrene having a narrow molecular weight distribution.

100 g of the obtained alcohol-carboxylic acid-terminated polyhydroxystyrene was dissolved in 700 ml of tetrahydrofuran, and a catalytic amount of methanesulfonic acid was added. After stirring at 20 ° C., 30 g of ethoxypropenyl ether was added. After reacting for 2 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 10 L of water to obtain a white solid. After filtration, this was dissolved in 500 ml of acetone, dropped into 10 L of water, filtered, and dried in vacuo. The obtained polymer was represented by the following formula Polym. Has a structure represented by 5, ¹ H-N
From MR, it was confirmed that the hydrogen atom of the hydroxyl group of the alcohol-carboxylic acid-terminated polyhydroxystyrene was 28% ethoxypropylated. The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were as shown in Table 1.

[Synthesis Example 6] Carboxylic acid ester-terminated triethylene glycol divinyl ether cross-linked poly (p-
Synthesis of 1-ethoxyethoxystyrene-p-hydroxystyrene) In a 2 L flask, tetrahydrofuran 1,0
00 ml, sec-butyllithium 1.6 as initiator
× 10 ^-2 mol was charged. 200 g of p-tert-butoxystyrene was added to this mixed solution at -78 ° C, and 1
The polymerization was carried out with stirring for an hour. The reaction solution turned red. Further, in order to make the carboxylic acid ester terminal, the polymerization termination reaction is carried out by adding 1.4 × 10 4 ethyl chlorocarbonate to the reaction solution.
^The reaction was performed by adding ^-2 mol.

Next, the reaction mixture was poured into methanol,
After the obtained polymer was precipitated, separated and dried, 198 g of a white polymer (carboxylate-terminated poly p-tert-butoxystyrene) was obtained. This polymer had a weight average molecular weight of 1.2 × 1 by a light scattering method.
0 is ⁴ g / mol, was confirmed to be a polymer having a high point in very monodisperse molecular weight distribution by the GPC elution curve (Mw / Mn = 1.03).

The above carboxylic acid ester-terminated poly p-te
190 g of rt-butoxystyrene in 900 ml of acetone
Was added at 60 ° C., a small amount of concentrated hydrochloric acid was added, and the mixture was stirred for 7 hours, then poured into water to precipitate a polymer, and washed and dried to obtain 60 g of a polymer. The weight average molecular weight of the obtained polymer was 8,500 g / mol. In addition, no peak derived from a tert-butyl group was observed in ¹ H-NMR, and a polymer obtained by the presence of 170 ppm of C ＝ O in ¹³ C-NMR was a carboxylate-terminated polyhydroxystyrene having a narrow molecular weight distribution. It was confirmed that there was.

100 g of the obtained carboxylic acid ester-terminated polyhydroxystyrene was placed in a 2 L flask, dissolved in 1,000 ml of dimethylformamide, and a catalytic amount of p-toluenesulfonic acid was added. After adding 4 g of ethylene glycol divinyl ether and reacting for 1 hour, ethyl vinyl ether 2 was added.
2 g and 4 g of triethylene glycol 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 10 L of water to obtain a white solid. After filtration, 500 ml of acetone
, And added dropwise to 10 L of water, filtered, and dried in vacuo. The obtained polymer was represented by the following formula Polym. It has a structure represented by 6, and it was confirmed from ¹ H-NMR that the hydrogen atom of the hydroxyl group of the carboxylic acid ester-terminated polyhydroxystyrene was 30% ethoxyethylated and 3% was crosslinked, and the weight average molecular weight was As shown in Table 1.

[Synthesis Example 7] Synthesis of poly (p-1-ethoxyethoxystyrene-p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene) crosslinked with alcohol-terminated 1,4-divinyloxymethylcyclohexane 2 L flask And tetrahydrofuran 3,0 as a solvent
00 ml, sec-butyllithium 2.1 as an initiator
× 10 ^-3 mol was charged. 300 g of p-tert-butoxystyrene was added to this mixed solution at -78 ° C, and 1
The polymerization was carried out with stirring for an hour. The reaction solution turned red. Further, in order to make the terminal of the alcohol, the polymerization termination reaction is carried out by adding 1.0 × 10 ^-1 mol of ethylene oxide to the reaction solution.
1 was added.

