JP2021076636A - Chemically amplified positive photosensitive resin composition, photosensitive dry film, production method of photosensitive dry film, production method of patterned resist film, method for manufacturing substrate with template and method for manufacturing plated molded article - Google Patents

Abstract

To provide a chemically amplified positive photosensitive resin composition applicable to exposure to h-line rays and excellent in plating solution resistance and crack resistance, a photosensitive dry film including a photosensitive resin layer formed of the chemically amplified positive photosensitive resin composition, a production method of the photosensitive dry film, a production method of a patterned resist film using the chemically amplified positive photosensitive resin composition, a method for manufacturing a substrate with a template using the chemically amplified positive photosensitive resin composition, and a method for manufacturing a plated molded article using the substrate with a template.SOLUTION: The chemically amplified positive photosensitive resin composition is to be used for making a template for forming a plated molded article on a substrate having a metal surface, and the composition comprises an acid generator (A) and a resin (B) the solubility of which with an alkali increases by an action of an acid. The acid generator (A) comprises an acid generator having a specific naphthalimide skeleton, and the proportion of an acrylic resin with respect to the total of the resin (B) and resin other than the resin (B) is 70 mass% or more.SELECTED DRAWING: None

Description

The present invention comprises a chemically amplified positive photosensitive resin composition, a photosensitive dry film comprising a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition, and a method for producing the photosensitive dry film. A method for producing a patterned resist film using the above-mentioned chemically amplified positive photosensitive resin composition, a method for producing a molded substrate using the above-mentioned chemically amplified positive photosensitive resin composition, and a method for producing the molded substrate. The present invention relates to a method for manufacturing a plated model using a substrate.

Currently, photofabrication is the mainstream of precision microfabrication technology. Photofabrication is a method of applying a photoresist composition to the surface of a work piece to form a photoresist layer, patterning the photoresist layer by photolithography technology, and chemically etching and electrolyzing the patterned photoresist layer (photoresist pattern) as a mask. It is a general term for technologies for manufacturing various precision parts such as semiconductor packages by performing etching or electroforming mainly by electroplating.

In recent years, along with the downsizing of electronic devices, high-density mounting technology for semiconductor packages has advanced, and the packaging has become multi-pin thin film mounting, package size miniaturization, two-dimensional mounting technology by flip chip method, and three-dimensional mounting technology. Based on this, the mounting density has been improved. In such a high-density mounting technology, as connection terminals, for example, a protruding electrode (mounting terminal) such as a bump protruding on a package, or a rewiring (RDL) extending from a peripheral terminal on a wafer and a mounting terminal are connected. Metal posts and the like are arranged on the substrate with high accuracy.

Photoresist compositions are used for photofabrication as described above, and as such photoresist compositions, chemically amplified photoresist compositions containing an acid generator are known. In the chemically amplified polyether composition, acid is generated from the acid generator by irradiation (exposure), the diffusion of the acid is promoted by the heat treatment, and an acid catalytic reaction is caused with the base resin or the like in the composition. The alkali solubility changes.

Such a chemically amplified positive photoresist composition is often used for producing an etching mask when processing a substrate by etching (Patent Documents 1 and 2). Specifically, a photoresist layer having a desired thickness is formed on a substrate using a chemically amplified photoresist composition, and then only a portion corresponding to an etching target portion of the photoresist layer is exposed via a predetermined mask pattern. After that, the exposed photoresist layer is developed to form a photoresist pattern used as an etching mask.

The chemically amplified positive photoresist composition is also used to form molds used in the production of plated shaped objects such as bumps, metal posts, and Cu rewiring. Specifically, a chemically amplified photoresist composition is used to form a photoresist layer of a desired film thickness on a support such as a metal substrate, exposed through a predetermined mask pattern, developed, and plated. A photoresist pattern is formed in which the portion forming the modeled object is selectively removed (peeled) and used as a mold. Then, by embedding a conductor such as copper in the removed portion (non-resist portion) by plating and then removing the photoresist pattern around the removed portion (non-resist portion), bumps, metal posts, and Cu rewiring can be formed. ..

JP-A-2018-169543 International Publication No. 2018/179641 Special Table 2017-535595 Special Table 2018-513113 Special Table 2018-523640 JP-A-2018-0877970 Japanese Unexamined Patent Publication No. 2015-08779 Japanese Unexamined Patent Publication No. 2017-107211 Japanese Unexamined Patent Publication No. 2018-018087

In a panel level package having a larger area than the wafer level, it is conceivable to use h-rays as the exposure light. Therefore, it is desirable that the photoresist composition is applicable to exposure by h-line.

For example, Patent Documents 3 to 5 disclose chemically amplified negative or positive phosphate compositions used for exposure to g-line, h-line and i-line.
However, when the photosensitive resin compositions described in Patent Documents 3 to 5 are used, there is a problem that the resistance to the plating solution is poor and the shape of the resist pattern is changed by the plating treatment.

