JP7125476B2 - Actinic ray- or radiation-sensitive resin composition, actinic ray- or radiation-sensitive film, pattern forming method, and electronic device manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, an electronic device manufacturing method, and a polyester.

Since the resist for KrF excimer laser (248 nm), a pattern forming method using chemical amplification has been used in order to compensate for the sensitivity reduction due to light absorption. For example, in a positive chemical amplification method, first, a photoacid generator contained in an exposed area is decomposed by light irradiation to generate an acid. Then, in a post-exposure bake (PEB: Post Exposure Bake) process or the like, the alkali-insoluble groups contained in the photosensitive composition are converted into alkali-soluble groups by the catalytic action of the generated acid. After that, development is performed using, for example, an alkaline solution. Thereby, the exposed portion is removed to obtain a desired pattern.
In the above method, various alkaline developers have been proposed. For example, a water-based alkaline developer containing 2.38 mass % TMAH (tetramethylammonium hydroxide aqueous solution) is commonly used as the alkaline developer.

For the miniaturization of semiconductor devices, the wavelength of the exposure light source is shortened and the numerical aperture (NA) of the projection lens is increased. Currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source has been developed. ing. As a technique for further improving the resolution, a method of filling a high-refractive-index liquid (hereinafter also referred to as "immersion liquid") between the projection lens and the sample (that is, the liquid immersion method) has been proposed.
For example, in Patent Document 1, a repeating unit derived from a resin, a photoacid generator, and an acrylic acid ester whose solubility in an alkaline developer is increased by the action of an acid and containing a fluorine atom is disclosed. A positive resist composition is described which contains a resin having a
In Patent Document 2, a resin that increases the solubility in an alkaline developer by the action of an acid, a photoacid generator, and a linking group that hydrolyzes by the action of an alkaline developer are included in the main chain, and a fluorine atom is included. A positive resist composition is described which contains a polymer having a

Japanese Patent Application Laid-Open No. 2012-242800 Japanese Patent Application Laid-Open No. 2017-90674

2. Description of the Related Art In recent years, along with the demand for improved productivity of various electronic devices, there is a growing demand for formation of an intended resist pattern in a shorter period of time.
Therefore, the inventors of the present invention have studied to improve the scanning speed in the exposure process using an immersion exposure apparatus as one method of shortening the formation time of the resist pattern. It has been found that it is very difficult to suppress various defects while maintaining high followability of the immersion liquid to the exposure apparatus when the speed is set to be ultrahigh.

According to the present invention, even if the scanning speed for exposure is set to an ultra-high speed (for example, 700 mm/sec or more), the immersion liquid (typically ultrapure water) has high followability to the exposure device during exposure (i.e., The dynamic receding contact angle of the actinic ray-sensitive or radiation-sensitive film with respect to water is large), and the hydrophilicity of the surface of the pattern after development is high (that is, the static contact angle (SCA) of the pattern surface with respect to water is Actinic ray-sensitive or radiation-sensitive resin composition capable of reducing both scum (liquid immersion defect) and development defect, and actinic ray- or radiation-sensitive film and pattern formation using the same An object of the present invention is to provide a method, a method for producing an electronic device, and a polyester that can be suitably used for the actinic ray-sensitive or radiation-sensitive resin composition.

Conventionally, as a polymer added to a resist composition, as in Patent Document 1, a resin having a repeating unit derived from an acrylic acid ester and containing a fluorine atom (also referred to as an "acrylic fluorine-containing resin" are known. Since the acrylic fluorine-containing resin is unevenly distributed on the surface of the resist film, the dynamic receding contact angle (also referred to as "DRCA") of the resist film to water can be increased compared to when the acrylic fluorine-containing resin is not added. is known to be possible.
In the present invention, it has been found that by including polyester in the resist composition, the DRCA can be made even higher than in the case of using an acrylic fluorine-containing resin. This is because when a resin (also referred to as an "acrylic resin") having a repeating unit derived from the (meth)acrylic acid ester described above is used as the resin (A), the polyester has a high separability from the acrylic resin. It is presumed that this is because (easily phase-separated), it is more likely to be unevenly distributed on the surface of the film than the acrylic fluorine-containing resin, and a high DRCA can be obtained even with a small addition amount. In addition, as described above, when polyester is used, high DRCA can be obtained with a small addition amount compared to acrylic fluorine-containing resin, so both scum (liquid immersion defect) and development defect are reduced. is considered to be possible.

Further, a resist film formed from a positive resist composition containing a fluorine atom-containing polymer (polyester) containing a linking group in the main chain that is hydrolyzed by the action of an alkaline developer disclosed in the aforementioned Patent Document 2 is In some cases, the DRCA can be improved more than the resist film containing the acrylic fluorine-containing resin described above, but there is a problem that defects are likely to occur when developed with an alkaline developer. This has been found by the inventors' studies.
This is because the addition of polyester to the resist composition enhances the hydrophobicity (water repellency) of the resist film, thereby improving the DRCA and improving the water followability during immersion exposure. This is probably because polyester has a low affinity with an alkaline developer, so that it is difficult to remove during alkaline development, and defects tend to occur. Especially in the case of positive resist compositions, defects tend to occur in unexposed areas. One possible means for suppressing defects is to increase the affinity of the polyester for the alkaline developer. That is, in order to solve the above problem, it is important to develop a technique to make the surface hydrophilic (water-repellent) during development while the surface is hydrophobic (water-repellent) during immersion exposure.
In addition, the amount of the resin (also referred to as "additive polymer") used to hydrophobize the film surface increases in the resist film in proportion to the added amount. Since the remaining additive polymer has high water repellency, it is considered that the larger the remaining amount, the worse the scum and development defects by remaining on the resist pattern surface. Therefore, it is considered that scum and development defects can be improved by suppressing the amount of additive polymer. In addition, if the added polymer has a high affinity for an alkaline developer during development, it is likely to be easily removed during development, thereby improving scum and development defects.
Since the polyester (B) of the present invention has an alkali-decomposable group in the side chain, it is considered to have higher alkali-decomposability than the polyester of Patent Document 2 having an alkali-decomposable group in the main chain. This is because the polymer is in a state of being entangled in a filamentous state, and in the polyester of Patent Document 2 having alkali-decomposable groups in the main chain, the alkali-decomposable groups are less likely to come into contact with an alkaline developer, and the side chains of the present invention This is probably because the reactivity is inferior to that of the polyester having an alkali-decomposable group. If the polyester has a high alkali decomposability, the polyester is easily decomposed by an alkaline developer, and therefore easily removed by the alkaline developer during alkaline development. The fact that the polyester was removed by the alkaline developer can be confirmed by the fact that the static contact angle (SCA) of the surface of the pattern (resist pattern) after development is lowered.
Therefore, the polyester having an alkali-decomposable group in the side chain of the present invention can form a resist film with a high receding contact angle (DRCA) during exposure, and is decomposed by an alkaline developer during development to become hydrophilic. Since it becomes high, it is easily removed with an alkaline developer, and it is an extremely useful material that can reduce scum and development defects.
The term "defect" refers to defects in general that are detected when a resist film after development is observed from directly above, for example, using a surface defect observation apparatus (trade name "KLA") manufactured by KLA-Tencor. These defects include, for example, scum, bubbles, dust, bridges (bridge structures between resist patterns), color unevenness, deposits, and residues after development. It is speculated that these problems can be solved by using a material that is hydrophobic during immersion exposure and hydrophilic during development.

一般式（ＥＺ－２）中、Ｍ_２１及びＭ_２２は各々独立に、単結合又は２価の連結基を表し、ＥＺ_２は有機基を表す。＊は結合位置を表す。
＜２＞
（Ａ）酸の作用により分解し極性が増大する基を有する樹脂、（Ｂ）側鎖にアルカリ分解性基を有するポリエステル、及び（Ｃ）光酸発生剤を含む、感活性光線性又は感放射線性樹脂組成物であって、
上記（Ｂ）ポリエステルが、下記一般式（１）で表され、
上記（Ｂ）ポリエステルが、側鎖に下記一般式（ＥＺ－２）で表される基を有する、感活性光線性又は感放射線性樹脂組成物。

一般式（１）中、Ｅ_１及びＥ_２はそれぞれ独立に、ヘテロ原子を含んでもよい鎖状脂肪族基、ヘテロ原子を含んでもよい脂環基、芳香族基、又はこれらを組み合わせてなる基を表す。ただし、Ｅ_１は下記一般式（１ｄ）～（１ｆ）のいずれかで表される基を表す。

一般式（１ｄ）中、Ｗ_７及びＷ_８は、それぞれ独立に、単結合又はアルキレン基若しくはシクロアルキレン基を表し、Ｚ_４は、シクロアルキレン基、ヘテロ原子を含んでもよいスピロ環基、又はアリーレン基を表し、Ｙ_１及びＹ_２は、それぞれ独立に、単結合又は２価の連結基を表し、Ｑ_５はハロゲン原子を有する有機基を表し、ｋ２は１以上の整数を表す。ｋ２が２以上の整数を表す場合、複数のＹ_１、複数のＹ_２、及び複数のＱ_５はそれぞれ同一でも異なっていてもよい。
一般式（１ｅ）中、Ｗ_９、Ｗ_１０及びＷ_１１は、それぞれ独立に、単結合又はアルキレン基若しくはシクロアルキレン基を表し、Ｚ_５及びＺ_６は、それぞれ独立に、シクロアルキレン基、ヘテロ原子を含んでもよいスピロ環基、又はアリーレン基を表し、Ｙ_３、Ｙ_４、Ｙ_５及びＹ_６は、それぞれ独立に、単結合又は２価の連結基を表し、Ｑ_６及びＱ_７は、それぞれ独立に、ハロゲン原子を有する有機基を表し、ｋ３及びｋ４は、それぞれ独立に、１以上の整数を表す。ｋ３が２以上の整数を表す場合、複数のＹ_３、複数のＹ_４、及び複数のＱ_６はそれぞれ同一でも異なっていてもよい。ｋ４が２以上の整数を表す場合、複数のＹ_５、複数のＹ_６、及び複数のＱ_７はそれぞれ同一でも異なっていてもよい。
一般式（１ｆ）中、Ｙ_７及びＹ_８は、それぞれ独立に、単結合又は２価の連結基を表し、Ｑ_８は水素原子又は置換基を表し、Ｑ_９はハロゲン原子を有する有機基を表し、ｋ５は１以上の整数を表し、ｋ６は１又は２を表す。ｋ５が２以上の整数を表す場合、複数のＹ_７、複数のＹ_８、複数のＱ_８、及び複数のＱ_９はそれぞれ同一でも異なっていてもよい。

一般式（ＥＺ－２）中、Ｍ _２１ 及びＭ _２２ は各々独立に、単結合又は２価の連結基を表し、ＥＺ _２ は有機基を表す。＊は結合位置を表す。
＜３＞
上記（Ｂ）ポリエステルの含有量が、上記感活性光線性又は感放射線性樹脂組成物の全固形分に対して、０．１質量％以上１５質量％以下である、＜１＞又は＜２＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜４＞
上記（Ｂ）ポリエステルが、下記一般式（１）で表される、＜１＞に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（１）中、Ｅ_１及びＥ_２はそれぞれ独立に、ヘテロ原子を含んでもよい鎖状脂肪族基、ヘテロ原子を含んでもよい脂環基、芳香族基、又はこれらを組み合わせてなる基を表す。
＜５＞
上記一般式（１）中のＥ_１及びＥ_２の少なくとも１つが、下記一般式（１ｄ）～（１ｆ）のいずれかで表される基を表す、＜４＞に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（１ｄ）中、Ｗ_７及びＷ_８は、それぞれ独立に、単結合又はアルキレン基若しくはシクロアルキレン基を表し、Ｚ_４は、シクロアルキレン基、ヘテロ原子を含んでもよいスピロ環基、又はアリーレン基を表し、Ｙ_１及びＹ_２は、それぞれ独立に、単結合又は２価の連結基を表し、Ｑ_５はハロゲン原子を有する有機基を表し、ｋ２は１以上の整数を表す。ｋ２が２以上の整数を表す場合、複数のＹ_１、複数のＹ_２、及び複数のＱ_５はそれぞれ同一でも異なっていてもよい。
一般式（１ｅ）中、Ｗ_９、Ｗ_１０及びＷ_１１は、それぞれ独立に、単結合又はアルキレン基若しくはシクロアルキレン基を表し、Ｚ_５及びＺ_６は、それぞれ独立に、シクロアルキレン基、ヘテロ原子を含んでもよいスピロ環基、又はアリーレン基を表し、Ｙ_３、Ｙ_４、Ｙ_５及びＹ_６は、それぞれ独立に、単結合又は２価の連結基を表し、Ｑ_６及びＱ_７は、それぞれ独立に、ハロゲン原子を有する有機基を表し、ｋ３及びｋ４は、それぞれ独立に、１以上の整数を表す。ｋ３が２以上の整数を表す場合、複数のＹ_３、複数のＹ_４、及び複数のＱ_６はそれぞれ同一でも異なっていてもよい。ｋ４が２以上の整数を表す場合、複数のＹ_５、複数のＹ_６、及び複数のＱ_７はそれぞれ同一でも異なっていてもよい。
一般式（１ｆ）中、Ｙ_７及びＹ_８は、それぞれ独立に、単結合又は２価の連結基を表し、Ｑ_８は水素原子又は置換基を表し、Ｑ_９はハロゲン原子を有する有機基を表し、ｋ５は１以上の整数を表し、ｋ６は１又は２を表す。ｋ５が２以上の整数を表す場合、複数のＹ_７、複数のＹ_８、複数のＱ_８、及び複数のＱ_９はそれぞれ同一でも異なっていてもよい。
＜６＞
上記（Ｂ）ポリエステルが、フッ素原子を含有する、＜１＞～＜５＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜７＞
＜１＞～＜６＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物により形成された感活性光線性又は感放射線性膜。
＜８＞
＜１＞～＜６＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物によって感活性光線性又は感放射線性膜を形成する工程、
上記感活性光線性又は感放射線性膜に活性光線又は放射線を照射する工程、及び、
上記活性光線又は放射線が照射された感活性光線性又は感放射線性膜を、現像液を用いて現像する工程、を有するパターン形成方法。
＜９＞
上記現像液が、アルカリ現像液又は有機溶剤を含む現像液である、＜８＞に記載のパターン形成方法。
＜１０＞
＜８＞又は＜９＞に記載のパターン形成方法を含む、電子デバイスの製造方法。
本発明は、上記＜１＞～＜１０＞に関するものであるが、本明細書には参考のためその他の事項についても記載した。
That is, the inventors have found that the above problems can be solved by the following configuration.
<1>
(A) a resin having a group that is decomposed by the action of an acid to increase polarity, (B) a polyester having an alkali-decomposable group in a side chain, and (C) a photoacid generator, which is sensitive to actinic rays or radiation. a flexible resin composition,
Actinic ray-sensitive or radiation-sensitive resin composition, wherein the polyester (B) has a group represented by the following general formula (EZ-2) in the side chain.

In general formula (EZ-2), M ₂₁ and M ₂₂ each independently represent a single bond or a divalent linking group, and EZ ₂ represents an organic group. * represents a binding position.
< 2 >
(A) a resin having a group that is decomposed by the action of an acid to increase polarity, (B) a polyester having an alkali-decomposable group in a side chain, and (C) a photoacid generator, which is sensitive to actinic rays or radiation. a flexible resin composition,
The (B) polyester is represented by the following general formula (1) ,
Actinic ray-sensitive or radiation-sensitive resin composition, wherein the polyester (B) has a group represented by the following general formula (EZ-2) in the side chain .