Next, the reaction mixture was poured into methanol,
The resulting polymer was precipitated, separated and dried to obtain 295 g of a white polymer (alcohol-terminated poly p-
tert-butoxystyrene) was obtained. This polymer had a weight average molecular weight of 1.4 × 10 ⁴ g / by a light scattering method.
mol, and it was confirmed from the GPC elution curve that the polymer was very highly monodisperse (Mw / Mn = 1.05) in terms of molecular weight distribution.

200 g of the above-mentioned alcohol-terminated poly-p-tert-butoxystyrene was dissolved in 2,000 ml of acetone, a small amount of concentrated hydrochloric acid was added at 60 ° C., and the mixture was stirred for 7 hours, poured into water to precipitate a polymer, and washed and dried. After doing
130 g of polymer were obtained. The weight average molecular weight of the obtained polymer was 1.0 × 10 ⁴ g / mol. Moreover, a peak attributable to tert- butyl group ¹ H-NMR is not observed, from 4.17 to 4 in ¹ H-NMR.
28 ppm, 58 ppm CH ₂ —OH by ¹³ C-NMR
It was confirmed that the obtained polymer was an alcohol-terminated polyhydroxystyrene having a narrow molecular weight distribution.

Alcohol end obtained in 2 L flask
Add 100 g of polyhydroxystyrene and add
Dissolved in 1,000 ml of muamide and a catalytic amount of p-torr.
After adding the enesulfonic acid, stir at 20 ° C.
15 g of tyl vinyl ether, 1,4-divinyloxymethi
9 g of lecyclohexane were added. After reacting for 1 hour
, Neutralized with concentrated aqueous ammonia and neutralized with 10 L of water
When the liquid was dropped, a white solid was obtained. Filter this
Then, it is dissolved in 500 ml of acetone and dropped into 10 L of water.
After filtration, the resultant was dried under vacuum. The resulting polymer is¹H
-NMR and¹³C -NMR to alcohol-terminated polyhydrido
18% of hydrogen atoms in hydroxyl groups of roxystyrene are ethoxylated
It was confirmed that the product was chilled and 4% was crosslinked.

Furthermore, the obtained partially crosslinked alcohol-terminated ethoxyethoxylated polyhydroxystyrene 50
g was dissolved in 500 ml of pyridine, and 12 g of di-tert-butyl dicarbonate was added while stirring at 45 ° C. 1
After reacting for an hour, the reaction solution was dropped into 3 L of water.
A white solid was obtained. After filtration, acetone 50 ml
, And added dropwise to 2 L of water, filtered, and dried in vacuum.
A polymer was obtained. The resulting polymer has the following formula Pol
ym. 1H-NMR shows that the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of the alcohol-terminated polyhydroxystyrene is 18%, the crosslinking rate is 4%, and the tert-butoxycarbonylation rate of the hydrogen atom of the hydroxyl group is ¹ H-NMR. Is 10
%, And the weight average molecular weight was as shown in Table 1.

[Synthesis Example 8] Carboxylic acid terminal 1,2-ethane
Diol divinyl ether cross-linked poly (p-1-ethoxy)
(Ethoxyethoxystyrene-p-hydroxystyrene)
Synthesis The termination reaction of Synthesis Example 1 was CO_TwoSynthetic except that
Carboxylic acid-terminated polyhydroxy obtained in the same manner as in Example 1.
200 g of styrene to 2,000 m of tetrahydrofuran
and added 4 g of methanesulfonic acid.
While stirring at 0 ° C., 2-chloro-2-ethoxyethyl 4
4 g was added and reacted for 3 hours. Next,
10 g of tandiol divinyl ether was added, and 0.5 g
After reacting for an hour, the mixture was neutralized with concentrated aqueous ammonia. This
Solvent exchange of the reaction solution with ethyl acetate, pure water and a small amount of
After performing liquid separation purification 6 times using a ton, solvent exchange with acetone was performed.
When the solution was dropped into 20 L of pure water, a white solid was obtained.
Was. This is filtered, washed twice with pure water, filtered, and dried under vacuum.
Dried. The obtained polymer was represented by the following formula Polym. 8
Having a structure represented by¹H-NMR and¹³C -NMR
From the carboxylic acid-terminated polyhydroxystyrene
20% of the hydrogen atoms are ethoxyethylated and 4% are crosslinked.
20% of the carboxylic acid ends are ethoxyethylated,
The weight average molecular weight was as shown in Table 1.