Patent Documents 4 to 9 disclose chemically amplified positive phosphate compositions used for producing a mold for forming a plated model. However, when the chemically amplified positive resist composition described in these documents is used, the shape of the resist pattern changes due to contact with the plating solution during the plating process of embedding a conductor such as copper by plating. It is often difficult to form plated objects such as bumps, metal posts, and Cu rewiring with the desired shape.

Therefore, in the chemically amplified positive-type resist composition used for producing a mold for forming a plated molded product, the shape change of the resist pattern is suppressed by the plating treatment, that is, the plating solution resistance is excellent. Is required.

Further, if cracks are formed in the resist pattern that serves as a mold for forming the plated model, it is difficult to form the plated model having a desired shape. Therefore, the chemically amplified positive photoresist composition used for producing a mold for forming a plated model is also required to suppress the occurrence of cracks, that is, to have excellent crack resistance. ..

The present invention has been made in view of the above problems, and is a chemically amplified positive photosensitive resin composition which can be applied to exposure by h-line and can easily form a resist pattern having excellent plating solution resistance and crack resistance. , A photosensitive dry film provided with a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition, a method for producing the photosensitive dry film, and a pattern using the above-mentioned chemically amplified positive photosensitive resin composition. An object of the present invention is to provide a method for producing a resist film, a method for producing a molded substrate using the above-mentioned chemically amplified positive photosensitive resin composition, and a method for producing a plated molded product using the molded substrate. And.

As a result of intensive studies to achieve the above object, the present inventors have made an acid generator (A) that generates an acid by irradiation with active light or radiation, and a resin whose solubility in an alkali is increased by the action of the acid. In the chemically amplified positive photosensitive resin composition containing (B), the compound represented by the following formula (a1-i) or the following formula (a1-ii) as the acid generator (A), the following formula ( It contains at least one selected from the compound represented by a2-i) or the following formula (a2-ii) and the compound represented by the following formula (a3-i) or the following formula (a3-ii). Acrylic resin, which is a resin containing 70 mol% or more of an acrylic constituent unit, which is a constituent unit derived from (meth) acrylic acid or a (meth) acrylic acid derivative, is a resin (B) and a resin other than the resin (B). It has been found that the above-mentioned problems can be solved by blending 70% by mass or more with respect to the total, and the present invention has been completed. Specifically, the present invention provides the following.

（式（ａ１−ｉ）及び式（ａ１−ｉｉ）中、Ｘ^１ａは酸素原子又は硫黄原子であり、
Ｒ^１ａは、１つ以上のハロゲン原子によって置換されていてもよい炭素原子数１以上１８以下の脂肪族基；
−Ｓ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数２以上１８以下の脂肪族基；
下記式（ａ１１）：

で表される基；
下記式（ａ１２）：

で表される基；並びに
下記式（ａ１３）：

で表される基からなる群から選択され、
式（ａ１１）中、Ｒ^３ａは、単結合、又は−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａ−からなる群から選択される少なくとも１つの部分を含んでいてもよい、炭素原子数１以上２０以下の脂肪族基であり、
Ａｒは、ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい芳香族基であり、
式（ａ１２）中、Ｒ^４ａ、及びＲ^５ａは、それぞれ独立に、炭素原子数１以上５以下の脂肪族基であり、
Ｙ^１ａは、酸素原子であり、
Ｒ^６ａは、炭素原子数１以上１０以下の脂肪族基であり、
Ｒ^７ａは、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含む、炭素原子数１以上１８以下の脂肪族基であり、
式（ａ１３）中、Ｒ^８ａは、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−からなる群から選択される少なくとも１つの部分を含んでいてもよい、炭素原子数２以上１８以下の脂肪族基であり、
Ｙ^２ａは、酸素原子であり、
Ｒ^９ａは、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含む、炭素原子数１以上１８以下の脂肪族基であり、
Ｒ^１０ａ及びＲ^１１ａは、それぞれ、炭素原子数１以上１０以下の脂肪族基であり、−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａにおいて、Ｒ^１０ａ及びＲ^１１ａは、互いに同一であっても異なっていてもよく、且つ互いに結合して脂環式基を形成してもよく、
Ｒ^２ａは、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝
Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数３以上１８以下の脂肪族基；
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい、炭素原子数４以上１８以下の芳香族基；並びに
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい、炭素原子数４以上１８以下の芳香族基で置換されたアルキル基からなる群から選択される。）
で表される化合物：
下記式（ａ２−ｉ）又は下記式（ａ２−ｉｉ）：