In general formula (1), E ₁ and E ₂ are each independently a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, an aromatic group, or a group formed by combining these represents However, E ₁ represents a group represented by any one of the following general formulas (1d) to (1f).

In general formula (1d), W ₇ and W ₈ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₄ is a cycloalkylene group, a spirocyclic group optionally containing a hetero atom, or arylene Y ₁ and Y ₂ each independently represent a single bond or a divalent linking group, Q ₅ represents an organic group having a halogen atom, and k2 represents an integer of 1 or more. When k2 represents an integer of 2 or more, the plurality of Y ₁ s, the plurality of Y ₂ s, and the plurality of Q ₅ may be the same or different.
In general formula (1e), W ₉ , W ₁₀ and W ₁₁ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₅ and Z ₆ each independently represent a cycloalkylene group, a heteroatom represents a spirocyclic group or an arylene group, Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a single bond or a divalent linking group, and Q ₆ and Q ₇ each represent Each independently represents an organic group having a halogen atom, and k3 and k4 each independently represents an integer of 1 or more. When k3 represents an integer of 2 or more, multiple Y ₃ s, multiple Y ₄ s, and multiple Q _6s may be the same or different. When k4 represents an integer of 2 or more, the plurality of Y ₅ s, the plurality of Y ₆ s, and the plurality of Q ₇ may be the same or different.
_In general formula ₍ 1f), Y7 and Y8 each independently represent a single bond or a divalent linking group, _Q8 represents a hydrogen atom or a substituent, and _Q9 represents an organic group having a halogen atom. , k5 represents an integer of 1 or more, and k6 represents 1 or 2. When k5 represents an integer of 2 or more, multiple Y ₇ , multiple Y ₈ , multiple Q ₈ , and multiple Q ₉ may be the same or different.

In general formula (EZ-2), M ₂₁ and M ₂₂ each independently represent a single bond or a divalent linking group, and EZ ₂ represents an organic group. * represents a binding position.
< 3 >
<1> or <2> , wherein the content of the (B) polyester is 0.1% by mass or more and 15% by mass or less with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition Actinic ray-sensitive or radiation-sensitive resin composition according to .
< 4 >
The actinic ray-sensitive or radiation-sensitive resin composition according to <1 >, wherein the (B) polyester is represented by the following general formula (1).

In general formula (1), E ₁ and E ₂ are each independently a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, an aromatic group, or a group formed by combining these represents
< 5 >
_The actinic ray _- sensitive or A radiation-sensitive resin composition.

In general formula (1d), W ₇ and W ₈ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₄ is a cycloalkylene group, a spirocyclic group optionally containing a hetero atom, or arylene Y ₁ and Y ₂ each independently represent a single bond or a divalent linking group, Q ₅ represents an organic group having a halogen atom, and k2 represents an integer of 1 or more. When k2 represents an integer of 2 or more, the plurality of Y ₁ s, the plurality of Y ₂ s, and the plurality of Q ₅ may be the same or different.
In general formula (1e), W ₉ , W ₁₀ and W ₁₁ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₅ and Z ₆ each independently represent a cycloalkylene group, a heteroatom represents a spirocyclic group or an arylene group, Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a single bond or a divalent linking group, and Q ₆ and Q ₇ each represent Each independently represents an organic group having a halogen atom, and k3 and k4 each independently represents an integer of 1 or more. When k3 represents an integer of 2 or more, multiple Y ₃ s, multiple Y ₄ s, and multiple Q _6s may be the same or different. When k4 represents an integer of 2 or more, the plurality of Y ₅ s, the plurality of Y ₆ s, and the plurality of Q ₇ may be the same or different.
_In general formula ₍ 1f), Y7 and Y8 each independently represent a single bond or a divalent linking group, _Q8 represents a hydrogen atom or a substituent, and _Q9 represents an organic group having a halogen atom. , k5 represents an integer of 1 or more, and k6 represents 1 or 2. When k5 represents an integer of 2 or more, multiple Y ₇ , multiple Y ₈ , multiple Q ₈ , and multiple Q ₉ may be the same or different.
< 6 >
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to < 5 >, wherein the polyester (B) contains a fluorine atom.
< 7 >
An actinic ray- or radiation-sensitive film formed from the actinic ray- or radiation-sensitive resin composition according to any one of <1> to < 6 >.
< 8 >
A step of forming an actinic ray-sensitive or radiation-sensitive film from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to < 6 >;
a step of irradiating the actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation; and
A pattern forming method comprising the step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation with a developer.
< 9 >
The pattern forming method according to < 8 >, wherein the developer is an alkaline developer or a developer containing an organic solvent.
< 10 >
A method for manufacturing an electronic device, comprising the pattern forming method according to < 8 > or < 9 >.
Although the present invention relates to the above <1> to < 10 >, other matters are also described in this specification for reference.

[1]
(A) a resin having a group that is decomposed by the action of an acid to increase its polarity, (B) a polyester having an alkali-decomposable group in its side chain, and (C) an actinic ray-sensitive or radiation-sensitive resin containing a photoacid generator elastic resin composition.
[2]
The sensitizer according to [1], wherein the content of the polyester (B) is 0.1% by mass or more and 15% by mass or less with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Actinic ray or radiation sensitive resin composition.
[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the polyester (B) has a group represented by the following general formula (EZ-1) in a side chain.

In general formula (EZ- ₁ ), _M20 represents a single bond or a divalent linking group, and EZ1 represents an organic group. * represents a binding position.
[4]
The actinic ray-sensitive or radiation-sensitive resin according to any one of [1] to [3], wherein the (B) polyester has a group represented by the following general formula (EZ-2) in the side chain Composition.

In general formula (EZ-2), M ₂₁ and M ₂₂ each independently represent a single bond or a divalent linking group, and EZ ₂ represents an organic group. * represents a binding position.
[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the (B) polyester is represented by the following general formula (1).

In general formula (1), E ₁ and E ₂ are each independently a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, an aromatic group, or a group formed by combining these represents
[6]
Actinic ray-sensitive or according to [5], wherein at least one of E ₁ and E ₂ in the general formula (1) represents a group represented by any one of the following general formulas (1d) to (1f) A radiation-sensitive resin composition.

In general formula (1d), W ₇ and W ₈ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₄ is a cycloalkylene group, a spirocyclic group optionally containing a hetero atom, or arylene Y ₁ and Y ₂ each independently represent a single bond or a divalent linking group, Q ₅ represents an organic group having a halogen atom, and k2 represents an integer of 1 or more. When k2 represents an integer of 2 or more, the plurality of Y ₁ s, the plurality of Y ₂ s, and the plurality of Q ₅ may be the same or different.
In general formula (1e), W ₉ , W ₁₀ and W ₁₁ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₅ and Z ₆ each independently represent a cycloalkylene group, a heteroatom represents a spirocyclic group or an arylene group, Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a single bond or a divalent linking group, and Q ₆ and Q ₇ each represent Each independently represents an organic group having a halogen atom, and k3 and k4 each independently represents an integer of 1 or more. When k3 represents an integer of 2 or more, multiple Y ₃ s, multiple Y ₄ s, and multiple Q _6s may be the same or different. When k4 represents an integer of 2 or more, the plurality of Y ₅ s, the plurality of Y ₆ s, and the plurality of Q ₇ may be the same or different.
_In general formula ₍ 1f), Y7 and Y8 each independently represent a single bond or a divalent linking group, _Q8 represents a hydrogen atom or a substituent, and _Q9 represents an organic group having a halogen atom. , k5 represents an integer of 1 or more, and k6 represents 1 or 2. When k5 represents an integer of 2 or more, multiple Y ₇ , multiple Y ₈ , multiple Q ₈ , and multiple Q ₉ may be the same or different.
[7]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the polyester (B) contains a fluorine atom.
[8]
An actinic ray- or radiation-sensitive film formed from the actinic ray- or radiation-sensitive resin composition according to any one of [1] to [7].
[9]
A step of forming an actinic ray-sensitive or radiation-sensitive film from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7];
a step of irradiating the actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation; and
A pattern forming method comprising the step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation with a developer.
[10]
The pattern forming method of [9], wherein the developer is an alkaline developer or a developer containing an organic solvent.
[11]
A method for manufacturing an electronic device, comprising the pattern forming method according to [9] or [10].
[12]
represented by the following general formula (1), and at least one of E ₁ and E ₂ in the following general formula (1) represents a group represented by any one of the following general formulas (1d) to (1f); polyester.

In general formula (1), E ₁ and E ₂ are each independently a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, an aromatic group, or a group formed by combining these represents

In general formula (1d), W ₇ and W ₈ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₄ is a cycloalkylene group, a spirocyclic group optionally containing a hetero atom, or arylene Y ₁ and Y ₂ each independently represent a single bond or a divalent linking group, Q ₅ represents an organic group having a halogen atom, and k2 represents an integer of 1 or more. When k2 represents an integer of 2 or more, the plurality of Y ₁ s, the plurality of Y ₂ s, and the plurality of Q ₅ may be the same or different.
In general formula (1e), W ₉ , W ₁₀ and W ₁₁ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₅ and Z ₆ each independently represent a cycloalkylene group, a heteroatom represents a spirocyclic group or an arylene group, Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a single bond or a divalent linking group, and Q ₆ and Q ₇ each represent Each independently represents an organic group having a halogen atom, and k3 and k4 each independently represents an integer of 1 or more. When k3 represents an integer of 2 or more, multiple Y ₃ s, multiple Y ₄ s, and multiple Q _6s may be the same or different. When k4 represents an integer of 2 or more, the plurality of Y ₅ s, the plurality of Y ₆ s, and the plurality of Q ₇ may be the same or different.
_In general formula ₍ 1f), Y7 and Y8 each independently represent a single bond or a divalent linking group, _Q8 represents a hydrogen atom or a substituent, and _Q9 represents an organic group having a halogen atom. , k5 represents an integer of 1 or more, and k6 represents 1 or 2. When k5 represents an integer of 2 or more, multiple Y ₇ , multiple Y ₈ , multiple Q ₈ , and multiple Q ₉ may be the same or different.

According to the present invention, even if the exposure scanning speed is ultra-high (for example, 700 mm/sec or more), the immersion liquid (typically ultrapure water) has high followability to the exposure device during exposure ( That is, the dynamic receding contact angle of the actinic ray-sensitive or radiation-sensitive film with respect to water is large), and the hydrophilicity of the surface of the pattern after development is high (that is, the static contact angle of the pattern surface with respect to water is small. ), actinic ray- or radiation-sensitive resin composition capable of reducing both scum (liquid immersion defect) and development defect, and actinic ray- or radiation-sensitive film and pattern forming method using the same , a method for producing an electronic device, and a polyester that can be suitably used for the actinic ray-sensitive or radiation-sensitive resin composition.

The present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
Regarding the notation of groups (atomic groups) in the present specification, notations that do not describe substitution and unsubstituted include those not having substituents as well as those having substituents. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the term "organic group" as used herein refers to a group containing at least one carbon atom.
The term "actinic ray" or "radiation" as used herein refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam) and the like. As used herein, "light" means actinic rays or radiation.
The term "exposure" as used herein means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also electron beams and ion beams. It also includes drawing with particle beams such as beams.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.

As used herein, (meth)acrylate refers to acrylate and methacrylate, and (meth)acryl refers to acrylic and methacrylic.
In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw/Mn) of the resin are measured using a GPC (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by Tosoh Corporation). ) by GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index It is defined as a polystyrene conversion value by a detector (Refractive Index Detector).

[Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") will be described.
The composition of the present invention comprises (A) a resin having a group that is decomposed by the action of an acid to increase polarity, (B) a polyester having an alkali-decomposable group in its side chain, and (C) a photoacid generator.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a resist composition, and may be a positive resist composition or a negative resist composition. Moreover, it may be a resist composition for alkali development or a resist composition for organic solvent development.
The resist composition of the present invention is typically a chemically amplified resist composition.
The components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention are described in detail below.

<Resin (A)>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin ("acid-decomposable resin" or Also referred to as "resin (A)").
In this case, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, the positive pattern is preferably formed. , a negative pattern is preferably formed.

Resin (A) preferably has a repeating unit having an acid-decomposable group.
Resin (A) is preferably a polymer obtained by polymerizing a monomer having an ethylenically unsaturated double bond.

As the resin (A), known resins can be appropriately used. For example, paragraphs [0055] to [0191] of US Patent Application Publication No. 2016/0274458A1, paragraphs [0035] to [0085] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0147150A1 Known resins disclosed in paragraphs [0045] to [0090] of the specification can be suitably used as resin (A).

The acid-decomposable group preferably has a structure in which a polar group is protected by a group that decomposes and leaves by the action of an acid (leaving group).
Polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, and (alkylsulfonyl)(alkylcarbonyl)imide groups. , bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, tris(alkylsulfonyl)methylene group, etc. (a group that dissociates in a 2.38% by mass tetramethylammonium hydroxide aqueous solution), an alcoholic hydroxyl group, and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). It excludes aliphatic alcohols substituted with functional groups (eg, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group with a pKa (acid dissociation constant) of 12 or more and 20 or less.

Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.

Preferred groups as acid-decomposable groups are groups in which the hydrogen atoms of these groups are substituted with groups (leaving groups) that leave under the action of acid.
Examples of groups that leave by the action of an acid (leaving groups) include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and - C(R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and the like.
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group. R ₃₆ and R ₃₇ may combine with each other to form a ring.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl. groups, octyl groups, and the like.
Cycloalkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. As the polycyclic type, cycloalkyl groups having 6 to 20 carbon atoms are preferable, and examples thereof include adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, and tetracyclododecyl. group, androstanyl group, and the like. At least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl groups represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl, naphthyl and anthryl groups.
Aralkyl groups represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably aralkyl groups having 7 to 12 carbon atoms, such as benzyl, phenethyl and naphthylmethyl groups.
Alkenyl groups represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably alkenyl groups having 2 to 8 carbon atoms, such as vinyl, allyl, butenyl and cyclohexenyl groups.
The ring formed by combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. .

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group, and more preferably an acetal group or a tertiary alkyl ester group.

Resin (A) preferably has a repeating unit represented by the following general formula (AI) as a repeating unit having an acid-decomposable group.

In general formula (AI),
Xa ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group.
T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group.
Any two of Rx ₁ to Rx ₃ may or may not combine to form a ring structure.

Examples of the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group or an arylene group.
T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably -CH ₂ -, -(CH ₂ ) ₂ -, or -(CH ₂ ) ₃ -. More preferably T is a single bond.

Xa ₁ is preferably a hydrogen atom or an alkyl group.
The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group of Xa ₁ preferably has 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, hydroxymethyl and trifluoromethyl groups. The alkyl group of Xa ₁ is preferably a methyl group.

The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched and include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl. and t-butyl group are preferred. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3. Some of the carbon-carbon bonds in the alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be double bonds.
Cycloalkyl groups for Rx ₁ , Rx ₂ and Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, tetracyclododecanyl and adamantyl groups. is preferred.

The ring structure formed by combining Rx ₁ , Rx ₂ and Rx ₃ includes monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring and cyclooctane ring, norbornane ring, tetracyclo Polycyclic cycloalkyl rings such as decane ring, tetracyclododecane ring and adamantane ring are preferred. A cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferred. As the ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ , the structures shown below are also preferable.

Specific examples of the monomer corresponding to the repeating unit represented by formula (AI) are shown below, but the present invention is not limited to these specific examples. The following specific examples correspond to cases where Xa ₁ in general formula (AI) is a methyl group, but Xa ₁ can optionally be substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

The resin (A) preferably has repeating units described in paragraphs [0336] to [0369] of US Patent Application Publication No. 2016/0070167A1 as repeating units having an acid-decomposable group.