[Synthesis Example 9] Alcohol-terminated 1,4-dimethylcyclohexyldichloroethyl ether cross-linked poly (p-1-ethoxypropoxystyrene-p-tert)
Synthesis of -butoxycarbonyloxystyrene-p-hydroxystyrene) In a 2 L flask, tetrahydrofuran 1,0
00 ml, sec-butyl lithium 5 × 1 as an initiator
0 ^-3 mol was charged. P- at -78 ° C.
100 g of tert-butoxystyrene was added and polymerized while stirring for 1 hour. The reaction solution turned red. Further, 5 × 10 ⁻² mol of ethylene oxide was added to the polymerization solution in order to make the alcohol terminal.

Next, the reaction mixture was poured into methanol,
The resulting polymer was precipitated, separated and dried to obtain 99 g of a white polymer (alcohol-terminated polypt).
tert-butoxystyrene) was obtained. This polymer had a weight average molecular weight of 1.9 × 10 ⁴ g / m by a light scattering method.
ol, and it was confirmed from the GPC elution curve that the polymer had a very high monodispersity (Mw / Mn = 1.09) in terms of molecular weight distribution.

90 g of the above-mentioned alcohol-terminated poly p-tert-butoxystyrene was dissolved in 1,000 ml of acetone, a small amount of concentrated hydrochloric acid was added at 60 ° C., the mixture was stirred for 7 hours, poured into water to precipitate a polymer, and washed and dried. After doing, 6
0 g of the polymer was obtained. The weight average molecular weight of the obtained polymer was 1.0 × 10 ⁴ g / mol. Also ¹
No peak derived from the tert-butyl group was observed in ¹ H-NMR, and 4.17 to 4.28 p in ¹ H-NMR.
pm, ¹³ C-NMR confirmed that the obtained polymer was alcohol-terminated polyhydroxystyrene having a narrow molecular weight distribution due to the presence of 58 ppm of CH ₂ —OH.

50 g of the obtained alcohol-terminated polyhydroxystyrene was placed in a 2 L flask, dissolved in 1,000 ml of tetrahydrofuran, and methanesulfonic acid was added.
After the addition of 9 g, 2-chloro-
After adding 9 g of 2-ethoxypropyl and reacting for 3 hours, 4 g of 1,4-dimethylcyclohexyldichloroethyl ether was added. After reacting for 0.5 hour, the mixture was neutralized with concentrated aqueous ammonia. This reaction solution was solvent-exchanged to ethyl acetate, purified by liquid separation and purification six times using pure water and a small amount of acetone, and then solvent-exchanged to acetone and dropped into 20 L of pure water to obtain a white solid. After filtering this,
After washing twice with pure water, filtration and vacuum drying.

Further, the obtained partially crosslinked alcohol
Ethoxy propoxylated polyhydroxystyrene 5
0 g in 300 g of pyridine and stir at 40 ° C.
4 g of di-tert-butyl dicarbonate were added. 1 o'clock
After the reaction, the reaction solution was dropped into 10 L of water.
A white solid was obtained. After filtering this, acetone 200m
and then added dropwise to 2 L of water, filtered, and dried in vacuum.
To obtain a polymer. The resulting polymer has the following chemical formula P
olym. Has a structure shown by 9,¹H-NMR and
¹³C -NMR from alcohol-terminated polyhydroxystyrene
19% of the hydrogen atoms in the hydroxyl groups of ethoxy
Tert-butoxycarbonylation, 4%
Is cross-linked and 19% of the alcohol ends are ethoxypro
It was confirmed that 4% had been cross-linked,
The weight average molecular weight was as shown in Table 1.