（式（ａ２−ｉ）〜（ａ２−ｉｉ）中、Ｒ^２１ａは、水素原子；
１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；又は
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含んでいてもよく、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数２以上１８以下の脂肪族基であり、
Ｒ^２２ａは、−ＣＨ_３、−ＣＨ_２Ｆ、−ＣＨＦ_２、−ＣＦ_３、又は１つ以上のハロゲン原子で置換されていてもよい炭素原子数２以上１８以下の脂肪族基；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数２以上１８以下の脂肪族基；
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい炭素原子数４以上１８以下の芳香族基；並びに
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい炭素原子数４以上１８以下の芳香族基で置換されたアルキル基からなる群から選択され、
ただし、Ｒ^２２ａが−ＣＦ_３である場合、Ｒ^２１ａは水素原子；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含んでいてもよく、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数２以上１８以下の脂肪族基；
−ＣＨ_２ＣＨ（ＣＨ_３）_２、−ＣＨ_２ＣＨ＝ＣＨＣＨ_３又は−ＣＨ_２ＣＨ_２ＣＨ＝ＣＨ_２；
下記式（ａ２１）：

で表される基；並びに
下記式（ａ２２）：

で表される基からなる群から選択される基であり、
Ｒ^１０ａ及びＲ^１１ａは、それぞれ、炭素原子数１以上１０以下の脂肪族基であり、−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａにおいて、Ｒ^１０ａ及びＲ^１１ａは、互いに同一であっても異なっていてもよく、且つ互いに結合して脂環式基を形成してもよく、
式（ａ２１）中、Ｒ^２３ａは炭素原子数４以上１８以下の脂肪族基であり、
式（ａ２２）中、Ｒ^２４ａは水素原子、又は炭素原子数１以上１０以下のアルキル基であり、ｎａは１〜５の整数である。）
で表される化合物；並びに
下記式（ａ３−ｉ）又は下記式（ａ３−ｉｉ）：

（式ａ３−ｉ）〜（ａ３−ｉｉ）中、Ｒ^３１ａ、及びＲ^３２ａは、それぞれ独立に、水素原子；
シアノ基；
１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−ＯＣ（＝Ｏ）−Ｏ−、−ＣＮ、−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；並びに
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい炭素原子数４以上１８以下の芳香族基からなる群から選択される基であり、
Ｒ^３１ａ、及びＲ^３２ａは、互いに同一であっても異なっていてもよく、且つ互いに結合して脂環式基又は複素環式基を形成してもよく、
Ｒ^３３ａは、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＣＮ、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；並びに
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい炭素原子数４以上１８以下の芳香族基からなる群から選択され、
Ｒ^１０ａ及びＲ^１１ａは、それぞれ、炭素原子数１以上１０以下の脂肪族基であり、−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａにおいて、Ｒ^１０ａ及びＲ^１１ａは、互いに同一であっても異なっていてもよく、且つ互いに結合して脂環式基を形成してもよい。）
で表される化合物から選択される少なくとも１種を含み、
（メタ）アクリル酸又は（メタ）アクリル酸誘導体に由来する構成単位であるアクリル構成単位を７０モル％以上含む樹脂であるアクリル樹脂を含有し、
樹脂（Ｂ）と樹脂（Ｂ）以外の樹脂との合計に対するアクリル樹脂の割合が、７０質量％以上である、化学増幅型ポジ型感光性樹脂組成物である。 The first aspect of the present invention is used to prepare a mold for forming a plated model by embedding a metal on a substrate having a metal surface by a plating process, and an acid is irradiated by irradiation with active light or radiation. A chemically amplified positive photosensitive resin composition containing an acid generator (A) for generating an acid and a resin (B) whose solubility in an alkali is increased by the action of an acid.
The acid generator (A) has the following formula (a1-i) or the following formula (a1-ii):

(In the formula (a1-i) and the formula (a1-ii), X ^1a is an oxygen atom or a sulfur atom.
R ^1a is an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;
-S-, -C (= O) -S-, _{-O-S (= O) 2-} , -OC (= O) -O-, -C (= O) -NH-, -C ( = ^{O) -NR 10a} -, and -C ^{(= O)} -NR ^10a comprises at least one moiety selected from the group consisting of ^{R 11a,} which may be substituted by one or more halogen atoms, carbon atoms Aliphatic groups of number 2 or more and 18 or less;
The following formula (a11):

Group represented by;
The following formula (a12):

Group represented by; and the following formula (a13):