In addition, the resin (A) is a repeating unit having an acid-decomposable group, which is decomposed by the action of an acid described in paragraphs [0363] to [0364] of US Patent Application Publication No. 2016/0070167A1 to form an alcoholic It may have a repeating unit containing a group that produces a hydroxyl group.

The resin (A) may contain a repeating unit having an acid-decomposable group singly or in combination of two or more.

The content of the repeating units having an acid-decomposable group contained in the resin (A) (the total when there are a plurality of repeating units having an acid-decomposable group) is 10 to 90 mol % is preferred, 20 to 80 mol % is more preferred, and 30 to 70 mol % is even more preferred.

Resin (A) preferably has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

As the lactone structure or sultone structure, any structure having a lactone structure or sultone structure can be used. A membered lactone structure to which another ring structure is condensed to form a bicyclo structure or spiro structure, or a 5- to 7-membered sultone structure to which a bicyclo structure or spiro structure is formed to form another ring structure is more preferably fused. Having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3) It is more preferable to have repeating units. Also, the lactone structure or sultone structure may be directly bonded to the main chain. Preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), (LC1-16), (LC1-21) and (SL1-1).

The lactone structure portion or sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , halogen atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. More preferred are alkyl groups having 1 to 4 carbon atoms, cyano groups, and acid-decomposable groups. _n2 represents an integer of 0-4. When n ₂ is 2 or more, the multiple substituents (Rb ₂ ) may be the same or different. Also, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

A repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).

In the above general formula (III),
A represents an ester bond (group represented by -COO-) or an amide bond (group represented by -CONH-).
n is the number of repetitions of the structure represented by -R ₀ -Z- and represents an integer of 0 to 5, preferably 0 or 1, more preferably 0; When n is 0, -R ₀ -Z- is absent and becomes a single bond.
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are more than one R ₀ , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
Z represents a single bond, ether bond, ester bond, amide bond, urethane bond or urea bond. When Z is plural, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
_R8 represents a monovalent organic group having a lactone structure or a sultone structure.
_R7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

The alkylene group or cycloalkylene group of R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, more preferably an ester bond.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and specific examples of the monomer corresponding to the repeating unit represented by the general formula (A-1) are given below. It is not limited to these specific examples. The following specific examples correspond to cases where R ₇ in general formula (III)) and R _A ¹ in general formula (A-1) are methyl groups, and R ₇ and R _A ¹ are hydrogen atoms, halogen Atoms or monovalent organic groups can be optionally substituted.

In addition to the above monomers, monomers shown below are also suitably used as raw materials for the resin (A).

Resin (A) may have a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure. The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by general formula (A-1) below.

In general formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
n represents an integer of 0 or more.
R _A ² represents a substituent. Each R _A ² independently represents a substituent when n is 2 or more.
A represents a single bond or a divalent linking group.
Z represents an atomic group that forms a monocyclic or polycyclic structure together with the group represented by -OC(=O)-O- in the formula.

Resin (A) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, as described in paragraphs [0370] to [0414] of US Patent Application Publication No. 2016/0070167A1. It is also preferable to have the repeating unit described in .

The resin (A) may contain a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, singly or in combination of two or more.

Content of repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in the resin (A) (selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure When there are multiple repeating units having at least one type, the total) is preferably 5 to 70 mol%, preferably 10 to 65 mol%, based on the total repeating units of the resin (A). More preferably, 20 to 60 mol% is even more preferable

Resin (A) preferably has a repeating unit having a polar group.
Polar groups include hydroxyl groups, cyano groups, carboxyl groups, and fluorinated alcohol groups.
The repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Moreover, the repeating unit having a polar group preferably does not have an acid-decomposable group. Among the alicyclic hydrocarbon structures substituted with a polar group, the alicyclic hydrocarbon structure is preferably an adamantyl group or a norbornane group.

Specific examples of the monomer corresponding to the repeating unit having a polar group are shown below, but the present invention is not limited to these specific examples.

In addition, specific examples of repeating units having a polar group include repeating units disclosed in paragraphs [0415] to [0433] of US Patent Application Publication No. 2016/0070167A1. The resin (A) may contain a repeating unit having a polar group singly or in combination of two or more.
The content of repeating units having a polar group is preferably 5 to 40 mol %, more preferably 5 to 30 mol %, still more preferably 10 to 25 mol %, based on all repeating units in the resin (A).

Resin (A) can further have repeating units that have neither acid-decomposable groups nor polar groups. A repeating unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure. Examples of repeating units having neither an acid-decomposable group nor a polar group include repeating units described in paragraphs [0236] to [0237] of US Patent Application Publication No. 2016/0026083A1. Preferred examples of monomers corresponding to repeating units having neither acid-decomposable groups nor polar groups are shown below.

In addition, specific examples of the repeating unit having neither an acid-decomposable group nor a polar group include repeating units disclosed in paragraph [0433] of US Patent Application Publication No. 2016/0070167A1. can be done. The resin (A) may contain a repeating unit having neither an acid-decomposable group nor a polar group, either singly or in combination of two or more.
The content of repeating units having neither an acid-decomposable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on the total repeating units in the resin (A). 5 to 25 mol % is more preferred.

In addition to the repeating structural unit described above, the resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and generally required properties of resist such as resolution, heat resistance, and sensitivity. It can have various repeating structural units for the purpose of Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to monomers.

Examples of monomers include compounds having one addition-polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. can be mentioned.
In addition, any addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the above-mentioned various repeating structural units may be copolymerized.
In the resin (A), the content molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.

When the composition of the present invention is for ArF exposure, the resin (A) preferably does not substantially have an aromatic group from the viewpoint of ArF light transmission. More specifically, in all the repeating units of the resin (A), the repeating units having an aromatic group are preferably 5 mol% or less, more preferably 3 mol% or less, ideally is 0 mol %, that is, it is more preferable not to have a repeating unit having an aromatic group. Moreover, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

It is preferable that all the repeating units of the resin (A) are composed of (meth)acrylate repeating units. In this case, all repeating units may be methacrylate repeating units, all repeating units may be acrylate repeating units, or all repeating units may be methacrylate repeating units and acrylate repeating units. Although it can be used, it is preferable that the acrylate-based repeating unit is 50 mol % or less based on the total repeating units of the resin (A).

When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (A) preferably contains a repeating unit having an aromatic hydrocarbon group. More preferably, the resin (A) contains a repeating unit containing a phenolic hydroxyl group. Examples of repeating units containing phenolic hydroxyl groups include hydroxystyrene repeating units and hydroxystyrene (meth)acrylate repeating units.
When the composition of the present invention is used for KrF exposure, EB exposure or EUV exposure, the resin (A) contains a group (leaving group) in which the hydrogen atom of the phenolic hydroxyl group is decomposed and eliminated by the action of an acid. It is preferred to have a structure protected with
The content of the repeating unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, based on the total repeating units in the resin (A). , 50 to 100 mol % is more preferable.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, and 3,000 to 11,000. Especially preferred. The dispersity (Mw/Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, further preferably 1.1 to 2.0. preferable.

Resin (A) may be used individually by 1 type, and may use 2 or more types together.
The content of resin (A) in the total solid content of the composition of the present invention is generally 20% by mass or more. 40% by mass or more is preferable, 60% by mass or more is more preferable, and 80% by mass or more is even more preferable. Although the upper limit is not particularly limited, it is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 97% by mass or less.

<(B) Polyester having an alkali-decomposable group in the side chain>
The composition of the present invention contains (B) a polyester having an alkali-decomposable group in its side chain (also referred to as "polyester (B)" or "component (B)").
As described above, since the polyester (B) of the present invention has an alkali-decomposable group in the side chain, the composition of the present invention can be used at an ultra-high exposure scanning speed (e.g., 700 mm/sec or higher). Also, during exposure, the immersion liquid (typically ultrapure water) has high followability to the exposure device (that is, the dynamic receding contact angle of the actinic ray-sensitive or radiation-sensitive film to water is large). In addition, during development, the polyester (B) is decomposed by the alkali of the alkaline developer, etc., and the hydrophilicity (affinity with the alkaline developer) increases (easily removed by the alkaline developer), so scum and development defects are reduced. be done.

The polyester as component (B) in the present invention is a polymer having an ester bond in its main chain. That is, the polyester as the component (B) in the present invention is not a polymer having an ester bond in the side chain of a polymer (for example, an acrylic resin) obtained by polymerizing a monomer having an ethylenically unsaturated double bond.
Moreover, the polyester as the component (B) in the present invention is a component different from the resin (A) described above.
It is preferable that the polyester as the component (B) in the present invention is not a surfactant. The polyester (B) may have a carboxylate or sulfonate structure, or may not have a carboxylate or sulfonate structure. Moreover, the polyester (B) preferably does not have nonionic hydrophilic groups such as ethyleneoxy groups and propyleneoxy groups.

The alkali-decomposable group is a group that is decomposed by the action of alkali to increase the polarity, and more specifically, is a group that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer. As the alkali-decomposable group, for example, a group obtained by substituting a hydrogen atom of an alkali-soluble group such as a --COOH group or --OH group with a group that is eliminated by the action of an alkali is preferable. More specifically, a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylic acid thioester group ( -COS-), carbonate group (-OC(O)O-), sulfate group (-OSO ₂ O-), sulfonate group (-SO ₂ O-) and the like.

Polyester (B) preferably has a group represented by the following general formula (EZ-1) in a side chain.
The group represented by the general formula (EZ-1) below is preferably a group containing an alkali-decomposable group.

In general formula (EZ- ₁ ), _M20 represents a single bond or a divalent linking group, and EZ1 represents an organic group. * represents a binding position.

In the general formula (EZ-1), when M ₂₀ represents a divalent linking group, -O-, -CO-, -COO-, an alkylene group (preferably having 1 to 15 carbon atoms, more preferably 1 to 10), a cycloalkylene group (preferably 3 to 15 carbon atoms, more preferably 5 to 10 carbon atoms), an arylene group (preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms), or these A divalent linking group formed by combining is preferred.
In general formula (EZ-1), EZ ₁ represents an organic group.
The organic group represented by EZ ₁ is preferably an electron-withdrawing group.
EZ ₁ preferably represents an organic group having a halogen atom.
The organic group having a halogen atom includes a halogenated alkyl group, a halogenated cycloalkyl group, a halogenated aryl group, or a monovalent group formed by combining these groups, or an alkyl group or a cycloalkyl group substituted with these groups. and the like.
When the organic group represented by EZ ₁ represents an electron-withdrawing group such as an organic group having a halogen atom, the group further contains an oxy group, a carbonyl group, a sulfonyl group, a sulfinyl group, or a combination thereof 2 may contain a valence group.
EZ ₁ is preferably a halogenated alkyl group, more preferably a halogenated alkyl group having 1 to 16 carbon atoms, even more preferably a halogenated alkyl group having 1 to 8 carbon atoms. Further, the halogenated alkyl group is preferably a fluorinated alkyl group. ,

The polyester (B) particularly preferably has a group represented by the following general formula (EZ-2) in the side chain. The group represented by the general formula (EZ-2) below is chain-lengthened by providing a linking group that serves as a spacer between the bonding position that bonds to the main chain of the polyester and the group that can be an alkali-decomposable group. Even when the polyester molecules are entangled in a string, the alkali-decomposable groups are likely to come into contact with the alkali developing solution, resulting in excellent alkali-decomposability. As a result, the SCA after exposure and development is lowered, the washability of the rinsing liquid is enhanced, and development defects can be further reduced.

In general formula (EZ-2), M ₂₁ and M ₂₂ each independently represent a single bond or a divalent linking group, and EZ ₂ represents an organic group. * represents a binding position.

In the general formula (EZ-2), when M ₂₁ and M ₂₂ represent a divalent linking group, detailed explanations such as preferred ranges are the same as for M ₂₀ in the general formula (EZ-1).
Detailed descriptions such as the preferred range of EZ2 in general formula (EZ- ₂ ) are the same as those for EZ1 in general formula (EZ- ₁ ).

Polyester (B) has an alkali-decomposable group in its side chain, and may further have an alkali-decomposable group in its main chain.

Polyester (B) is preferably represented by the following general formula (1).

In general formula (1), E ₁ and E ₂ are each independently a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, an aromatic group, or a group formed by combining these represents

In general formula (1), chain aliphatic groups as E ₁ and E ₂ are divalent groups, preferably alkylene groups, more preferably alkylene groups having 1 to 20 carbon atoms. , more preferably an alkylene group having 6 to 12 carbon atoms. Although the chain aliphatic group may contain a heteroatom (eg, an oxygen atom, a sulfur atom, or a nitrogen atom) in the chain, it preferably does not. The chain aliphatic group may have a substituent, and the substituents include a halogen atom, a cycloalkyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, a cycloalkyloxycarbonyl group, a cycloalkylcarbonyloxy group, An aryloxycarbonyl group, an arylcarbonyloxy group, a fluoroalkyloxycarbonyl group and the like are preferred, a halogen atom is more preferred, and a fluorine atom is particularly preferred.

In the general formula (1), the alicyclic group as E ₁ and E ₂ is a divalent group, preferably a cycloalkylene group or a spirocyclic group, a cycloalkylene group having 4 to 20 carbon atoms or a spiro A cyclic group is more preferred, and a cycloalkylene group or spirocyclic group having 4 to 12 carbon atoms is even more preferred. Here, the spirocyclic group as a divalent group is a divalent group obtained by removing any two hydrogen atoms from a spirocyclic compound. The alicyclic group may contain a heteroatom (eg, oxygen atom, sulfur atom, or nitrogen atom) as a ring member. A spirocyclic group containing an oxygen atom is particularly preferred. The alicyclic group may have a substituent, and the substituent is preferably a halogen atom, an alkyl group, an alkyloxycarbonyl group, a fluoroalkyloxycarbonyl group, etc., and more preferably a fluoroalkyloxycarbonyl group.

In general formula (1), the aromatic group as E ₁ and E ₂ is a divalent group, preferably an arylene group or a heteroarylene group (a divalent aromatic heterocyclic group), an arylene group is more preferred, an arylene group having 6 to 20 carbon atoms is even more preferred, and an arylene group having 6 to 12 carbon atoms is particularly preferred. The aromatic group may have a substituent, and the substituent is preferably a halogen atom, an alkyl group, an alkyloxycarbonyl group, a fluoroalkyloxycarbonyl group, or the like.

E ₁ and E ₂ in the general formula (1) are a combination of two or more selected from a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, and an aromatic group. It may be a divalent group. The combined group includes, for example, a group formed by combining an alkylene group and a cycloalkylene group, a group formed by combining an alkylene group and an arylene group, a group formed by combining an alkylene group and a spirocyclic group, and these groups. Groups containing heteroatoms in the chain or ring members, groups having substituents on these groups, and the like are included.

It is preferable that each of E ₁ and E ₂ in general formula (1) is independently a group represented by any one of the following general formulas (1a) to (1f). In particular, at least one of E ₁ and E ₂ in general formula (1) preferably represents a group represented by any one of general formulas (1d) to (1f) below.

In general formula (1a), Q ₁ to Q ₄ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and W ₁ represents a single bond, an alkylene group, or a cycloalkylene group.
In general formula (1b), W ₂ and W ₃ each independently represent a single bond, an alkylene group, or a cycloalkylene group, and Z ₁ is a cycloalkylene group, a spirocyclic group optionally containing a heteroatom, or an arylene group. represents
In general formula (1c), W ₄ , W ₅ and W ₆ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₂ and Z ₃ each independently represent a cycloalkylene group, a heteroatom represents a spirocyclic group which may contain, or an arylene group.