Synthesis Example 10 Carboxylic Acid Both Terminals 1,4-
Butanediol divinyl ether cross-linked poly (p-1-
Synthesis of ethoxyethoxystyrene-p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene) In a 2 L flask, tetrahydrofuran 2,0
00ml, Naphthalene sodium 3 as both terminal initiator
× 10 ^-3 mol was charged. 100 g of p-tert-butoxystyrene was added to this mixed solution at -78 ° C, and 1
The polymerization was carried out with stirring for an hour. The reaction solution turned red. Further, in order to make both terminals of the carboxylic acid, the polymerization termination reaction was carried out by adding 2 × 10 ^-1 mol of carbon dioxide dissolved in tetrahydrofuran to the reaction solution.

Next, the reaction mixture was poured into methanol,
The resulting polymer was precipitated, separated, and dried to obtain 99 g of a white polymer (carboxylic acid-terminated poly-p-terminal).
tert-butoxystyrene) was obtained. This polymer had a weight average molecular weight of 1.5 × 10 ⁴ g / by a light scattering method.
mol, and it was confirmed from the GPC elution curve that the polymer was very monodisperse (Mw / Mn = 1.15) in terms of molecular weight distribution.

The above carboxylic acid at both ends poly p-tert-
90 g of butoxystyrene was dissolved in 900 ml of acetone, a small amount of concentrated hydrochloric acid was added at 60 ° C., and the mixture was stirred for 7 hours, poured into water to precipitate a polymer, and washed and dried.
0 g of the polymer was obtained. The weight average molecular weight of the obtained polymer was 1.0 × 10 ⁴ g / mol. Also ¹
No peak derived from a tert-butyl group was observed in H-NMR, and 170 ppm C =
It was confirmed that the polymer obtained by the presence of O was polyhydroxystyrene having carboxylic acid at both ends with a narrow molecular weight distribution.

A 2-L flask was charged with 90 g of the obtained polyhydroxystyrene having carboxylic acid at both ends and dissolved in 1,000 ml of tetrahydrofuran.
g of 2-chloro-2 while stirring at 30 ° C.
-21 g of ethoxyethyl was added and reacted for 1 hour.
Then, 7 g of 1,4-butanediol divinyl ether
Was added and reacted for 0.5 hour, and then neutralized with concentrated aqueous ammonia. Solvent exchange of this reaction solution to ethyl acetate,
After separating and purifying 6 times with pure water, the solvent was exchanged with acetone and
When dropped into 0 L of pure water, a white solid was obtained. This was filtered, washed twice with pure water, filtered, and vacuum dried.

Furthermore, the obtained partially ethoxyethoxylated
50 g of polyhydroxystyrene at both ends of rubonic acid
Dissolved in 500 ml of dicarbonate and stirred at 45 ° C.
7 g of di-tert-butyl were added. Let react for 1 hour
After that, when the reaction solution was dropped into 3 L of water, a white solid was obtained.
Was done. This is filtered and dissolved in 50 ml of acetone,
It was dropped into 2 L of water, filtered, and dried under vacuum to obtain a polymer.
Was. The obtained polymer was represented by the following formula Polym. At ten
Having the structure shown,¹H-NMR and¹³C -NMR or
Of the hydroxyl groups of the carboxylic acid terminal hydroxypolystyrene
25% of hydrogen atoms are ethoxyethylated, 5% is BOC
5.5% cross-linked, one end of carboxylic acid and both ends
It was confirmed that the ends were totally 25% ethoxyethylated.
The weight average molecular weight was as shown in Table 1.