Selected from the group consisting of the groups represented by
In formula (a11), R ^3a is a single bond, or -O-, -S-, -C (= O) -O-, -C (= O) -S-, -OS (= O). _2- , -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , and- It is an aliphatic group having 1 to 20 carbon atoms and may contain at least one moiety selected from the group consisting of C (= O) -NR ^10a-.
Ar is a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group and an aryl group. , An aromatic group which may have one or more substituents selected from the group consisting of an alkylaryl group, a cyano group, and a nitro group.
In the formula (a12), R ^4a and R ^5a are independently aliphatic groups having 1 or more and 5 or less carbon atoms.
Y ^1a is an oxygen atom,
R ^6a is an aliphatic group having 1 or more and 10 or less carbon atoms.
R ^7a is -O-, -S-, -C (= O) -S-, -O-S (= O) _2- , -OC (= O) -O-, -C (= O). ) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C (= O) -NR An aliphatic group having 1 to 18 carbon atoms and containing at least one moiety selected from the group consisting of ^10a R ^11a.
In the formula (a13), R ^8a is −O−, −S−, −C (= O) −S−, −OS (= O) _2- , −OC (= O) −O−. , -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , and -OC (= O) -NR ^10a- An aliphatic group having 2 to 18 carbon atoms, which may contain at least one moiety selected from the above.
Y ^2a is an oxygen atom
R ^9a is −O−, −S−, −C (= O) −O−, −C (= O) −S−, −OS (= O) _{2-, −OC (= O).} ) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -O-C (= O) -NR ^10a- , And -C (= O) -NR ^10a R ^11a , which is an aliphatic group having 1 to 18 carbon atoms and containing at least one moiety selected from the group.
R ^10a and R ^11a are aliphatic groups having 1 or more and 10 or less carbon atoms, respectively, and in -C (= O) -NR ^10a R ^11a , R ^10a and R ^11a are different even if they are the same as each other. And may be bonded to each other to form an alicyclic group.
R ^2a is an aliphatic group having 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms;
-O-, -S-, -C (= O) -O-, -C (= O) -S-, -O-S (= O) _2- , -O-C (= O) -O- , -C (= O) -NH-, -OC (= O) -NH-, -C (=
^{O) -NR 10a -, - O} -C (= O) -NR 10a -, and -C ^{(= O)} comprising at least one moiety selected from the group consisting of -NR ^{10a R 11a,} one or more Aliphatic groups with 3 to 18 carbon atoms, which may be substituted with halogen atoms;
Halogen atom, aliphatic group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl An aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of groups, cyano groups, and nitro groups; as well as halogen atoms, aliphatic groups, haloalkyl groups, Consists of an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group. Selected from the group Selected from the group consisting of alkyl groups substituted with aromatic groups having 4 or more and 18 or less carbon atoms, which may have one or more substituents. )
Compound represented by:
The following formula (a2-i) or the following formula (a2-ii):

(In formulas (a2-i) to (a2-ii), R ^21a is a hydrogen atom;
Aliphatic groups with 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms; or -O-, -S-, -C (= O)-, -C (= O)- O-, -C (= O) -S-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C ( ^{= O) -NR 10a -, -} O-C (= O) -NR 10a -, and -C ^{(= O)} may contain at least one moiety selected from the group consisting of -NR ^{10a R 11a} An aliphatic group having 2 to 18 carbon atoms, which may be substituted with one or more halogen atoms.
R ^22a is an aliphatic group having 2 to 18 carbon atoms which may be substituted with _{-CH 3} , -CH ₂ F, -CHF ₂ , -CF _{3, or one or more halogen atoms;}
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C (= O) ) -NR ^10a R ^11a contains at least one moiety selected from the group and may be substituted with one or more halogen atoms, an aliphatic group having 2 to 18 carbon atoms;
Halogen atom, aliphatic group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl An aromatic group having 4 to 18 carbon atoms which may have one or more substituents selected from the group consisting of a group, a cyano group, and a nitro group; as well as a halogen atom, an aliphatic group, a haloalkyl group, and an alkoxy. Group consisting of group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl group, cyano group, and nitro group. Selected from the group consisting of alkyl groups substituted with aromatic groups having 4 or more and 18 or less carbon atoms which may have one or more substituents.
However, when R ^22a is −CF ₃ , R ^21a is a hydrogen atom;
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C (= O) ) -NR ^10a An aliphatic group having 2 or more and 18 or less carbon atoms, which may contain at least one moiety selected from the group consisting of R ^{11a and may be substituted with one or more halogen atoms;}
-CH ₂ CH (CH ₃ ) ₂ , -CH ₂ CH = CH CH ₃ or -CH ₂ CH ₂ CH = CH ₂ ;
The following formula (a21):

Group represented by; and the following formula (a22):

A group selected from the group consisting of the groups represented by
R ^10a and R ^11a are aliphatic groups having 1 or more and 10 or less carbon atoms, respectively, and in -C (= O) -NR ^10a R ^11a , R ^10a and R ^11a are different even if they are the same as each other. And may be bonded to each other to form an alicyclic group.
In the formula (a21), R ^23a is an aliphatic group having 4 or more and 18 or less carbon atoms.
In the formula (a22), R ^24a is a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms, and na is an integer of 1 to 5. )
The compound represented by; and the following formula (a3-i) or the following formula (a3-ii):