In general formula (1d), W ₇ and W ₈ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₄ is a cycloalkylene group, a spirocyclic group optionally containing a hetero atom, or arylene Y ₁ and Y ₂ each independently represent a single bond or a divalent linking group, Q ₅ represents an organic group having a halogen atom, and k2 represents an integer of 1 or more. When k2 represents an integer of 2 or more, the plurality of Y ₁ s, the plurality of Y ₂ s, and the plurality of Q ₅ may be the same or different.
In general formula (1e), W ₉ , W ₁₀ and W ₁₁ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₅ and Z ₆ each independently represent a cycloalkylene group, a heteroatom represents a spirocyclic group or an arylene group, Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a single bond or a divalent linking group, and Q ₆ and Q ₇ each represent Each independently represents an organic group having a halogen atom, and k3 and k4 each independently represents an integer of 1 or more. When k3 represents an integer of 2 or more, multiple Y ₃ s, multiple Y ₄ s, and multiple Q _6s may be the same or different. When k4 represents an integer of 2 or more, the plurality of Y ₅ s, the plurality of Y ₆ s, and the plurality of Q ₇ may be the same or different.
_In general formula ₍ 1f), Y7 and Y8 each independently represent a single bond or a divalent linking group, _Q8 represents a hydrogen atom or a substituent, and _Q9 represents an organic group having a halogen atom. , k5 represents an integer of 1 or more, and k6 represents 1 or 2. When k5 represents an integer of 2 or more, multiple Y ₇ , multiple Y ₈ , multiple Q ₈ , and multiple Q ₉ may be the same or different.

In general formula (1a), Q ₁ to Q ₄ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, preferably a halogen atom or an alkyl group.
Halogen atoms as Q ₁ to Q ₄ are preferably fluorine atoms.
The alkyl groups for Q ₁ to Q ₄ are preferably alkyl groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms. In addition, the alkyl groups as Q ₁ to Q ₄ may have a substituent, and when having a substituent, the substituent includes a halogen atom, an alkyl group, an alkyloxycarbonyl group, a fluoroalkyloxycarbonyl group, and the like. A halogen atom is preferred, and a fluorine atom is even more preferred.

In general formula (1a), W1 represents a _single bond, an alkylene group, or a cycloalkylene group.
The alkylene group for W ₁ is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 3 to 10 carbon atoms.
The alkylene group as W ₁ may have a substituent, and when it has a substituent, the substituent is preferably a halogen atom, more preferably a fluorine atom.
The cycloalkylene group for W ₁ is preferably a cycloalkylene group having 4 to 20 carbon atoms, more preferably a cycloalkylene group having 4 to 8 carbon atoms.
The cycloalkylene group as W ₁ may have a substituent, and when it has a substituent, the substituent is preferably a halogen atom, more preferably a fluorine atom.

W2 and W3 in general _formula ( _1b ) _are the same as W1 in general formula (1a).

In general formula (1b), Z ₁ represents a cycloalkylene group, a spirocyclic group which may contain a heteroatom, or an arylene group.
The cycloalkylene group as Z ₁ is preferably a cycloalkylene group having 4 to 20 carbon atoms, more preferably a cycloalkylene group having 4 to 8 carbon atoms.
The spirocyclic group as Z ₁ is preferably a C5-30 spirocyclic group, more preferably a C6-20 spirocyclic group.
The spirocyclic group as Z ₁ may contain a heteroatom as a ring member, and preferably contains an oxygen atom.
The arylene group as Z ₁ is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms.
The cycloalkylene group, optionally heteroatom-containing spirocyclic group, or arylene group represented by Z ₁ may optionally have a substituent, and the substituent may be a halogen atom, an alkyl group, an alkyloxycarbonyl group, or a fluoroalkyl group. An oxycarbonyl group and the like are preferred, and a fluoroalkyloxycarbonyl group is more preferred.

W ₄ , W ₅ and W ₆ in general formula (1c) are the same as W ₁ in general formula (1a).
Z ₂ and Z ₃ are the same as Z ₁ in general formula (1b) above.

_W7 and W8 in general formula ( _1d ) are the same as W1 _in general formula (1a).
Z ₄ is the same as Z ₁ in the above general formula (1b).
Q ₅ represents an organic group having a halogen atom, and the preferred range and the like are the same as those described for EZ ₁ in general formula (EZ-1) above.
Y ₁ and Y ₂ each independently represent a single bond or a divalent linking group.
When Y ₁ and Y ₂ represent a divalent linking group, -O-, -CO-, -COO-, an alkylene group (preferably having 1 to 20 carbon atoms, more preferably 2 to 6 carbon atoms), cyclo An alkylene group (preferably having 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms), an arylene group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), or a bivalent combination thereof is preferred.
When Y ₁ and Y ₂ represent an alkylene group, a cycloalkylene group, or an arylene group, they may further have substituents. The substituent is preferably a halogen atom, more preferably a fluorine atom.
k2 represents an integer of 1 or more, preferably an integer of 1 to 5, more preferably an integer of 1 to 3.

W ₉ , W ₁₀ and W ₁₁ in general formula (1e) are the same as W ₁ in general formula (1a).
Z ₅ and Z ₆ are the same as Z ₁ in the above general formula (1b).
Q6 and _Q7 are the _same as Q5 in general formula ₍ 1d).
Y ₃ to Y ₆ are the same as Y ₁ and Y ₂ in general formula (1d), respectively.
k3 and k4 each represent an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-3.

_Q9 in general formula (1f) is the _same as Q5 in general formula (1d).
_Y7 and Y8 _are the _same as Y1 and Y2 in general formula ( _1d ), respectively.
k5 represents an integer of 1 or more, preferably an integer of 1-20, more preferably an integer of 1-10.
_Q8 represents a hydrogen atom or a substituent, and although the substituent is not particularly limited, an alkyl group, a cycloalkyl group, an aryl group, or the like is preferable.

The repeating number of the structure (repeating structural unit) represented by the general formula (1) in the polyester (B) is preferably 3 or more, more preferably 5 to 200, and more preferably 5 to 100. It is more preferably 10-70, and most preferably 10-50. That is, polyester (B) preferably has a structure represented by the following general formula (1p).

In general formula (1p), E _1p and E _2p are each independently a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, an aromatic group, or a group formed by combining these represents k1 represents a number of 3 or more.

k1 is the average value for the entire polymer. k1 preferably represents 3 or more, more preferably 5 to 200, still more preferably 5 to 100, particularly preferably 10 to 70, and most preferably 10 to 50.
In general formula (1p), _E1p and _{E2p are} the same as E1 and E2 in general formula ( ₁ ), respectively.

Moreover, the polyester (B) of the present invention may have an acid-decomposable group in its main chain or side chain for the reason that the SCA after development can be further reduced.

An acid-decomposable group is a group that is decomposed by the action of an acid to increase its polarity. Examples of the acid-decomposable group include those described in the resin (A) above.

The polyester (B) may have an acid-decomposable group in its main chain, may have an acid-decomposable group in its side chain, or may have an acid-decomposable group in its main chain and side chains. It's okay to be

As the polyester (B), a polyester having an acid-decomposable group in the main chain is preferable, and a polyester having a structure represented by the following formula (P1) in the main chain is preferable.

In formula (P1), *1 to *4 represent binding positions.
*1 and *3, *1 and *4, *2 and *3, *2 and *4, or *3 and *4 in formula (P1) are preferably bonding positions with the polyester main chain. .

Polyester (B) preferably has at least one group represented by any one of the following general formulas (RZ-1) to (RZ-4).

In general formula (RZ-1), M ₁ represents a single bond or a divalent linking group, and TL ₁ and TL ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a halogen atom. and TL ₁ and TL ₂ may combine with each other to form a ring. L ₀ represents a single bond or an alkylene group. L ₀ and any one of TL ₁ and TL ₂ may combine with each other to form a ring. * represents a binding position.
In general formula (RZ-2), M ₂ and M ₃ each independently represent a single bond or a divalent linking group, TL ₃ and TL ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or represents an aryl group, and TL ₃ and TL ₄ may combine with each other to form a ring. * represents a binding position.
In general formula (RZ-3), M ₄ and M ₅ each independently represent a single bond or a divalent linking group, TL ₅ and TL ₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, represents an aryl group or a halogen atom. ZL1 represents a ring structure. ZL1 may represent a spiro ring structure. * represents a binding position.
In general formula (RZ-4), M ₆ and M ₇ each independently represent a single bond or a divalent linking group, TL ₇ and TL ₈ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, represents an aryl group or a halogen atom. ZL2 represents a ring structure. ZL2 may represent a spiro ring structure. * represents a binding position.

In general formula (RZ- ₁ ), M1 represents a single bond or a divalent linking group. When M ₁ represents a divalent linking group, it preferably represents an oxygen atom, an alkylene group, a cycloalkylene group, CR ^Z1 R ^Z2 , NR ^Z3 , or a divalent linking group formed by combining these, R ^Z1 , R ^Z2 and R ^Z3 each independently represent a hydrogen atom, an alkyl group, or a halogen atom, and R ^Z1 and R ^Z2 may combine with each other to form a ring.
The alkylene group for M ₁ is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms.
The alkylene group as M ₁ may have a substituent, and preferred examples of the substituent include a cycloalkyl group, an alkyloxycarbonyl group, a fluoroalkyloxycarbonyl group, and a halogen atom.
The cycloalkylene group for M ₁ is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 4 to 15 carbon atoms.
The cycloalkylene group as M ₁ may have a substituent, and preferred examples of the substituent include an alkyl group, an alkyloxycarbonyl group, a fluoroalkyloxycarbonyl group, and a halogen atom.
When R ^Z1 , R ^Z2 and R ^Z3 represent an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
The alkyl groups as R ^Z1 , R ^Z2 and R ^Z3 may have a substituent, and preferred examples of the substituent include a cycloalkyl group, an alkyloxycarbonyl group, a fluoroalkyloxycarbonyl group and a halogen atom.
When R ^Z1 , R ^Z2 and R ^Z3 represent a halogen atom, they are preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom.

In general formula (RZ- ₁ ), TL ₁ and TL _{2 each} independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a halogen atom; may be formed.
The alkyl groups for TL ₁ and TL ₂ are preferably alkyl groups having 1 to 20 carbon atoms, more preferably alkyl groups having 1 to 10 carbon atoms.
The alkyl groups as TL ₁ and TL ₂ may have a substituent, and preferred examples of the substituent include a cycloalkyl group and a halogen atom.
Cycloalkyl groups for TL ₁ and TL ₂ are preferably cycloalkyl groups having 3 to 20 carbon atoms, more preferably cycloalkyl groups having 5 to 15 carbon atoms.
The cycloalkyl groups as TL ₁ and TL ₂ may have a substituent, and preferred examples of the substituent include an alkyl group and a halogen atom.
The aryl group for TL ₁ and TL ₂ is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms.
The aryl group as TL ₁ and TL ₂ may have a substituent, and preferred examples of the substituent include an alkyl group and a halogen atom.
A halogen atom as TL ₁ and TL ₂ is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom.
TL ₁ and TL ₂ may combine with each other to form a ring, and the ring to be formed is preferably a cycloalkane ring (preferably having 3 to 10 carbon atoms).

In general formula (RZ-1), L ₀ represents a single bond or an alkylene group. L ₀ and any one of TL ₁ and TL ₂ may combine with each other to form a ring.
The alkylene group for L ₀ is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms.
The alkylene group as L ₀ may have a substituent, and preferred examples of the substituent include a cycloalkyl group, an alkyloxycarbonyl group, a fluoroalkyloxycarbonyl group, and a halogen atom.
L ₀ and any one of TL ₁ and TL ₂ may combine with each other to form a ring, and the ring to be formed is preferably a cycloalkane ring (preferably having 3 to 10 carbon atoms).

In general formula (RZ-2), M ₂ and M ₃ each represent a single bond or a divalent linking group. When M ₂ and M ₃ represent a divalent linking group, detailed explanations such as preferred ranges are the same as for M ₁ in general formula (RZ-1).
In general formula (RZ-2), TL ₃ and TL ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and TL ₃ and TL ₄ are bonded together to form a ring. Also good. Detailed descriptions such as preferred ranges of TL ₃ and TL ₄ are the same as those of TL ₁ and TL ₂ in general formula (RZ-1).

In general formula (RZ- ₃ ), M4 and _M5 represent a single bond or a divalent linking group. Detailed descriptions such as a preferred range when M ₄ and M ₅ represent a divalent linking group are the same as for M ₁ in general formula (RZ-1).
In general formula (RZ-3), TL ₅ and TL ₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a halogen atom. Detailed descriptions such as preferred ranges of TL ₅ and TL ₆ are the same as for TL ₁ and TL ₂ in general formula (RZ-1).
In general formula (RZ-3), ZL1 represents a ring structure. ZL1 preferably represents a spiro ring structure.

The group represented by general formula (RZ-3) is preferably a group represented by general formula (RZ-3-1) below.

In general formula (RZ-3-1), M ₄₁ and M ₅₁ each independently represent a single bond or a divalent linking group, TL ₅₁ and TL ₆₁ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, aryl group, or halogen atom. _D12 represents a carbon atom or a tetravalent hydrocarbon group. * represents a binding position.

Detailed descriptions such as the preferred ranges of M ₄₁ , M ₅₁ , TL ₅₁ and TL ₆₁ in general formula (RZ-3-1) refer to M ₄ , M ₅ and TL ₅ in general formula (RZ-3) respectively. and TL ₆ .
In general formula (RZ-3-1), D ₁₂ represents a carbon atom or a tetravalent hydrocarbon group, preferably a carbon atom or a hydrocarbon group having 2 to 10 carbon atoms.

In general formula (RZ- ₄ ), M6 and _M7 represent a single bond or a divalent linking group. Detailed descriptions such as a preferred range when M ₆ and M ₇ represent a divalent linking group are the same as for M ₁ in general formula (RZ-1).
In general formula (RZ-4), TL ₇ and TL ₈ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a halogen atom. Detailed descriptions such as preferred ranges of TL ₇ and TL ₈ are the same as those of TL ₁ and TL ₂ in general formula (RZ-1).

The group represented by general formula (RZ-4) is preferably a group represented by general formula (RZ-4-1) below.

In general formula (RZ-4-1), M ₆₁ and M ₇₁ each independently represent a single bond or a divalent linking group, TL ₇₁ and TL ₈₁ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, aryl group, or halogen atom. _D13 represents a carbon atom or a tetravalent hydrocarbon group. * represents a binding position.

Detailed descriptions such as the preferred ranges of M ₆₁ , M ₇₁ , TL ₇₁ and TL ₈₁ in general formula (RZ-4-1) refer to M ₄ , M ₅ and TL ₅ in general formula (RZ-3) respectively. and TL ₆ .
In general formula (RZ-4-1), D ₁₃ represents a carbon atom or a tetravalent hydrocarbon group, preferably a carbon atom or a hydrocarbon group having 2 to 10 carbon atoms.

The polyester (B) preferably has at least one group represented by any one of the following general formulas (QZ-1) to (QZ-4).