[Synthesis Example 11] Synthesis of hydroxyl-terminated propylene glycol divinyl ether crosslinked poly (pn-butoxyethoxystyrene-p-hydroxystyrene) In a 2 L flask, tetrahydrofuran 3,0 was used as a solvent.
00 ml and 1 × 10 ^-2 mol of sec-butyllithium were charged as both terminal initiators. -78 ° C
Add 200 g of p-tert-butoxystyrene with
The polymerization was carried out with stirring for 1 hour. The reaction solution turned red. Further, in order to terminate the hydroxyl group, the polymerization termination reaction is performed by adding 1 × 10 ⁻² mol of trimethoxyborane dissolved in tetrahydrofuran to the reaction solution and reacting, and then adding 1 × 10 ⁻² mol of acetic acid and an aqueous solution of hydrogen peroxide. 1.5 × 10 ^-2 mo
1 was added.

Next, the reaction mixture was poured into methanol,
After the obtained polymer was precipitated, separated and dried, 198 g of a white polymer (hydroxy-terminated poly p-te) was obtained.
rt-butoxystyrene) was obtained. This polymer had a weight average molecular weight of 2.1 × 10 ⁴ g / mo by a light scattering method.
1 and it was confirmed from the GPC elution curve that the polymer had a very high monodispersity (Mw / Mn = 1.16) in terms of molecular weight distribution.

The above hydroxyl-terminated poly p-tert-butoxystyrene (150 g) was dissolved in acetone (900 ml).
At 0 ° C., a small amount of concentrated hydrochloric acid was added, and the mixture was stirred for 7 hours and poured into water.
After precipitating the polymer, washing and drying, 100 g
Was obtained. The weight average molecular weight of the obtained polymer was 1.4 × 10 ⁴ g / mol. Also, ¹ H−
No peak derived from the tert-butyl group was observed in NMR, and 4.17 to 4.28 pp in ¹ H-NMR.
m, ¹³ C-NMR confirmed that the obtained polymer was a hydroxyl-terminated polyhydroxystyrene having a narrow molecular weight distribution due to the presence of 58 ppm of CH ₂ —OH.

The hydroxyl-terminated poly obtained in a 2 L flask was used.
Add 90 g of hydroxystyrene and add tetrahydrofuran
Dissolve in 1,000 ml and add 1 g of methanesulfonic acid
After the addition, the mixture was stirred at 30 ° C with 2-chloro-2-ethoxy.
21 g of xybutyl was added and reacted for 1 hour. Next
Add 7 g of propylene glycol divinyl ether
And after reacting for 1 hour, neutralize with concentrated aqueous ammonia
Was. This reaction solution was solvent-exchanged with ethyl acetate, and pure water was used six times.
After separation and purification, the solvent was exchanged with acetone, and 20 L of pure water was used.
, A white solid was obtained. Filter this
After that, it was washed twice with pure water, filtered and dried in vacuum.
I got The obtained polymer was represented by the following formula Polym. 1
Having the structure shown by 1,¹H-NMR and¹³C -NM
From R to hydroxyl group-terminated polyhydroxystyrene water
25% of the atoms are butoxyethylated and 5.5% are bridged
Bridged and 6% of hydroxyl groups were butoxyethylated
And the weight average molecular weight is as shown in Table 1.
Was.

[Synthesis Example 12] 1,4-buta, both ends of hydroxyl group
Divinyl divinyl ether cross-linked poly (pn-but
(Ethoxyethoxystyrene-p-hydroxystyrene)
Synthesis The termination reaction of Synthesis Example 10 was chloromethyl vinyl ether.
Water obtained in the same manner as in Synthesis Example 10 except that
200 g of polyhydroxystyrene having both terminal acid groups
Dissolve in 2,000 ml of drofuran and add methanesulfone
After the addition of 4 g of acid, 2-chloro
44 g of 2-ethoxybutyl was added and reacted for 3 hours.
Was. Then, 1,4-butanediol divinyl ether
After adding 10 g and reacting for 0.5 hour, concentrated ammonia was added.
A. Neutralized with water. This reaction solution was solvent-exchanged with ethyl acetate.
And then purify 6 times using pure water and a small amount of acetone.
After that, the solvent was exchanged with acetone and dropped into 20 L of pure water.
However, a white solid was obtained. This is filtered and then purified with pure water.
After washing, filtering and drying in vacuo. The resulting polymer is below
Indicative formula Polym. Having a structure shown by 12,¹H
--- NMR and¹³C -Hydroxy-terminated polyhydrido from NMR
20% of hydrogen atoms in hydroxyl groups of roxystyrene are butoxy
Toxified, 4% cross-linked, one end of hydroxyl group and both ends
Confirmed that a total of 20% of the terminals were butoxyethylated
The weight average molecular weight was as shown in Table 1.