In formulas a3-i to (a3-ii), R ^31a and R ^32a are independently hydrogen atoms;
Cyano group;
Aliphatic groups with 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms;
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -CN,- One or more including at least one portion selected from the group consisting of C (= O) -NH-, -C (= O) -NR ^10a- , and -C (= O) -NR ^10a R ^11a. An aliphatic group having 1 to 18 carbon atoms which may be substituted with a halogen atom; and a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, A carbon having one or more substituents selected from the group consisting of an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group. A group selected from the group consisting of aromatic groups having 4 or more and 18 or less atoms.
R ^31a and R ^32a may be the same or different from each other, and may be bonded to each other to form an alicyclic group or a heterocyclic group.
R ^33a is an aliphatic group having 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms;
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -CN , -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C An aliphatic group having at least one moiety selected from the group consisting of (= O) -NR ^{10a R 11a and optionally substituted with one or more halogen atoms;} Halogen atom, aliphatic group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl Selected from the group consisting of groups consisting of groups, cyano groups, and nitro groups, selected from the group consisting of aromatic groups having 4 or more and 18 or less carbon atoms which may have one or more substituents.
R ^10a and R ^11a are aliphatic groups having 1 or more and 10 or less carbon atoms, respectively, and in -C (= O) -NR ^10a R ^11a , R ^10a and R ^11a are different even if they are the same as each other. They may be bonded to each other to form an alicyclic group. )
Containing at least one selected from the compounds represented by
Contains acrylic resin, which is a resin containing 70 mol% or more of acrylic constituent units, which are constituent units derived from (meth) acrylic acid or (meth) acrylic acid derivatives.
This is a chemically amplified positive photosensitive resin composition in which the ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is 70% by mass or more.

The second aspect of the present invention has a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer is a chemically amplified positive photosensitive resin according to the first aspect. It is a photosensitive dry film composed of a composition.

A third aspect of the present invention comprises applying the chemically amplified positive photosensitive resin composition according to the first aspect on a base film to form a photosensitive resin layer. It is a manufacturing method of.

A fourth aspect of the present invention is
A laminating step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive resin composition according to the first aspect on a substrate.
An exposure process in which the photosensitive resin layer is exposed by regioselectively irradiating active light rays or radiation,
A method for producing a patterned resist film, which comprises a developing step of developing a photosensitive resin layer after exposure.

A fifth aspect of the present invention is
A laminating step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive resin composition according to the first aspect on a substrate having a metal surface.
An exposure process in which the photosensitive resin layer is exposed by regioselectively irradiating active light rays or radiation,
It is a method for manufacturing a substrate with a mold, which includes a developing step of developing a photosensitive resin layer after exposure to prepare a mold for forming a plated molded product.

A sixth aspect of the present invention is a method for producing a plated model, which comprises a step of plating a molded substrate produced by the method according to the fifth aspect to form a plated model in the mold. ..

According to the present invention, a chemically amplified positive photosensitive resin composition that is applicable to h-line exposure and easily forms a resist pattern having excellent plating solution resistance and crack resistance, and the chemically amplified positive photosensitive resin composition. A photosensitive dry film having a photosensitive resin layer made of a resin composition, a method for producing the photosensitive dry film, and a method for producing a patterned resist film using the above-mentioned chemically amplified positive photosensitive resin composition. A method for producing a molded substrate using the above-mentioned chemically amplified positive photosensitive resin composition and a method for producing a plated molded product using the molded substrate can be provided.

<< Chemically amplified positive photosensitive resin composition >>
The chemically amplified positive photosensitive resin composition (hereinafter, also referred to as a photosensitive resin composition) is a mold for forming a plated molded product by embedding a metal on a substrate having a metal surface by a plating treatment. Used to make. The photosensitive resin composition includes an acid generator (A) that generates an acid when irradiated with active light or radiation (hereinafter, also referred to as an acid generator (A)), and a resin whose solubility in alkali is increased by the action of the acid. (B) (hereinafter, also referred to as resin (B)) is contained. In the present invention, the acid generator (A) is a compound represented by the following formula (a1-i) or the following formula (a1-ii), the following formula (a2-i) or the following formula (a2-iii). ), And at least one selected from the compounds represented by the following formula (a3-i) or the following formula (a3-ii). The photosensitive resin composition contains an acrylic resin which is a resin containing 70 mol% or more of an acrylic constituent unit which is a constituent unit derived from (meth) acrylic acid or a (meth) acrylic acid derivative. The ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is 70% by mass or more.

In a photosensitive resin composition containing an acid generator (A) that generates an acid by irradiation with active light or radiation and a resin (B) whose solubility in an alkali is increased by the action of the acid, a specific acid generator is used. By containing the acrylic resin in a specific range and setting the ratio of the content of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) in a specific range, the photosensitive resin composition is h. It can be applied to line exposure, and it is easy to form a resist pattern with excellent plating solution resistance and crack resistance by using a photosensitive resin composition.

The photosensitive resin composition contains, if necessary, a phenolic hydroxyl group-containing low molecular weight compound (C), an alkali-soluble resin (D), a sulfur-containing compound (E), an acid diffusion inhibitor (F), and an organic solvent (S). Etc. may be contained.

Hereinafter, essential or arbitrary components contained in the photosensitive resin composition and a method for producing the photosensitive resin composition will be described.

<Acid generator (A)>
The acid generator (A) is a compound that generates an acid by irradiation with active light or radiation, and is a compound that directly or indirectly generates an acid by light. The acid generator (A) is a compound represented by the following formula (a1-i) or the following formula (a1-ii), a compound represented by the following formula (a2-i) or the following formula (a2-ii), And at least one selected from the compounds represented by the following formula (a3-i) or the following formula (a3-ii).