In general formula (QZ-1), M ₁₁ represents a single bond or a divalent linking group, and TL ₁₁ and TL ₁₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a halogen atom. and TL ₁₁ and TL ₁₂ may combine with each other to form a ring. _X11 represents a hydrogen atom, a halogen atom, or a monovalent organic group. X ₁₁ may combine with at least one of TL ₁₁ and TL ₁₂ to form a ring. * represents a binding position.
In general formula (QZ-2), M ₁₂ and M ₁₃ each independently represent a single bond or a divalent linking group, TL ₁₃ and TL ₁₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or represents an aryl group, and TL ₁₃ and TL ₁₄ may combine with each other to form a ring. _X12 represents a hydrogen atom, a halogen atom, or a monovalent organic group. X ₁₂ may combine with at least one of TL ₁₃ and TL ₁₄ to form a ring. * represents a binding position.
In general formula (QZ-3), M ₁₄ and M ₁₅ each independently represent a single bond or a divalent linking group, TL ₁₅ and TL ₁₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, represents an aryl group or a halogen atom. ZL3 represents a ring structure. ZL3 may represent a spiro ring structure. _X13 represents a hydrogen atom, a halogen atom, or a monovalent organic group. * represents a binding position.
In general formula (QZ-4), M ₁₆ and M ₁₇ each independently represent a single bond or a divalent linking group, TL ₁₇ and TL ₁₈ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, represents an aryl group or a halogen atom. ZL4 represents a ring structure. ZL4 may represent a spiro ring structure. _X14 represents a hydrogen atom, a halogen atom, or a monovalent organic group. * represents a binding position.

In general formula (QZ- ₁ ), M11 represents a single bond or a divalent linking group. Detailed descriptions such as a preferred range when M ₁₁ represents a divalent linking group are the same as for M ₁ in general formula (RZ-1).
In general formula (QZ-1), TL ₁₁ and TL ₁₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and TL ₁₁ and TL ₁₂ are bonded to each other to form a ring. Also good. Detailed descriptions such as preferred ranges of TL ₁₁ and TL ₁₂ are the same as those of TL ₁ and TL ₂ in general formula (RZ-1).
In general formula (QZ-1), X ₁₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group. Preferred monovalent organic groups are alkyl groups, cycloalkyl groups and aryl groups. X ₁₁ may combine with at least one of TL ₁₁ and TL ₁₂ to form a ring. Detailed descriptions such as the preferred range of X ₁₁ are the same as for TL ₁ and TL ₂ in general formula (RZ-1). When X ₁₁ combines with at least one of TL ₁₁ and TL ₁₂ to form a ring, the ring to be formed is preferably a cycloalkane ring (preferably having 3 to 10 carbon atoms).

In general formula (QZ-2), M ₁₂ and M ₁₃ each represent a single bond or a divalent linking group. Detailed descriptions such as a preferred range when M ₁₂ and M ₁₃ represent a divalent linking group are the same as for M ₁ in general formula (RZ-1).
In general formula (QZ-2), TL ₁₃ and TL ₁₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and TL ₁₃ and TL ₁₄ are bonded to each other to form a ring. Also good. Detailed descriptions such as preferred ranges of TL ₁₃ and TL ₁₄ are the same as those of TL ₁ and TL ₂ in general formula (RZ-1).
In general formula (QZ-2), X ₁₂ represents a hydrogen atom, a halogen atom, or a monovalent organic group. Preferred monovalent organic groups are alkyl groups, cycloalkyl groups and aryl groups. Detailed descriptions such as the preferred range of X ₁₂ are the same as for TL ₁ and TL ₂ in general formula (RZ-1).

In general formula (QZ-3), M ₁₄ and M ₁₅ each represent a single bond or a divalent linking group. Detailed descriptions such as a preferred range when M ₁₄ and M ₁₅ represent a divalent linking group are the same as for M ₁ in general formula (RZ-1).
In general formula (QZ-3), TL ₁₅ and TL ₁₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a halogen atom. Detailed descriptions such as preferred ranges of TL ₁₅ and TL ₁₆ are the same as those of TL ₁ and TL ₂ in general formula (RZ-1).
In general formula (QZ-3), X ₁₃ represents a hydrogen atom, a halogen atom, or a monovalent organic group. Preferred monovalent organic groups are alkyl groups, cycloalkyl groups and aryl groups. Detailed descriptions such as the preferred range of X ₁₃ are the same as for TL ₁ and TL ₂ in general formula (RZ-1).
In general formula (QZ-3), ZL3 represents a ring structure. ZL3 preferably represents a spiro ring structure.

The group represented by general formula (QZ-3) is preferably a group represented by general formula (QZ-3-1) below.

In general formula (QZ-3-1), M ₄₂ and M ₅₂ each independently represent a single bond or a divalent linking group, TL ₅₂ and TL ₆₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, aryl group, or halogen atom. _D22 represents a carbon atom or a tetravalent hydrocarbon group. _X23 represents a hydrogen atom, a halogen atom, or a monovalent organic group. * represents a binding position.

Detailed descriptions such as the preferred ranges of M ₄₂ , M ₅₂ , TL ₅₂ and TL ₆₂ in general formula (QZ-3-1) refer to M ₄ , M ₅ and TL ₅ in general formula (RZ-3) respectively. and TL ₆ .
In general formula (QZ-3-1), detailed descriptions such as the preferred range of X ₂₃ are the same as those of X ₁₃ in general formula (QZ-3).
In general formula (QZ-3-1), D ₂₂ represents a carbon atom or a tetravalent hydrocarbon group, preferably a carbon atom or a hydrocarbon group having 2 to 10 carbon atoms.

In general formula (QZ-4), M ₁₆ and M ₁₇ each represent a single bond or a divalent linking group. Detailed descriptions such as a preferred range when M ₁₆ and M ₁₇ represent a divalent linking group are the same as for M ₁ in general formula (RZ-1).
In general formula (QZ-4), TL ₁₇ and TL ₁₈ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a halogen atom. Detailed descriptions such as preferred ranges of TL ₁₇ and TL ₁₈ are the same as those of TL ₁ and TL ₂ in general formula (RZ-1).
In general formula (QZ-4), X ₁₄ represents a hydrogen atom, a halogen atom, or a monovalent organic group. Preferred monovalent organic groups are alkyl groups, cycloalkyl groups and aryl groups. Detailed descriptions such as the preferred range of X ₁₄ are the same as for TL ₁ and TL ₂ in general formula (RZ-1).

The group represented by general formula (QZ-4) is preferably a group represented by general formula (QZ-4-1) below.

In general formula (QZ-4-1), M ₆₂ and M ₇₂ each independently represent a single bond or a divalent linking group, TL ₇₂ and TL ₈₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, aryl group, or halogen atom. _D23 represents a carbon atom or a tetravalent hydrocarbon group. _X24 represents a hydrogen atom, a halogen atom, or a monovalent organic group. * represents a binding position.

Detailed descriptions such as the preferred ranges of M ₆₂ , M ₇₂ , TL ₇₂ and TL ₈₂ in general formula (QZ-4-1) refer to M ₄ , M ₅ and TL ₅ in general formula (RZ-3) respectively. and TL ₆ .
In general formula (QZ-4-1), detailed descriptions such as the preferred range of X ₂₄ are the same as those of X ₁₄ in general formula (QZ-4).
In general formula (QZ-4-1), D ₂₃ represents a carbon atom or a tetravalent hydrocarbon group, preferably a carbon atom or a hydrocarbon group having 2 to 10 carbon atoms.

The polyester (B) preferably contains a fluorine atom from the viewpoint that the DRCA to water of the film formed from the composition of the present invention can be increased.

Preferred specific examples of the polyester (B) are listed below, but are not limited thereto.
PE-2 is a polyester having acid-decomposable groups in its main chain and alkali-decomposable groups in its side chains.

The weight average molecular weight (Mw) of the polyester (B) is preferably 4,000 to 30,000, more preferably 6,000 to 20,000, even more preferably 8,000 to 16,000. The dispersity (Mw/Mn) is usually 1.0 to 3.0, preferably 1.5 to 2.6.

Polyester (B) can be obtained by, for example, synthesizing by a known method. For example, it can be synthesized by polycondensation reaction of dicarboxylic acid halide and diol, polyaddition reaction of dianhydride and diol, polycondensation reaction of dicarboxylic acid and diol, ring-opening polymerization of cyclic lactone, and the like.

Polyester (B) may be used individually by 1 type, and may use 2 or more types together.
The content of the polyester (B) in the composition of the present invention is preferably 0.1% by mass or more and 30% by mass or less with respect to the total solid content of the composition of the present invention, and 0.1% by mass It is more preferably 15% by mass or less, further preferably 0.5% by mass or more and 8% by mass or less, particularly preferably 1% by mass or more and 6% by mass or less, and 2% by mass or more and 4% by mass. % or less.

<Photoacid generator (C)>
The composition of the present invention contains a photoacid generator (also referred to as "photoacid generator (C)" or "acid generator").
A photoacid generator is a compound that generates an acid upon exposure to actinic rays or radiation.
As the photoacid generator, a compound that generates an organic acid upon exposure to actinic rays or radiation is preferred. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oximesulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

As the photoacid generator, a known compound that generates an acid upon exposure to actinic rays or radiation can be appropriately selected and used either singly or as a mixture thereof. For example, paragraphs [0125] to [0319] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0086] to [0094] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1 Known compounds disclosed in paragraphs [0323] to [0402] of the specification can be suitably used as the photoacid generator (C).

Suitable examples of the photoacid generator (C) include compounds represented by the following general formulas (ZI), (ZII) and (ZIII).

In the above general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The number of carbon atoms in the organic groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Also, two of R ₂₀₁ to R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (e.g., butylene group, pentylene group) and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —. can.
Z ⁻ represents an anion.

Preferred embodiments of the cation in general formula (ZI) include corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.
The photoacid generator (C) may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by general formula (ZI) are single bonds. Alternatively, it may be a compound having a structure bonded via a linking group.

First, compound (ZI-1) will be described.
Compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in general formula (ZI) is an aryl group, that is, a compound having an arylsulfonium cation.
In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or part of R ₂₀₁ to R ₂₀₃ may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
Arylsulfonium compounds include, for example, triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues, and the like. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group optionally possessed by the arylsulfonium compound is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. Groups such as methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl, and cyclohexyl groups are preferred.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are each independently an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 15 carbon atoms), an aryl group (eg, 6 to 14), an alkoxy group (eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

Next, compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in formula (ZI) each independently represent an aromatic ring-free organic group. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (eg, methyl, ethyl, propyl, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, compound (ZI-3) will be described.
Compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, or a hydroxyl group , represents a nitro group, an alkylthio group or an arylthio group.
_{R6c and R7c each} independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represent an alkyl group, cycloalkyl group, 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxycarbonylalkyl group, allyl group or vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may each combine to form a ring structure. This ring structure may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings in which two or more of these rings are combined. The ring structure includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

Examples of groups formed by bonding two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
^Zc- represents an anion.

Next, compound (ZI-4) will be described.
Compound (ZI-4) is represented by the following general formula (ZI-4).

In general formula (ZI-4),
l represents an integer of 0 to 2;
r represents an integer of 0 to 8;
_R13 represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have a substituent.
R ₁₄ represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. These groups may have a substituent. R ₁₄ each independently represents the above group such as a hydroxyl group when there are more than one.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be joined together to form a ring. When two R ₁₅ are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R ₁₅ are alkylene groups, preferably joined together to form a ring structure.
Z ⁻ represents an anion.

In general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched, preferably having 1 to 10 carbon atoms, methyl group, ethyl group, n- A butyl group, a t-butyl group, or the like is more preferable.

Next, general formulas (ZII) and (ZIII) will be described.
In general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
The aryl group represented by R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of skeletons of aryl groups having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).

The aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, 3 to 3 carbon atoms). 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
Z ⁻ represents an anion.

Z - in general formula (ZI), Z ^- in general formula (ZII), Zc ^- in general formula (ZI-3), ^{and Z - in} general formula (ZI-4) are represented by the following general formula (3) The anions represented are preferred.

In general formula (3),
o represents an integer of 1 to 3; p represents an integer from 0 to 10; q represents an integer from 0 to 10;
Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₄ and R _{5 each} independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at _least one fluorine atom; but can be different.
L represents a divalent linking group, and when multiple Ls are present, they may be the same or different.
W represents an organic group containing a cyclic structure.
o represents an integer of 1 to 3; p represents an integer from 0 to 10; q represents an integer from 0 to 10;

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. Also, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group. Xf is more preferably a fluorine atom or _CF3 . In particular, both Xf are preferably fluorine atoms.

_R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at _least one fluorine atom. R ₄ and R ₅ when there are more than one may be the same or different.
The alkyl groups for R ₄ and R ₅ may have substituents, and preferably have 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.
Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as those of Xf in general formula (3).

L represents a divalent linking group, and when multiple Ls are present, they may be the same or different.
Examples of divalent linking groups include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, - SO—, —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a combination of a plurality of these and a divalent linking group. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene group-, -OCO-alkylene group-, -CONH- Alkylene group- or -NHCO-alkylene group- is preferred, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene group- or -OCO-alkylene group- is more preferred.

W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.
Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
Alicyclic groups may be monocyclic or polycyclic. Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

Aryl groups may be monocyclic or polycyclic. The aryl group includes, for example, phenyl group, naphthyl group, phenanthryl group and anthryl group.
A heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further suppress acid diffusion. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Non-aromatic heterocycles include, for example, tetrahydropyran, lactone, sultone and decahydroisoquinoline rings. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the resins described above. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

The cyclic organic group may have a substituent. Examples of this substituent include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic or spirocyclic). preferably 3 to 20 carbon atoms), aryl groups (preferably 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acids Ester groups are mentioned. In addition, carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic|annular organic group.

Examples of anions represented by the general formula (3) include SO ₃ ⁻ —CF ₂ —CH ₂ —OCO-(L)q′-W, SO ₃ ^— —CF ₂ —CHF—CH ₂ —OCO-(L) q′-W, SO ₃ ⁻ —CF ₂ —COO-(L)q′-W, SO ₃ ⁻ —CF ₂ —CF ₂ —CH ₂ —CH ₂ —(L)qW, SO ₃ ^— —CF ₂ -CH(CF ₃ )-OCO-(L)q'-W is preferred. Here, L, q and W are the same as in general formula (3). q' represents an integer from 0 to 10;

In one embodiment, Z - in general formula (ZI), Z ^- in general formula (ZII), Zc ^- in general formula (ZI-3), ^{and Z - in} general formula (ZI-4) are the following general Anions of formula (4) are also preferred.

In general formula (4),
X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms.
X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. At least one of X ^B3 and X ^B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both of X ^B3 and X ^B4 are a fluorine atom or a monovalent organic group having a fluorine atom is more preferred. More preferably, both X ^B3 and X ^B4 are fluorine-substituted alkyl groups. L, q and W are the same as in general formula (3).

Z - in general formula (ZI), Z ^- in general formula (ZII), Zc ^- in general formula (ZI-3), ^{and Z - in} general formula (ZI-4) are represented by the following general formula (5) The anions represented are preferred.

In general formula (5), each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Each Xb independently represents an organic group having no hydrogen atom or fluorine atom. The definitions and preferred embodiments of o, p, q, R ₄ , R ₅ , L, and W are the same as in general formula (3).

Z - in general formula (ZI), Z ^- in general formula (ZII), Zc ^- in general formula (ZI-3), ^{and Z - in} general formula (ZI-4) may be benzenesulfonate anions. A benzenesulfonate anion substituted by a branched alkyl group or a cycloalkyl group is often preferred.

Z - in general formula (ZI), Z ^- in general formula (ZII), Zc ^- in general formula (ZI-3), ^{and Z - in} general formula (ZI-4) are represented by the following general formula (SA1) An aromatic sulfonate anion represented by is also preferred.