The structure of the obtained polymer was as shown by the following descriptive formula, and the substitution ratio of each was as shown in Table 1. In the following formula, R represents a cross-linking group that cross-links the following unit U between molecules or within a molecule, and (R) is a cross-linking group R
Indicates a state in which are connected.

[0297]

Embedded image

[0298]

Embedded image

[0299]

Embedded image

[0300]

Embedded image

[0301]

Embedded image

[0302]

Embedded image

[0303]

Embedded image

[0304]

Embedded image

[0305]

Embedded image

[0306]

[Table 1]

[Examples] The polymer compound (Polyms. 1 to 12) obtained in the above synthesis example was used as a base resin, an acid generator represented by the following formula (PAG. 1 to 10), and an acid generator represented by the following formula (D)
RR. A dissolution controlling agent represented by 1, 2), a basic compound,
In the molecule represented by the following formula (ACC.
A resist material component selected from aromatic compounds having a group represented by OOH was dissolved in a solvent, and a resist solution having a composition shown in Tables 2 and 3 was prepared. If necessary, use the surfactant Florad “FC-430 (Sumitomo 3M Limited)
Manufactured) was added to improve the film formability.

Each of these compositions was filtered through a 0.1 μm Teflon filter to prepare a resist solution. This was spin-coated on a silicon wafer, and the silicon wafer was baked on a hot plate at 100 ° C. for 90 seconds. In addition, the film thickness was set to 0.55 μm.

Then, exposure was performed by using an excimer laser stepper (Nikon Corporation, NSR-2005EX NA = 0.5) through a mask for forming a target pattern, and baked at 110 ° C. for 90 seconds. 60% aqueous solution of 38% tetramethylammonium hydroxide
After developing for 2 seconds, a positive pattern could be obtained.

[0310] The obtained resist pattern was evaluated as follows. First, the sensitivity (Eth) was determined. Then 0.24
μm line and space top and bottom 1: 1
And the minimum line width of the separated line and space at this exposure amount was taken as the resolution of the evaluation resist. The resolution was also observed when the time lapse (PED) from the exposure at the same exposure amount to the heat treatment was 2 hours. The shape of the resolved resist pattern was observed using a scanning electron microscope.
Heating was performed on a hot plate at 0 ° C. for 10 minutes, and a change in pattern shape before and after heating was observed.

Tables 2 and 3 show the resist compositions, and Table 4 shows the evaluation results of the examples.

[0312]

Embedded image

[0313]

Embedded image

[0314]

Embedded image

[0315]

Embedded image

[0316]

[Table 2]

[0317]

[Table 3] PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate TEA: Triethanolamine PEA: Piperidineethanolamine TMMEA: Tris {2- (methoxymethoxy) ethyl} amine TMMEA: Tris [2-{(2-methoxyethoxy) methoxy} ethyl Amine

[0318]

[Table 4] Heat resistance ○: No change in pattern shape before and after heating

Next, in the resist compositions of Examples 6, 7, 8 and 9 described above, an acetylene alcohol derivative, Olfin E1004 (manufactured by Nissin Chemical Industry Co., Ltd.)
Was added so as to be 0.05% by weight of the whole, and the storage stability with respect to the increase of particles (foreign matter) was observed. Table 5 shows the results. At this time, KL-20A (manufactured by Rion Co., Ltd.) was used as a submerged particle counter, and a particle size of 0.3 μm or more was monitored in an accelerated test by storage at 40 ° C.

[0320]

Embedded image

[0321]

[Table 5]

Continuing from the front page (72) Inventor Takanobu Takeda 28-1 Nishifukushima, Oku-ku, Nakakushiro-gun, Niigata Pref. Shin-Etsu Chemical Co., Ltd.