（式（ａ１−ｉ）及び式（ａ１−ｉｉ）中、Ｘ^１ａは酸素原子又は硫黄原子であり、
Ｒ^１ａは、１つ以上のハロゲン原子によって置換されていてもよい炭素原子数１以上１８以下の脂肪族基；
−Ｓ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数２以上１８以下の脂肪族基；
下記式（ａ１１）：

で表される基；
下記式（ａ１２）：

で表される基；並びに
下記式（ａ１３）：

で表される基からなる群から選択され、
式（ａ１１）中、Ｒ^３ａは、単結合、又は−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａ−からなる群から選択される少なくとも１つの部分を含んでいてもよい、炭素原子数１以上２０以下の脂肪族基であり、
Ａｒは、ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい芳香族基であり、
式（ａ１２）中、Ｒ^４ａ、及びＲ^５ａは、それぞれ独立に、炭素原子数１以上５以下の脂肪族基であり、
Ｙ^１ａは、酸素原子であり、
Ｒ^６ａは、炭素原子数１以上１０以下の脂肪族基であり、
Ｒ^７ａは、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含む、炭素原子数１以上１８以下の脂肪族基であり、
式（ａ１３）中、Ｒ^８ａは、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−からなる群から選択される少なくとも１つの部分を含んでいてもよい、炭素原子数２以上１８以下の脂肪族基であり、
Ｙ^２ａは、酸素原子であり、
Ｒ^９ａは、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含む、炭素原子数１以上１８以下の脂肪族基であり、
Ｒ^１０ａ及びＲ^１１ａは、それぞれ、炭素原子数１以上１０以下の脂肪族基であり、−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａにおいて、Ｒ^１０ａ及びＲ^１１ａは、互いに同一であっても異なっていてもよく、且つ互いに結合して脂環式基を形成してもよく、
Ｒ^２ａは、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｓ（＝Ｏ）_２−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝
Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数３以上１８以下の脂肪族基；
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい、炭素原子数４以上１８以下の芳香族基；並びに
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい、炭素原子数４以上１８以下の芳香族基で置換されたアルキル基からなる群から選択される。）

(In the formula (a1-i) and the formula (a1-ii), X ^1a is an oxygen atom or a sulfur atom.
R ^1a is an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;
-S-, -C (= O) -S-, _{-O-S (= O) 2-} , -OC (= O) -O-, -C (= O) -NH-, -C ( = ^{O) -NR 10a} -, and -C ^{(= O)} -NR ^10a comprises at least one moiety selected from the group consisting of ^{R 11a,} which may be substituted by one or more halogen atoms, carbon atoms Aliphatic groups of number 2 or more and 18 or less;
The following formula (a11):

Group represented by;
The following formula (a12):

Group represented by; and the following formula (a13):

Selected from the group consisting of the groups represented by
In formula (a11), R ^3a is a single bond, or -O-, -S-, -C (= O) -O-, -C (= O) -S-, -OS (= O). _2- , -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , and- It is an aliphatic group having 1 to 20 carbon atoms and may contain at least one moiety selected from the group consisting of C (= O) -NR ^10a-.
Ar is a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group and an aryl group. , An aromatic group which may have one or more substituents selected from the group consisting of an alkylaryl group, a cyano group, and a nitro group.
In the formula (a12), R ^4a and R ^5a are independently aliphatic groups having 1 or more and 5 or less carbon atoms.
Y ^1a is an oxygen atom,
R ^6a is an aliphatic group having 1 or more and 10 or less carbon atoms.
R ^7a is -O-, -S-, -C (= O) -S-, -O-S (= O) _2- , -OC (= O) -O-, -C (= O). ) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C (= O) -NR An aliphatic group having 1 to 18 carbon atoms and containing at least one moiety selected from the group consisting of ^10a R ^11a.
In the formula (a13), R ^8a is −O−, −S−, −C (= O) −S−, −OS (= O) _2- , −OC (= O) −O−. , -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , and -OC (= O) -NR ^10a- An aliphatic group having 2 to 18 carbon atoms, which may contain at least one moiety selected from the above.
Y ^2a is an oxygen atom
R ^9a is −O−, −S−, −C (= O) −O−, −C (= O) −S−, −OS (= O) _{2-, −OC (= O).} ) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -O-C (= O) -NR ^10a- , And -C (= O) -NR ^10a R ^11a , which is an aliphatic group having 1 to 18 carbon atoms and containing at least one moiety selected from the group.
R ^10a and R ^11a are aliphatic groups having 1 or more and 10 or less carbon atoms, respectively, and in -C (= O) -NR ^10a R ^11a , R ^10a and R ^11a are different even if they are the same as each other. And may be bonded to each other to form an alicyclic group.
R ^2a is an aliphatic group having 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms;
-O-, -S-, -C (= O) -O-, -C (= O) -S-, -O-S (= O) _2- , -O-C (= O) -O- , -C (= O) -NH-, -OC (= O) -NH-, -C (=
^{O) -NR 10a -, - O} -C (= O) -NR 10a -, and -C ^{(= O)} comprising at least one moiety selected from the group consisting of -NR ^{10a R 11a,} one or more Aliphatic groups with 3 to 18 carbon atoms, which may be substituted with halogen atoms;
Halogen atom, aliphatic group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl An aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of groups, cyano groups, and nitro groups; as well as halogen atoms, aliphatic groups, haloalkyl groups, Consists of an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group. Selected from the group Selected from the group consisting of alkyl groups substituted with aromatic groups having 4 or more and 18 or less carbon atoms, which may have one or more substituents. )