In formula (SA1),
Ar represents an aryl group and may further have a substituent other than the sulfonate anion and -(D-B) group. Substituents which may be further included include a fluorine atom and a hydroxyl group.

n represents an integer of 0 or more. n is preferably 1-4, more preferably 2-3, most preferably 3.

D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group consisting of a combination of two or more thereof. .

B represents a hydrocarbon group.

Preferably D is a single bond and B is an aliphatic hydrocarbon structure. B is more preferably an isopropyl group or a cyclohexyl group.

Preferred examples of the sulfonium cation in general formula (ZI) and the iodonium cation in general formula (ZII) are shown below.

Preferable examples of the anion Z ⁻ in general formula (ZI) and general formula (ZII), Zc ⁻ in general formula (ZI-3), and Z ⁻ in general formula (ZI-4) are shown below.

Any combination of the above cations and anions can be used as the photoacid generator.

The acid generator may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of the polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
The photoacid generator is preferably in the form of a low molecular weight compound.
When the acid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less.
When the acid generator is in the form of being incorporated into part of the polymer, it may be incorporated into part of the resin (A) described above, or may be incorporated into a resin different from the resin (A).
The acid generator may be used singly or in combination of two or more.
The content of the acid generator in the composition of the present invention (in the case where multiple types are present, the total amount) is preferably 0.1 to 35% by mass, based on the total solid content of the composition of the present invention, and 0.1 to 35% by mass. 5 to 25% by mass is more preferable, 3 to 20% by mass is even more preferable, and 3 to 15% by mass is particularly preferable.
When the compound represented by the above general formula (ZI-3) or (ZI-4) is included as an acid generator, the content of the acid generator contained in the composition (the total if multiple types are present). is preferably 5 to 35% by mass, more preferably 7 to 30% by mass, based on the total solid content of the composition.

<Acid diffusion control agent (D)>
The composition of the present invention preferably contains an acid diffusion controller (D). The acid diffusion control agent (D) traps the acid generated from the acid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. . For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a relatively weak acid to an acid generator, and a nitrogen atom. and a low-molecular-weight compound (DD) having a group that leaves under the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation portion, or the like can be used as an acid diffusion controller. Known acid diffusion control agents can be used as appropriate in the composition of the present invention. For example, paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1. The known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 are suitably used as the acid diffusion control agent (D). can.

Preferred examples of the basic compound (DA) include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl represents a group (6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.

The alkyl groups in general formulas (A) and (E) may be substituted or unsubstituted. Regarding the above alkyl group, the substituted alkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, or piperidine are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, or an aniline derivative having a hydroxyl group and/or an ether bond is more preferred.

A basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)") has a proton acceptor functional group, and actinic rays or It is a compound whose proton acceptor property is reduced or lost, or whose proton acceptor property is changed to acidic by being decomposed by irradiation with radiation.

The proton-accepting functional group is a functional group having electrons or a group capable of electrostatically interacting with protons, for example, a functional group having a macrocyclic structure such as cyclic polyether, It means a functional group having a nitrogen atom with a non-contributing lone pair of electrons. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

Preferred partial structures of proton-accepting functional groups include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole, and pyrazine structures.

The compound (DB) is decomposed by exposure to actinic rays or radiation to reduce or eliminate its proton acceptor property, or to generate a compound whose proton acceptor property is changed to an acidic one. Here, the reduction or disappearance of proton acceptor property, or the change from proton acceptor property to acidity is a change in proton acceptor property due to the addition of protons to the proton acceptor functional group. means that when a proton adduct is produced from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.
Proton acceptor properties can be confirmed by measuring pH.

The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably -13<pKa<-1, and -13<pKa. <-3 is more preferred.

The acid dissociation constant pKa means the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Kagaku Binran (II) (revised 4th edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). A lower acid dissociation constant pKa indicates a higher acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, a value based on a database of Hammett's substituent constants and known literature values can be obtained by calculation using Software Package 1 described below. All pKa values described herein are calculated using this software package.

Software Package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

An onium salt (DC), which is a relatively weak acid relative to the acid generator, can be used as an acid diffusion control agent in the compositions of the present invention.
When an acid generator and an onium salt that generates an acid that is relatively weak to the acid generated from the acid generator are mixed and used, the acid generated from the acid generator by actinic rays or irradiation of radiation When an acid collides with an onium salt with an unreacted weak acid anion, salt exchange releases the weak acid to yield an onium salt with a strong acid anion. In this process, the strong acid is exchanged for a weak acid with a lower catalytic activity, so that the acid is apparently deactivated and acid diffusion can be controlled.

As the onium salt which becomes a relatively weak acid relative to the acid generator, compounds represented by the following general formulas (d1-1) to (d1-3) are preferred.

In the formula, R ⁵¹ is an optionally substituted hydrocarbon group, Z ^2c is an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon is not substituted with a fluorine atom), R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or arylene group, and Rf is a fluorine atom and each M ⁺ is independently an ammonium cation, a sulfonium cation, or an iodonium cation.

Preferred examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cations exemplified by general formula (ZI) and the iodonium cations exemplified by general formula (ZII).

An onium salt (DC), which is a relatively weak acid with respect to an acid generator, is a compound having a cation site and an anion site in the same molecule, and in which the cation site and the anion site are linked by a covalent bond (hereinafter referred to as , also referred to as “compound (DCA)”).
The compound (DCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

In general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond that links the cation site and the anion site.
—X ^— represents an anionic moiety selected from —COO ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , and —N ⁻ —R ₄ . R ₄ has a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) ₂ -), and a sulfinyl group (-S(=O)- ) represents a monovalent substituent having at least one of
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may combine with each other to form a ring structure. In general formula (C-3), two of R ₁ to R ₃ together represent one divalent substituent, which may be bonded to the N atom via a double bond.

Examples of substituents having 1 or more carbon atoms for R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino A carbonyl group, an arylaminocarbonyl group, and the like can be mentioned. An alkyl group, a cycloalkyl group, or an aryl group is preferred.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two of these A group formed by combining the above and the like can be mentioned. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

A low-molecular-weight compound (DD) having a nitrogen atom and a group that leaves under the action of an acid (hereinafter also referred to as "compound (DD)") has a group that leaves under the action of an acid on the nitrogen atom. It is preferably an amine derivative having
The group that leaves by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group. .
The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, even more preferably 100-500.
Compound (DD) may have a carbamate group with a protecting group on the nitrogen atom. A protective group constituting a carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group ( preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb's may be linked together to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, a functional group such as an oxo group, an alkoxy group, or It may be substituted with a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, more preferably a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two Rb's to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
Specific structures of the group represented by general formula (d-1) include, but are not limited to, structures disclosed in paragraph [0466] of US Patent Publication No. US2012/0135348A1. .

Compound (DD) preferably has a structure represented by the following general formula (6).

In general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l+m=3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ra's may be the same or different, and the two Ra's may be linked together to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocyclic ring may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same definition as Rb in formula (d-1) above, and preferred examples are also the same.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are each independently substituted with an alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. It may be substituted with the same groups as the groups described above as good groups.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) for Ra include the same groups as the specific examples described above for Rb. be done.
Specific structures of the particularly preferred compound (DD) in the present invention include, but are limited to, compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/0135348A1. is not.

The onium salt compound (DE) having a nitrogen atom in the cation moiety (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cation moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. More preferably all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Moreover, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly bonded to the nitrogen atom. Preferred specific structures of compound (DE) include, but are not limited to, compounds disclosed in paragraph [0203] of US Patent Application Publication No. 2015/0309408A1.

Preferred examples of the acid diffusion controller (D) are shown below.

In the composition of the present invention, the acid diffusion controller (D) may be used singly or in combination of two or more.
The content of the acid diffusion control agent (D) in the composition (the total if multiple types are present) is preferably 0.1 to 20% by mass, preferably 1 to 15% by mass, based on the total solid content of the composition. % is more preferred.

<Solvent (F)>
The composition of the invention usually contains a solvent.
Known resist solvents can be used as appropriate in the composition of the present invention. For example, paragraphs [0665]-[0670] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0210]-[0235] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1 Known solvents disclosed in paragraphs [0424] to [0426] of the specification and paragraphs [0357] to [0366] of US Patent Application Publication No. 2016/0274458A1 can be preferably used.
Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), Organic solvents such as monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates can be mentioned.

As the organic solvent, a mixed solvent in which a solvent containing a hydroxyl group in its structure and a solvent containing no hydroxyl group are mixed may be used.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-described exemplary compounds can be appropriately selected. (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate are more preferred. Further, as the solvent containing no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, or alkyl acetate are preferable, and among these, propylene glycol monomethyl Ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferable, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclohexanone, Cyclopentanone or 2-heptanone are more preferred. Propylene carbonate is also preferred as the solvent containing no hydroxyl group.
The mixing ratio (mass ratio) of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. preferable. A mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is preferable from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

<Crosslinking agent (G)>
The composition of the present invention may contain a compound that cross-links the resin by the action of acid (hereinafter also referred to as a cross-linking agent (G)). As the cross-linking agent (G), known compounds can be appropriately used. For example, cross-linking known compounds disclosed in paragraphs [0379] to [0431] of US Patent Application Publication No. 2016/0147154A1 and paragraphs [0064] to [0141] of US Patent Application Publication No. 2016/0282720A1. It can be suitably used as an agent (G).
The cross-linking agent (G) is a compound having a cross-linkable group capable of cross-linking the resin. and an oxetane ring.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring.
The cross-linking agent (G) is preferably a compound (including resin) having two or more cross-linkable groups.
The cross-linking agent (G) is more preferably a phenol derivative, a urea compound (compound having a urea structure) or a melamine compound (compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.
The cross-linking agents may be used singly or in combination of two or more.
The content of the cross-linking agent (G) is preferably 1 to 50% by mass, preferably 3 to 40% by mass, more preferably 5 to 30% by mass, based on the total solid content of the composition of the present invention.

<Surfactant (H)>
The compositions of the present invention may or may not contain a surfactant. When a surfactant is contained, a fluorine-based and/or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both fluorine atoms and silicon atoms ) is preferred.

Since the composition of the present invention contains a surfactant, it is possible to obtain a resist pattern with good sensitivity and resolution, good adhesion and few development defects when using an exposure light source of 250 nm or less, particularly 220 nm or less. can.
Fluorine-based and/or silicon-based surfactants may include surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425.
Also, other surfactants than the fluorine-based and/or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 can be used.

These surfactants may be used singly or in combination of two or more.
When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, and 0.0005 to 1% by mass, based on the total solid content of the composition. more preferred.

<Resin (J)>
When the composition of the present invention contains a cross-linking agent (G), the composition of the present invention may contain an alkali-soluble resin (J) having a phenolic hydroxyl group (hereinafter also referred to as "resin (J)"). preferable. Resin (J) preferably contains a repeating unit having a phenolic hydroxyl group.
In this case, typically a negative pattern is preferably formed.
The cross-linking agent (G) may be in the form supported by the resin (J).
The resin (J) may contain the acid-decomposable group described above.

Although the repeating unit having a phenolic hydroxyl group contained in the resin (J) is not particularly limited, it is preferably a repeating unit represented by the following general formula (II).

In the general formula (II),
R ₂ represents a hydrogen atom, an optionally substituted alkyl group (preferably a methyl group), or a halogen atom (preferably a fluorine atom).
B' represents a single bond or a divalent linking group.
Ar' represents an aromatic ring group.
m represents an integer of 1 or more.
The resin (J) may be used alone or in combination of two or more.
The content of resin (J) in the total solid content of the composition of the present invention is generally 30% by mass or more. 40% by mass or more is preferable, and 50% by mass or more is more preferable. Although the upper limit is not particularly limited, it is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.
Resins disclosed in paragraphs [0142] to [0347] of US Patent Application Publication No. 2016/0282720A1 can be suitably used as the resin (J).

(Other additives)
The composition of the present invention may further contain acid multipliers, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, dissolution accelerators, and the like.

<Preparation method>
The film thickness of the actinic ray-sensitive film or radiation-sensitive film comprising the composition of the present invention is preferably 200 nm or less, more preferably 100 nm or less, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improve the coatability or film-forming property.
The solid content concentration of the composition of the present invention is generally 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, more preferably 2.0 to 5.3% by mass. The solid content concentration is the mass percentage of the mass of other resist components excluding the solvent relative to the total mass of the composition.

The composition of the present invention is used by dissolving the above components in a given organic solvent, preferably in the above mixed solvent, filtering the mixture, and coating it on a given support (substrate). The pore size of the filter used for filtration is preferably 0.1 µm or less, more preferably 0.05 µm or less, and even more preferably 0.03 µm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (JP 2002-62667), cyclic filtration may be performed, and multiple types of filters are connected in series or in parallel. Filtration may be performed by connecting to Also, the composition may be filtered multiple times. Furthermore, before and after filtering, the composition may be subjected to a degassing treatment or the like.

<Application>
The composition of the present invention relates to an actinic ray- or radiation-sensitive resin composition that reacts with irradiation of actinic rays or radiation to change its properties. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), circuit board manufacturing such as liquid crystals or thermal heads, manufacturing of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray- or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition. A resist pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, MEMS (Micro Electro Mechanical Systems), and the like.

[Actinic Ray-Sensitive or Radiation-Sensitive Film, Pattern Forming Method]
The present invention also relates to a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition. The pattern forming method of the present invention will be described below. In addition to the description of the pattern forming method, the actinic ray-sensitive or radiation-sensitive film (typically, resist film) of the present invention will also be described. The actinic ray-sensitive or radiation-sensitive film of the present invention preferably has a dynamic receding contact angle with water of 80° or more before exposure.

The pattern forming method of the present invention comprises
(i) a step of forming an actinic ray-sensitive or radiation-sensitive film on a support using the actinic ray-sensitive or radiation-sensitive resin composition described above (film-forming step);
(ii) a step of irradiating the actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation (exposure step);
(iii) a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation with a developer (developing step).

The pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further include the following steps.
In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be liquid immersion exposure.
The pattern forming method of the present invention preferably includes (iv) a pre-heating (PB: PreBake) step before the (ii) exposure step.
The pattern forming method of the present invention preferably includes (v) a post exposure bake (PEB) step after (ii) the exposure step and (iii) before the development step.
The pattern forming method of the present invention may include (ii) the exposure step multiple times.
The pattern forming method of the present invention may include (iv) the preheating step multiple times.
The pattern forming method of the present invention may include (v) the post-exposure heating step multiple times.

In the pattern forming method of the present invention, the above-described (i) film formation step, (ii) exposure step, and (iii) development step can be performed by generally known methods.
If necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), antireflection film) is formed between the actinic ray-sensitive or radiation-sensitive film and the support. may As the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (topcoat) may be formed on the actinic ray-sensitive or radiation-sensitive film. A known material can be used as appropriate for the protective film. For example, US2007/0178407, US2008/0085466, US2007/0275326, US2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016/157988A can be preferably used. As the composition for forming a protective film, a composition containing the acid diffusion control agent described above is preferable.
A protective film may be formed on the actinic ray-sensitive or radiation-sensitive film containing the hydrophobic resin.
As the hydrophobic resin, known resins can be appropriately selected and used either alone or as a mixture thereof. For example, the known resins disclosed in paragraphs [0451] to [0704] of US Patent Application Publication No. 2015/0168830A1 and paragraphs [0340] to [0356] of US Patent Application Publication No. 2016/0274458A1 are used as hydrophobic It can be suitably used as a flexible resin. Further, the repeating units disclosed in paragraphs [0177] to [0258] of US Patent Application Publication No. 2016/0237190A1 are also preferable as repeating units constituting the hydrophobic resin.