Claims (12)

[Claims] 1. A polymer compound having a weight average molecular weight of 1,000 to 500,000 represented by the following general formula (1) and having a terminal represented by the following P: Embedded image [Wherein, R represents a hydroxyl group or an OR ³ group, at least one of which is a hydroxyl group. R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear, branched, or R ³ represents an acid labile group, and represents a cyclic alkyl group.
Is 0 or a positive integer, y is a positive integer, a number satisfying x + y ≦ 5, k is 0 or a positive integer, m is 0 or a positive integer, n is a positive integer, and k + m + n It is a number that satisfies ≦ 5. p and q are positive numbers, 0 <q ≦ 0.8, p
It is a number that satisfies + q = 1. When n is 2 or more, R ³ may be the same or different.
Δ is a number that makes the weight average molecular weight 1,000 to 500,000. P is a hydrogen atom, a straight chain having 1 to 30 carbon atoms,
A branched or cyclic alkyl or alkenyl group, an aromatic hydrocarbon group having 6 to 50 carbon atoms, a carboxyl group, a hydroxyl group, or a group represented by the following general formula (2), (3) or (4) And all of the terminals cannot be hydrogen atoms at the same time. ) (Wherein, R ⁴ is an (r + 1) -valent aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic saturated hydrocarbon group or 6 to 50 carbon atoms.
R ⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 50 carbon atoms, an alkoxy group having 1 to 30 carbon atoms Or a hydroxyl group, and R ^5a represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 50 carbon atoms. H is 0 or 1, and r is 1 to
Indicates a positive integer of 3. In addition, any one or two of the phenolic hydroxyl group represented by R of the polymer compound represented by the general formula (1), the hydroxyl group represented by R ⁵ in the general formula (2), and the hydroxyl group represented by the general formula (3) The above hydroxyl group may be cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a C—O—C group obtained by reaction with an alkenyl ether compound or a halogenated alkyl ether compound. The total amount of the phenolic hydroxyl group of the formula (1), the hydroxyl group of R ⁵ in the general formula (2) and the total hydrogen atom of the hydroxyl group in the general formula (3) is more than 0 mol%. The ratio is not more than mol%. ] 2. The polymer compound according to claim 1, represented by the following general formula (5). Embedded image [Wherein, R represents a hydroxyl group or an OR ³ group, at least one of which is a hydroxyl group. R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear, branched, or R ³ represents an acid labile group, and R ⁹ and R ¹⁰ represent a cyclic alkyl group.
Represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ¹¹ represents a monovalent hydrocarbon group which may have a heteroatom having 1 to 18 carbon atoms. , R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , R ¹⁰ and R ¹¹ may form a ring, and when forming a ring, R ⁹ , R ¹⁰ , and R ¹¹ each have 1 to 18 carbon atoms. Represents a linear or branched alkylene group. R ¹² is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms,
An oxoalkyl group having 4 to 20 carbon atoms or —CR ⁹ R ¹⁰ O
It represents a group represented by R ^11. a is an integer of 0 to 6. Also, p1 and p2 are positive numbers, q1 and q2 are 0 or positive numbers, and 0 <p1 / (p1 + q1 + q2 + p2) ≦ 0.8,
0 ≦ q1 / (p1 + q1 + q2 + p2) ≦ 0.8, 0 ≦
q2 / (p1 + q1 + q2 + p2) ≦ 0.8, p1 + q
1 + q2 + p2 = 1, but q1 and q2
Do not become 0 at the same time. x, y, k, m, n,
Δ and P have the same meanings as above. In addition, any one or two of the phenolic hydroxyl group represented by R of the polymer compound represented by the general formula (5), the hydroxyl group represented by R ⁵ in the general formula (2), and the hydroxyl group represented by the general formula (3) Even if a hydrogen atom of the above hydroxyl group is removed and its oxygen atom is cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a C—O—C group represented by the following general formula (6a) or (6b) The total amount of the acid labile group and the crosslinking group is preferably the phenolic hydroxyl group represented by R in the polymer compound of the formula (5), the hydroxyl group of R ⁵ in the above formula (2) and the above formula (3) The ratio is more than 0 mol% and not more than 80 mol% of the average of all the hydrogen atoms of the hydroxyl group in the above. Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ⁷ each represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear alkylene group having 1 to 10 carbon atoms;