（式（ａ２−ｉ）〜（ａ２−ｉｉ）中、Ｒ^２１ａは、水素原子；
１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；又は
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含んでいてもよく、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数２以上１８以下の脂肪族基であり、
Ｒ^２２ａは、−ＣＨ_３、−ＣＨ_２Ｆ、−ＣＨＦ_２、−ＣＦ_３、又は１つ以上のハロゲン原子で置換されていてもよい炭素原子数２以上１８以下の脂肪族基；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数２以上１８以下の脂肪族基；
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい炭素原子数４以上１８以下の芳香族基；並びに
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい炭素原子数４以上１８以下の芳香族基で置換されたアルキル基からなる群から選択され、
ただし、Ｒ^２２ａが−ＣＦ_３である場合、Ｒ^２１ａは水素原子；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含んでいてもよく、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数２以上１８以下の脂肪族基；
−ＣＨ_２ＣＨ（ＣＨ_３）_２、−ＣＨ_２ＣＨ＝ＣＨＣＨ_３又は−ＣＨ_２ＣＨ_２ＣＨ＝ＣＨ_２；
下記式（ａ２１）：

で表される基；並びに
下記式（ａ２２）：

で表される基からなる群から選択される基であり、
Ｒ^１０ａ及びＲ^１１ａは、それぞれ、炭素原子数１以上１０以下の脂肪族基であり、−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａにおいて、Ｒ^１０ａ及びＲ^１１ａは、互いに同一であっても異なっていてもよく、且つ互いに結合して脂環式基を形成してもよく、
式（ａ２１）中、Ｒ^２３ａは炭素原子数４以上１８以下の脂肪族基であり、
式（ａ２２）中、Ｒ^２４ａは水素原子、又は炭素原子数１以上１０以下のアルキル基であり、ｎａは１〜５の整数である。）

(In formulas (a2-i) to (a2-ii), R ^21a is a hydrogen atom;
Aliphatic groups with 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms; or -O-, -S-, -C (= O)-, -C (= O)- O-, -C (= O) -S-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C ( ^{= O) -NR 10a -, -} O-C (= O) -NR 10a -, and -C ^{(= O)} may contain at least one moiety selected from the group consisting of -NR ^{10a R 11a} An aliphatic group having 2 to 18 carbon atoms, which may be substituted with one or more halogen atoms.
R ^22a is an aliphatic group having 2 to 18 carbon atoms which may be substituted with _{-CH 3} , -CH ₂ F, -CHF ₂ , -CF _{3, or one or more halogen atoms;}
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C (= O) ) -NR ^10a R ^11a contains at least one moiety selected from the group and may be substituted with one or more halogen atoms, an aliphatic group having 2 to 18 carbon atoms;
Halogen atom, aliphatic group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl An aromatic group having 4 to 18 carbon atoms which may have one or more substituents selected from the group consisting of a group, a cyano group, and a nitro group; as well as a halogen atom, an aliphatic group, a haloalkyl group, and an alkoxy. Group consisting of group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl group, cyano group, and nitro group. Selected from the group consisting of alkyl groups substituted with aromatic groups having 4 or more and 18 or less carbon atoms which may have one or more substituents.
However, when R ^22a is −CF ₃ , R ^21a is a hydrogen atom;
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C (= O) ) -NR ^10a An aliphatic group having 2 or more and 18 or less carbon atoms, which may contain at least one moiety selected from the group consisting of R ^{11a and may be substituted with one or more halogen atoms;}
-CH ₂ CH (CH ₃ ) ₂ , -CH ₂ CH = CH CH ₃ or -CH ₂ CH ₂ CH = CH ₂ ;
The following formula (a21):

Group represented by; and the following formula (a22):

A group selected from the group consisting of the groups represented by
R ^10a and R ^11a are aliphatic groups having 1 or more and 10 or less carbon atoms, respectively, and in -C (= O) -NR ^10a R ^11a , R ^10a and R ^11a are different even if they are the same as each other. And may be bonded to each other to form an alicyclic group.
In the formula (a21), R ^23a is an aliphatic group having 4 or more and 18 or less carbon atoms.
In the formula (a22), R ^24a is a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms, and na is an integer of 1 to 5. )