The support is not particularly limited, and is generally used in the manufacturing process of semiconductors such as ICs, the manufacturing process of circuit boards such as liquid crystals or thermal heads, and the lithography process of other photofabrications. A substrate can be used. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ , and SiN.

The heating temperature is preferably 70 to 130° C., more preferably 80 to 120° C. in both the (iv) pre-heating step and (v) post-exposure heating step.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds in both (iv) the preheating step and (v) the post-exposure heating step.
Heating can be performed by means provided in the exposure device and the development device, and may be performed using a hot plate or the like.

The wavelength of the light source used in the exposure process is not limited, but examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferred, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ₍ 157 nm), X-ray, EUV (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam are preferred.

(iii) In the developing step, an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer) may be used.

As the alkaline developer, quaternary ammonium salts such as tetramethylammonium hydroxide are usually used, but in addition to this, alkaline aqueous solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines, and cyclic amines are also used. Available.
Furthermore, the alkaline developer may contain appropriate amounts of alcohols and/or surfactants. The alkali concentration of the alkali developer is usually 0.1 to 20 mass %. The pH of the alkaline developer is usually 10-15.
The time for developing with an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.

The organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. It is preferable to have

Ketone solvents include, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butanoic acid Butyl, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate and the like can be mentioned.

As alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents, the solvents disclosed in paragraphs [0715] to [0718] of US Patent Application Publication No. 2016/0070167A1 can be used.

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass with respect to the total amount of the developer. The following are more preferable, and 95% by mass or more and 100% by mass or less are particularly preferable.

The organic developer can contain a suitable amount of a known surfactant as required.

The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, relative to the total amount of the developer.

The organic developer may contain the acid diffusion control agent described above.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), a method of raising the developer on the surface of the substrate by surface tension and resting the substrate for a certain period of time (paddle method), and a substrate. A method of spraying the developer onto the surface (spray method) or a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method) is applied. can do.

A step of developing using an alkaline aqueous solution (alkali developing step) and a step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined. As a result, the pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern can be formed.

(iii) It is preferable to include a step of washing with a rinse solution (rinse step) after the development step.

Pure water, for example, can be used as the rinsing solution used in the rinsing step after the developing step using the alkaline developer. The pure water may contain an appropriate amount of surfactant. In this case, after the developing process or the rinsing process, a process of removing the developing solution or rinsing solution adhering to the pattern with a supercritical fluid may be added. Further, after rinsing or supercritical fluid treatment, heat treatment may be performed to remove moisture remaining in the pattern.

The rinsing liquid used in the rinsing step after the development step using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a common solution containing an organic solvent can be used. As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. is preferred.
Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent are the same as those described for the developer containing an organic solvent.
As the rinse solution used in the rinse step in this case, a rinse solution containing a monohydric alcohol is more preferable.

Linear, branched, or cyclic monohydric alcohols may be used as monohydric alcohols used in the rinsing step. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 -heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methylisobutylcarbinol. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methylisobutylcarbinol. .

A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good developing properties can be obtained.

The rinse liquid may contain an appropriate amount of surfactant.
In the rinsing step, the substrate developed with the organic developer is washed with a rinse containing an organic solvent. The method of the cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse solution onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a bath filled with the rinse solution for a certain period of time. A method (dip method), a method of spraying a rinse liquid onto the substrate surface (spray method), or the like can be applied. Among them, it is preferable that the cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a rotation speed of 2,000 to 4,000 rpm to remove the rinse solution from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating process removes the developer and rinse remaining between the patterns and inside the patterns. In the heating step after the rinsing step, the heating temperature is usually 40 to 160°C, preferably 70 to 95°C, and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention (e.g., resist solvent, developer, rinse, antireflection film-forming composition, or The topcoat-forming composition, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above various materials is preferably 1 ppm (parts per million) or less, more preferably 100 ppt (parts per trillion) or less, further preferably 10 ppt or less, and substantially free of ( below the detection limit of the measuring device) is particularly preferred.

As a method for removing impurities such as metals from the above various materials, for example, filtration using a filter can be mentioned. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes and/or materials may be used in combination. Further, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulation filtration process. As the filter, those with reduced extractables as disclosed in Japanese Patent Application Publication No. 2016-201426 (JP 2016-201426) are preferable.
In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of metal adsorbents include those disclosed in Japanese Patent Application Publication No. 2016-206500 (JP 2016-206500).
In addition, as a method for reducing impurities such as metals contained in the various materials, selecting raw materials with a low metal content as raw materials constituting various materials, performing filter filtration on raw materials constituting various materials, Alternatively, distillation may be performed under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark). It is also preferable to apply glass lining to all processes of manufacturing equipment for synthesizing various materials (resins, photo-acid generators, etc.) for resist components in order to reduce metals to the ppt order. The preferred conditions for the filter filtration carried out by the method are the same as those described above.

In order to prevent contamination of impurities, the above various materials are described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (JP 2015-123351), Japanese Patent It is preferably stored in a container described in Published Application No. 2017-13804 (Japanese Patent Application Laid-Open No. 2017-13804).

A method for improving surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. As a method of improving the surface roughness of the pattern, for example, there is a method of treating the resist pattern with hydrogen-containing gas plasma, disclosed in US Patent Application Publication No. 2015/0104957. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Publication No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
Further, the resist pattern formed by the above method is, for example, the spacer disclosed in Japanese Patent Application Publication No. 1991-270227 (JP-A-3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as the core of the process.

[Method for producing electronic device]
The present invention also relates to a method of manufacturing an electronic device, including the pattern forming method described above. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted in electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.). be done.

〔polyester〕
The present invention is represented by the following general formula (1), and at least one of E ₁ and E ₂ in the following general formula (1) is represented by any one of the following general formulas (1d) to (1f) It also relates to polyesters, representing groups.
General formula (1) and general formulas (1d) to (1f) are as described above.

In general formula (1), E ₁ and E ₂ are each independently a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, an aromatic group, or a group formed by combining these represents

In general formula (1d), W ₇ and W ₈ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₄ is a cycloalkylene group, a spirocyclic group optionally containing a hetero atom, or arylene Y ₁ and Y ₂ each independently represent a single bond or a divalent linking group, Q ₅ represents an organic group having a halogen atom, and k2 represents an integer of 1 or more. When k2 represents an integer of 2 or more, the plurality of Y ₁ s, the plurality of Y ₂ s, and the plurality of Q ₅ may be the same or different.
In general formula (1e), W ₉ , W ₁₀ and W ₁₁ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₅ and Z ₆ each independently represent a cycloalkylene group, a heteroatom represents a spirocyclic group or an arylene group, Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a single bond or a divalent linking group, and Q ₆ and Q ₇ each represent Each independently represents an organic group having a halogen atom, and k3 and k4 each independently represents an integer of 1 or more. When k3 represents an integer of 2 or more, multiple Y ₃ s, multiple Y ₄ s, and multiple Q _6s may be the same or different. When k4 represents an integer of 2 or more, the plurality of Y ₅ s, the plurality of Y ₆ s, and the plurality of Q ₇ may be the same or different.
_In general formula ₍ 1f), Y7 and Y8 each independently represent a single bond or a divalent linking group, _Q8 represents a hydrogen atom or a substituent, and _Q9 represents an organic group having a halogen atom. , k5 represents an integer of 1 or more, and k6 represents 1 or 2. When k5 represents an integer of 2 or more, multiple Y ₇ , multiple Y ₈ , multiple Q ₈ , and multiple Q ₉ may be the same or different.

The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. The scope of the present invention is not limitedly interpreted by the examples shown below.

<Synthesis of Compound-A>
36.97 g of 1,1,1,3,3,3-hexafluoro-2-propanol (manufactured by Tokyo Kasei Co., Ltd.), pyridine (Tokyo Kasei Co., Ltd.) were added to a three-necked flask equipped with a condenser and a stirrer. 16.61 g of methylene chloride and 178 g of methylene chloride were weighed and cooled to -10°C. Then, 40.3 g of bromoacetyl bromide (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise over 1 hour. After dropping, the mixture was stirred at room temperature (20° C.) for 3 hours, transferred to a separating funnel, and washed with 100 mL of water three times. After concentrating the organic layer, it was purified by distillation to obtain 38.0 g of Compound-A. It was confirmed by NMR (nuclear magnetic resonance) that it was the target product.

<Synthesis of (PE-1)>
4.48 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Tokyo Kasei Co., Ltd.), 2,2-bis(4-hydroxycyclohexyl ) Propane 4.81 g (manufactured by Tokyo Kasei Co., Ltd.), N, N-dimethylaminopyridine 0.24 g (manufactured by Wako Pure Chemical Industries, Ltd.), pyridine 3.32 g (manufactured by Wako Pure Chemical Industries, Ltd.), super dehydration 17.3 g of tetrahydrofuran was weighed out and stirred at room temperature. Then, the inner temperature was raised to 60° C. and the reaction was carried out for 10 hours. This was poured into 300 ml of 0.5 mol/L aqueous hydrochloric acid and 50 mL of methanol, filtered and dried to obtain 9.5 g of (PE-1A). (PE-1A) had a weight average molecular weight of 11,200.
9.5 g of (PE-1A), 0.24 g of N,N-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.), and 22.2 g of ultra-dehydrated tetrahydrofuran were weighed, stirred at 45 ° C. and dissolved. let me Then, 8.4 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (manufactured by Tokyo Kasei Co., Ltd.), 10.1 g of 1,1,1,3,3,3-hexafluoro-2-propanol. 8 g (manufactured by Tokyo Kasei Co., Ltd.) was added and reacted at 60° C. for 8 hours. After the reaction, the reaction mixture was cooled to room temperature, diluted with 20 mL of acetone, added with 4.4 g of methanesulfonic acid, filtered to remove precipitates, poured into 300 mL of water, and filtered. Vacuum drying was carried out at 40° C. for 8 hours to obtain 10.2 g of polyester (PE-1). The polyester (PE-1) had a weight average molecular weight of 12800 and a dispersity (Mw/Mn) of 2.21.

<Synthesis of (PE-2)>
2.92 g of 2,5-dimethyl-2,5-hexanediol (manufactured by Tokyo Kasei Co., Ltd.) and 30.0 g of ultra-dehydrated tetrahydrofuran were weighed and dissolved in a nitrogen-purged flask, and the mixture was heated to -78°C. cooled. To this, 18.0 g of butyl lithium (about 15% by mass hexane solution, about 1.6 mol/L) was added dropwise over 1 hour. After dropping, 4.48 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Tokyo Kasei Co., Ltd.) was added, stirred for 30 minutes, then stirred at 0° C. for 1 hour, and Stirred for 8 hours. To this, 20 g of tetrahydrofuran was added and dissolved. This was poured into 300 mL of water and filtered. The filtrate was collected, dissolved in 30 mL of tetrahydrofuran, poured into 500 mL of water, filtered, washed with water and dried at 40° C. for 1 day to obtain 9.2 g of polyester (PE-2A). The polyester (PE-2A) had a weight average molecular weight of 10,500 and a dispersity (Mw/Mn) of 1.97.
9.2 g of (PE-2A), 0.24 g of N,N-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.), and 22.2 g of ultra-dehydrated tetrahydrofuran were weighed, stirred at 45 ° C. and dissolved. let me Then, 8.4 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (manufactured by Tokyo Kasei Co., Ltd.), 10.1 g of 1,1,1,3,3,3-hexafluoro-2-propanol. 8 g (manufactured by Tokyo Kasei Co., Ltd.) was added and reacted at 45° C. for 10 hours. After the reaction, cool to room temperature, add 300 mL of ethyl acetate, wash with 100 mL of 0.01 mol/L hydrochloric acid aqueous solution, then with 300 mL of water, then with 200 mL of saturated thorium chloride aqueous solution, dry over sodium sulfate, filter with filter paper. While filtering, it was transferred to an eggplant-shaped flask and concentrated using an evaporator. This concentrate was dissolved in 30 mL of tetrahydrofuran, poured into 500 mL of water, filtered, and vacuum-dried at 40° C. for 8 hours to obtain 8.9 g of polyester (PE-2). The polyester (PE-2) had a weight average molecular weight of 12,700 and a dispersity (Mw/Mn) of 2.11.

<Synthesis of (PE-3)>
3.96 g of meso-butane-1,2,3,4-tetracarboxylic dianhydride (manufactured by Tokyo Kasei Co., Ltd.), 2,2-bis(4 -Hydroxycyclohexyl)propane 4.81 g (manufactured by Tokyo Kasei Co., Ltd.), N,N-dimethylaminopyridine 0.24 g (manufactured by Wako Pure Chemical Industries, Ltd.), pyridine 3.32 g (manufactured by Wako Pure Chemical Industries, Ltd.) , superdehydrated N-methylpyrrolidone 16.3 was weighed out and stirred at room temperature. Then, the internal temperature was raised to 65° C. and the reaction was carried out for 18 hours. This was poured into 300 ml of 0.5 mol/L aqueous hydrochloric acid and 50 mL of methanol, filtered and dried to obtain 8.2 g of (PE-3A). (PE-3A) had a weight average molecular weight of 11,800.
8.2 g of (PE-3A), 0.24 g of N,N-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.), and 22.2 g of ultra-dehydrated tetrahydrofuran were weighed, stirred at 45 ° C. and dissolved. let me Then, 8.4 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (manufactured by Tokyo Kasei Co., Ltd.), 10.1 g of 1,1,1,3,3,3-hexafluoro-2-propanol. 8 g (manufactured by Tokyo Kasei Co., Ltd.) was added and reacted at 60° C. for 8 hours. After the reaction, the reaction mixture was cooled to room temperature, diluted with 20 mL of acetone, added with 4.4 g of methanesulfonic acid, filtered to remove precipitates, poured into 300 mL of water, and filtered. Vacuum drying was carried out at 40° C. for 8 hours to obtain 8.5 g of polyester (PE-3). The polyester (PE-3) had a weight average molecular weight of 13,200 and a dispersity (Mw/Mn) of 2.25.

<Synthesis of (PE-4)>
4.48 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Tokyo Kasei Co., Ltd.), 2,2-bis(4-hydroxycyclohexyl ) Propane 4.81 g (manufactured by Tokyo Kasei Co., Ltd.), N, N-dimethylaminopyridine 0.24 g (manufactured by Wako Pure Chemical Industries, Ltd.), pyridine 3.32 g (manufactured by Wako Pure Chemical Industries, Ltd.), super dehydration 17.3 g of tetrahydrofuran was weighed out and stirred at room temperature. Then, the inner temperature was raised to 60° C. and the reaction was carried out for 10 hours. This was poured into 300 ml of 0.5 mol/L aqueous hydrochloric acid and 50 mL of methanol, filtered and dried to obtain 9.4 g of (PE-4A). (PE-4A) had a weight average molecular weight of 11,800.
9.4 g of (PE-4A), 0.24 g of N,N-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.), 2.76 g of potassium carbonate, and 30.0 g of super-dehydrated N-methylpyrrolidone were weighed. , and stirred at 45°C. Then, 12.7 g of Compound-A was added and reacted at 45° C. for 8 hours. After the reaction, cool to room temperature, add 300 mL of ethyl acetate, wash with 200 mL of water, 100 mL of 0.2 mol/L hydrochloric acid aqueous solution, then 300 mL of water, then wash with 200 mL of saturated aqueous thorium chloride solution, and wash with sodium sulfate. After drying, while filtering with filter paper, it was transferred to an eggplant-shaped flask and concentrated using an evaporator. This concentrate was dissolved in 50 mL of tetrahydrofuran, poured into 500 mL of water, filtered, and vacuum-dried at 40° C. for 8 hours to obtain 8.3 g of polyester (PE-4). The polyester (PE-4) had a weight average molecular weight of 13,800 and a dispersity (Mw/Mn) of 2.26.