Represents a branched or cyclic alkylene group, d is 0 or 1
It is an integer of 10. A represents a c-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; A part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. B is -CO-O
—, —NHCO—O— or —NHCONH—. c
Is an integer of 2 to 8, and c 'is an integer of 1 to 7. )] 3. The polymer compound represented by the general formula (1) or (5), wherein R ³ is a group represented by the following general formula (7) or (8), and a tertiary alkyl having 4 to 20 carbon atoms. The polymer compound according to claim 1, wherein each of the groups and each alkyl group is one or more selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms. Embedded image (Wherein R ⁹ and R ¹⁰ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ¹¹ may have a heteroatom having 1 to 18 carbon atoms. R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , R ¹⁰ and R ¹¹ may form a ring, and when forming a ring, R ⁹ and R ¹⁰ ,
R ¹¹ represents a linear or branched alkylene group having 1 to 18 carbon atoms. R ¹² is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above general formula (7). Is shown. a is an integer of 0 to 6. ) 4. The crosslinking group having a C—O—C group represented by the general formula (6a) or (6b) is represented by the following general formula (6a ′)
Or the polymer compound according to claim 2, which is represented by (6b '). Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ^{7 each} represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, d is 0 or an integer of 1 to 5. A is a c ''-valent linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, Represents an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed, and a part of the hydrogen atoms bonded to the carbon atom is substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c '' is 2 to 4,
c ″ ′ is an integer of 1 to 3. ) 5. An organic solvent according to claim 1, wherein (A) is an organic solvent and (B) is a base resin.
4. A chemically amplified positive resist composition comprising the polymer compound (C): an acid generator. 6. A polymer having a repeating unit represented by the following general formula (9) as a base resin different from the component (D) :( B), wherein one or two hydrogen atoms of a phenolic hydroxyl group are contained. 6. A high molecular weight compound having a weight average molecular weight of 3,000 to 300,000 partially substituted by a total of at least 0 mol% and not more than 80 mol% as a whole with at least one kind of acid labile group. The polymer compound as described in the above. Embedded image [Wherein, R ¹ , R ² , R ⁹ , R ¹⁰ , and R ¹¹ have the same meanings as described above, and R ¹² is an acid labile group different from —CR ⁹ R ¹⁰ OR ¹¹ ; f is 0 or a positive number, g is a positive number, and e +
f + g = 1, 0 ≦ e / (e + f + g) ≦ 0.5,
0.4 ≦ g / (e + f + g) ≦ 0.9. In addition, the phenolic hydroxyl group of the polymer compound represented by the above general formula (9) is obtained by reacting a phenolic hydroxyl group with an alkenyl ether compound or a halogenated alkyl ether.
It may be cross-linked intramolecularly and / or intermolecularly by a cross-linking group having a -OC group. In the formula (9), the total amount of the acid labile group and the cross-linking group is e = 0, f = 0, g = 1
In this case, the ratio is more than 0 mol% and not more than 80 mol% on the average of all hydrogen atoms of the phenolic hydroxyl group. ] 7. The chemically amplified positive resist material according to claim 5, further comprising (E) a dissolution controlling agent. 8. The chemically amplified positive resist material according to claim 5, further comprising (F) a basic compound as an additive. 9. (G): In the molecule as an additive
9. The chemically amplified positive resist composition according to claim 5, further comprising an aromatic compound having a group represented by C-COOH. 10. The chemically amplified positive resist material according to claim 5, further comprising (H) an ultraviolet absorber. 11. The chemically amplified positive resist material according to claim 5, further comprising (I): an acetylene alcohol derivative. (I) any one of claims 5 to 11
(Ii) a step of applying a chemically amplified positive resist material as described in the above to a substrate, and (ii) exposing with a high-energy ray or an electron beam having a wavelength of 300 nm or less through a photomask after a heat treatment; And b.) Performing a heat treatment as needed, and then developing with a developing solution.