<Synthesis of (PE-5)>
3.96 g of meso-butane-1,2,3,4-tetracarboxylic dianhydride (manufactured by Tokyo Kasei Co., Ltd.), 2,2-bis(4 -Hydroxycyclohexyl)propane 4.81 g (manufactured by Tokyo Kasei Co., Ltd.), N,N-dimethylaminopyridine 0.24 g (manufactured by Wako Pure Chemical Industries, Ltd.), pyridine 3.32 g (manufactured by Wako Pure Chemical Industries, Ltd.) , 17.3 g of ultra-dehydrated tetrahydrofuran was weighed out and stirred at room temperature. Then, the inner temperature was raised to 60° C. and the reaction was carried out for 10 hours. This was poured into 300 ml of 0.5N aqueous hydrochloric acid and 50 mL of methanol, filtered and dried to obtain 9.4 g of (PE-5A). (PE-5A) had a weight average molecular weight of 12,500.
9.4 g of (PE-5A), 0.24 g of N,N-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.), 2.76 g of potassium carbonate, and 30.0 g of super-dehydrated N-methylpyrrolidone were weighed. , and stirred at 45°C. Then, 12.7 g of Compound-A was added and reacted at 45° C. for 8 hours. After the reaction, the mixture was cooled to room temperature, 300 mL of ethyl acetate was added, washed with 200 mL of water, 100 mL of 0.2N aqueous hydrochloric acid, then 300 mL of water, then 200 mL of saturated aqueous thorium chloride solution, and dried over sodium sulfate. Then, while filtering with filter paper, it was transferred to an eggplant-shaped flask and concentrated using an evaporator. This concentrate was dissolved in 50 mL of tetrahydrofuran, poured into 500 mL of water, filtered, and vacuum-dried at 40° C. for 8 hours to obtain 11.3 g of polyester (PE-5). The polyester (PE-5) had a weight average molecular weight of 14,800 and a dispersity (Mw/Mn) of 2.46.

<Synthesis of (R-1A)>
Monomer (a) and monomer (b) were used as monomers in a three-necked flask equipped with a condenser and a stirrer so that the molar ratio (monomer (a):monomer (b)) was 75:25. After mixing, methyl isobutyl ketone was added in an amount of 1.2 times the mass of the total amount of monomers to form a solution. To this solution, 3 mol % of azobis(2,4-dimethylvaleronitrile) was added as an initiator with respect to the total amount of monomers, and the mixture was heated at 70° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate a resin, which was filtered to obtain (R-1A) having a weight average molecular weight of 12,000.

<Synthesis of (R-2A)>
5.2 g of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (manufactured by Tokyo Kasei Co., Ltd.), 0.32 g of N,N-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.), 3.32 g of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.), and 16.0 g of ultra-dehydrated tetrahydrofuran are weighed and stirred at room temperature. did. Then, 3.38 g of dimethylmalonyl dichloride (manufactured by Tokyo Kasei Co., Ltd.) was added, reacted at room temperature for 2 hours, and then stirred at 45° C. for 8 hours. This was transferred to a separating funnel, 300 mL of ethyl acetate was added, washed with 100 mL of water, 100 mL of 0.5 mol/L hydrochloric acid, and 100 mL of water, followed by 200 mL of a saturated aqueous sodium chloride solution, followed by washing with sulfuric acid. After drying with sodium, it was transferred to an eggplant-shaped flask while filtering with filter paper, and concentrated using an evaporator to obtain 6.9 g of (R-2A). (R-2A) had a weight average molecular weight of 13,300 and a dispersity (Mw/Mn) of 2.31.

[Preparation and application of coating solution of resist composition]
Each component shown in Table 1 below was dissolved in the solvent shown in Table 1 to prepare a solution with a solid content concentration of 4% by mass, and this was filtered through a polyethylene filter having a pore size of 0.05 μm. was prepared.
In addition, Table 1 describes the amount of each component used. 1 g of resin (A) was used, and the amounts (mg) shown in Table 1 were used for the additive polymer, photoacid generator, basic compound, surfactant, and solvent.
An organic antireflection film ARC29SR (manufactured by Brewer) was coated on a silicon wafer and baked at 205° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. A resist composition of Comparative Example was applied and baked at 100° C. for 60 seconds to form a resist film with a thickness of 90 nm.

(2) ArF exposure and development Using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.730, inner sigma 0.630, XY deflection), a line width of 75 nm. Exposure was through a 6% halftone mask with a 1:1 line and space pattern. Ultrapure water was used as the immersion liquid. After heating at 120° C. for 60 seconds, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass %) for 30 seconds, rinsed with pure water, and spin-dried to obtain a resist pattern.

(3) Evaluation Using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.), the obtained resist pattern was evaluated for scum and development defects by the following method. In addition, DRCA before exposure and SCA after development were measured. The results are shown in Table 1 below.

[Scum (liquid immersion defect)]
The development residue (scum) in the resist pattern with a line width of 75 nm was observed using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The one in between was C, and the intermediate was B. At that time, the evaluation was performed at an exposure scanning speed of 700 mm/s.

[Development defect]
The pattern formed as described above (exposure scanning speed was set to 700 mm/s) on a silicon wafer (12-inch diameter) was inspected by a defect inspection apparatus KLA2360 (trade name) manufactured by KLA-Tencor Corporation. ), the pixel size of the defect inspection device is set to 0.16 μm, the threshold is set to 20, and the measurement is performed in random mode to detect the development defects extracted from the difference caused by the comparison image and the pixel-by-pixel overlay. Then, the number of development defects per unit area (defects/cm ² ) was calculated. Note that 1 inch is 0.0254 m. A is given when the value is less than 0.5, B is given when the value is 0.5 or more and less than 0.7, C is given when the value is 0.7 or more and less than 1.0, and D is 1.0 or more. A smaller value indicates better performance.

[Dynamic receding contact angle (DRCA) before exposure]
The prepared resist composition was applied onto a silicon wafer (8 inch diameter) and baked at 120° C. for 60 seconds to form a resist film with a thickness of 120 nm. Subsequently, the wafer was placed on a wafer stage of a contact angle meter (manufactured by Nikon Corporation). Droplets of pure water were ejected from a syringe and held while the droplets were brought into contact with the resist film. Next, the wafer stage was moved at a speed of 250 mm/sec while the syringe was fixed. The receding angle of the droplet during stage movement was measured, and the value at which the contact angle stabilized was defined as the dynamic receding angle. The contact angle was measured at 23±3°C.

[Static contact angle (SCA) after development]
The prepared resist composition was applied onto a silicon wafer (8 inch diameter) and baked at 120° C. for 60 seconds to form a resist film with a thickness of 120 nm. Subsequently, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38% by mass) for 30 seconds, rinsed with pure water, and spin-dried. After that, a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the static contact angle of the water droplet. Measurement was performed with a droplet size of 35 μL, and the value at which the contact angle stabilized was defined as the static contact angle after development. The measurement environment is 23° C. and 45% relative humidity. The smaller the contact angle value, the higher the hydrophilicity.

<Synthesis Example: Synthesis of Resin (A-1)>
In a nitrogen stream, 8.6 g of cyclohexanone was placed in a three-necked flask and heated to 80°C. To this, 9.8 g of 2-adamantyl isopropyl methacrylate, 4.4 g of dihydroxyadamantyl methacrylate, 8.9 g of norbornane lactone methacrylate, and a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added to the monomers at 8 mol % and 79 g of cyclohexanone. was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was further reacted at 80° C. for 2 hours. After the reaction solution was left to cool, it was added dropwise to a mixed solution of 800 ml of hexane/200 ml of ethyl acetate over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 19 g of resin (A-1). The weight average molecular weight of the obtained resin was 8800 in terms of standard polystyrene, and the degree of dispersion (Mw/Mn) was 1.9.
Similarly, another resin (A) shown below was synthesized.
The structure, weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) of resin (A) used in Examples are shown below. Moreover, the ratio of repeating units in each resin is a molar ratio.

The photoacid generators used are as follows.

The basic compounds used are as follows.

The surfactants used are as follows.
W-1: Megafac F176 (manufactured by Dainippon Ink and Chemicals Co., Ltd., fluorine-based)
W-2: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

The solvents used are as follows.
SL-2: Propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane)
SL-5: γ-butyrolactone

From Table 1, in Examples 1 to 11 using the polyester (B) of the present invention as the additive polymer, compared to Comparative Example 1 using an acrylic fluorine-containing resin as the additive polymer, DRCA before exposure is high, In addition, scum and development defects could be reduced. In Comparative Example 2, in which the content of the acrylic fluorine-containing resin was increased, the DRCA before exposure was high, but scum and development defects were worse. In addition, Examples 1 to 11 had a smaller contact angle after development than Comparative Example 3 in which a polyester having an alkali-decomposable group only in the main chain was used as the additive polymer, and was excellent in reducing scum.

According to the present invention, even if the exposure scanning speed is ultra-high (for example, 700 mm/sec or more), the immersion liquid (typically ultrapure water) has high followability to the exposure device during exposure ( That is, the dynamic receding contact angle of the actinic ray-sensitive or radiation-sensitive film with respect to water is large), and the hydrophilicity of the surface of the pattern after development is high (that is, the static contact angle of the pattern surface with respect to water is small. ), actinic ray- or radiation-sensitive resin composition capable of reducing both scum (liquid immersion defect) and development defect, and actinic ray- or radiation-sensitive film and pattern forming method using the same , a method for producing an electronic device, and a polyester that can be suitably used for the actinic ray-sensitive or radiation-sensitive resin composition.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2018-070301) filed on March 30, 2018, the contents of which are incorporated herein by reference.

Claims (10)

(A) a resin having a group that is decomposed by the action of an acid to increase polarity, (B) a polyester having an alkali-decomposable group in a side chain, and (C) a photoacid generator, which is sensitive to actinic rays or radiation. a flexible resin composition,
Actinic ray-sensitive or radiation-sensitive resin composition, wherein the (B) polyester has a group represented by the following general formula (EZ-2) in a side chain.

In general formula (EZ-2), M ₂₁ and M ₂₂ each independently represent a single bond or a divalent linking group, and EZ ₂ represents an organic group. * represents a binding position. (A) a resin having a group that is decomposed by the action of an acid to increase polarity, (B) a polyester having an alkali-decomposable group in a side chain, and (C) a photoacid generator, which is sensitive to actinic rays or radiation. a flexible resin composition,
The (B) polyester is represented by the following general formula (1) ,
Actinic ray-sensitive or radiation-sensitive resin composition, wherein the (B) polyester has a group represented by the following general formula (EZ-2) in a side chain .

In general formula (1), E ₁ and E ₂ are each independently a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, an aromatic group, or a group formed by combining these represents However, E ₁ represents a group represented by any one of the following general formulas (1d) to (1f).

In general formula (1d), W ₇ and W ₈ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₄ is a cycloalkylene group, a spirocyclic group optionally containing a hetero atom, or arylene Y ₁ and Y ₂ each independently represent a single bond or a divalent linking group, Q ₅ represents an organic group having a halogen atom, and k2 represents an integer of 1 or more. When k2 represents an integer of 2 or more, the plurality of Y ₁ s, the plurality of Y ₂ s, and the plurality of Q ₅ may be the same or different.
In general formula (1e), W ₉ , W ₁₀ and W ₁₁ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₅ and Z ₆ each independently represent a cycloalkylene group, a heteroatom represents a spirocyclic group or an arylene group, Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a single bond or a divalent linking group, and Q ₆ and Q ₇ each represent Each independently represents an organic group having a halogen atom, and k3 and k4 each independently represents an integer of 1 or more. When k3 represents an integer of 2 or more, multiple Y ₃ s, multiple Y ₄ s, and multiple Q _6s may be the same or different. When k4 represents an integer of 2 or more, the plurality of Y ₅ s, the plurality of Y ₆ s, and the plurality of Q ₇ may be the same or different.
_In general formula ₍ 1f), Y7 and Y8 each independently represent a single bond or a divalent linking group, _Q8 represents a hydrogen atom or a substituent, and _Q9 represents an organic group having a halogen atom. , k5 represents an integer of 1 or more, and k6 represents 1 or 2. When k5 represents an integer of 2 or more, multiple Y ₇ , multiple Y ₈ , multiple Q ₈ , and multiple Q ₉ may be the same or different.

In general formula (EZ-2), M ₂₁ and M ₂₂ each independently represent a single bond or a divalent linking group, and EZ ₂ represents an organic group. * represents a binding position. 3. The content of said (B) polyester is 0.1 mass % or more and 15 mass % or less with respect to the total solid content of said actinic ray-sensitive or radiation-sensitive resin composition, according to claim 1 or 2 . Actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein the (B) polyester is represented by the following general formula (1).

In general formula (1), E ₁ and E ₂ are each independently a chain aliphatic group which may contain a heteroatom, an alicyclic group which may contain a heteroatom, an aromatic group, or a group formed by combining these represents The actinic ray-sensitive or according to claim 4 , wherein at least one of E ₁ and E ₂ in the general formula (1) represents a group represented by any one of the following general formulas (1d) to (1f) A radiation-sensitive resin composition.

In general formula (1d), W ₇ and W ₈ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₄ is a cycloalkylene group, a spirocyclic group optionally containing a hetero atom, or arylene Y ₁ and Y ₂ each independently represent a single bond or a divalent linking group, Q ₅ represents an organic group having a halogen atom, and k2 represents an integer of 1 or more. When k2 represents an integer of 2 or more, the plurality of Y ₁ s, the plurality of Y ₂ s, and the plurality of Q ₅ may be the same or different.
In general formula (1e), W ₉ , W ₁₀ and W ₁₁ each independently represent a single bond, an alkylene group or a cycloalkylene group, Z ₅ and Z ₆ each independently represent a cycloalkylene group, a heteroatom represents a spirocyclic group or an arylene group, Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a single bond or a divalent linking group, and Q ₆ and Q ₇ each represent Each independently represents an organic group having a halogen atom, and k3 and k4 each independently represents an integer of 1 or more. When k3 represents an integer of 2 or more, multiple Y ₃ s, multiple Y ₄ s, and multiple Q _6s may be the same or different. When k4 represents an integer of 2 or more, the plurality of Y ₅ s, the plurality of Y ₆ s, and the plurality of Q ₇ may be the same or different.
_In general formula ₍ 1f), Y7 and Y8 each independently represent a single bond or a divalent linking group, _Q8 represents a hydrogen atom or a substituent, and _Q9 represents an organic group having a halogen atom. , k5 represents an integer of 1 or more, and k6 represents 1 or 2. When k5 represents an integer of 2 or more, multiple Y ₇ , multiple Y ₈ , multiple Q ₈ , and multiple Q ₉ may be the same or different. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5 , wherein the polyester (B) contains a fluorine atom. An actinic ray- or radiation-sensitive film formed from the actinic ray- or radiation-sensitive resin composition according to any one of claims 1 to 6 . A step of forming an actinic ray-sensitive or radiation-sensitive film from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6 ;
a step of irradiating the actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation; and
A pattern forming method comprising the step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation using a developer. 9. The pattern forming method according to claim 8 , wherein the developer is an alkaline developer or a developer containing an organic solvent. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 8 .