（式ａ３−ｉ）〜（ａ３−ｉｉ）中、Ｒ^３１ａ、及びＲ^３２ａは、それぞれ独立に、水素原子；
シアノ基；
１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−ＯＣ（＝Ｏ）−Ｏ−、−ＣＮ、−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；並びに
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい炭素原子数４以上１８以下の芳香族基からなる群から選択される基であり、
Ｒ^３１ａ、及びＲ^３２ａは、互いに同一であっても異なっていてもよく、且つ互いに結合して脂環式基又は複素環式基を形成してもよく、
Ｒ^３３ａは、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；
−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＣＮ、−Ｃ（＝Ｏ）−ＮＨ−、−Ｏ−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１０ａ−、及び−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａからなる群から選択される少なくとも１つの部分を含み、１つ以上のハロゲン原子によって置換されていてもよい、炭素原子数１以上１８以下の脂肪族基；並びに
ハロゲン原子、脂肪族基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、ジアルキルアミノ基、アシルオキシ基、アシルチオ基、アシルアミノ基、アルコキシカルボニル基、アルキルスルホニル基、アルキルスルフィニル基、アリール基、アルキルアリール基、シアノ基、及びニトロ基からなる群より選択される１以上の置換基を有してもよい炭素原子数４以上１８以下の芳香族基からなる群から選択され、
Ｒ^１０ａ及びＲ^１１ａは、それぞれ、炭素原子数１以上１０以下の脂肪族基であり、−Ｃ（＝Ｏ）−ＮＲ^１０ａＲ^１１ａにおいて、Ｒ^１０ａ及びＲ^１１ａは、互いに同一であっても異なっていてもよく、且つ互いに結合して脂環式基を形成してもよい。）

In formulas a3-i to (a3-ii), R ^31a and R ^32a are independently hydrogen atoms;
Cyano group;
Aliphatic groups with 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms;
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -CN,- One or more including at least one portion selected from the group consisting of C (= O) -NH-, -C (= O) -NR ^10a- , and -C (= O) -NR ^10a R ^11a. An aliphatic group having 1 to 18 carbon atoms which may be substituted with a halogen atom; and a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, A carbon having one or more substituents selected from the group consisting of an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group. A group selected from the group consisting of aromatic groups having 4 or more and 18 or less atoms.
R ^31a and R ^32a may be the same or different from each other, and may be bonded to each other to form an alicyclic group or a heterocyclic group.
R ^33a is an aliphatic group having 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms;
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -CN , -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C An aliphatic group having at least one moiety selected from the group consisting of (= O) -NR ^{10a R 11a and optionally substituted with one or more halogen atoms;} Halogen atom, aliphatic group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl Selected from the group consisting of groups consisting of groups, cyano groups, and nitro groups, selected from the group consisting of aromatic groups having 4 or more and 18 or less carbon atoms which may have one or more substituents.
R ^10a and R ^11a are aliphatic groups having 1 or more and 10 or less carbon atoms, respectively, and in -C (= O) -NR ^10a R ^11a , R ^10a and R ^11a are different even if they are the same as each other. They may be bonded to each other to form an alicyclic group. )

Formula (a1-i), formula (a1-ii), formula (a2-i), formula (a2-ii), formula (a3-i), formula (a3-ii), formulas (a11) to (a13) , The aliphatic groups in the formulas (a21) and (a22) are chain-like and may be cyclic, or may include a chain-like structure and a cyclic structure, respectively. Further, the aliphatic group may contain a hetero atom, and may be a chain aliphatic group containing a hetero atom such as a nitrogen atom or a sulfur atom, or a heterocyclic aliphatic group.
The chain-like aliphatic group may be linear or branched. Examples of the chain aliphatic group include an alkyl group, an alkenyl group, and an alkynyl group. The alkyl group includes methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group and n-undecyl group. , N-Dodecyl group and other linear alkyl groups, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, 2-ethylhexyl group, And branched alkyl groups such as 1,1,3,3-tetramethylbutyl group. Examples of the alkenyl group include a 3-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group and the like. Examples of the alkynyl group include a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a noninyl group, a decynyl group and the like. In the alkyl group, alkenyl group, and alkynyl group, the hydrogen atom bonded to these groups may be substituted with one or more substituents. Examples of the substituent include a halogen atom, a cyano group, an oxoalkoxy group, a hydroxy group, an amino group, a nitro group, an aryl group, and an alkyl group substituted with a halogen atom.
Cyclic aliphatic groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group, norbolinyl group, cubyl group, octahydro-indenyl group, decahydro-naphthyl group and bicyclo [3]. .2.1] Octyl group, bicyclo [2.2.2] octyl group, bicyclo [3.3.1] nonyl group, bicyclo [3.3.2] decyl group, bicyclo [2.2.2] octyl Examples thereof include a cycloalkyl group such as a group, an azacycloalkyl group, and a ((aminocarbonyl) cycloalkyl) cycloalkyl group.

The aromatic group in the above formula may be an aromatic hydrocarbon group or an aromatic heterocyclic group containing a heteroatom such as a nitrogen atom, an oxygen atom or a sulfur atom, respectively.
Aromatic hydrocarbon groups include aryl groups such as monocyclic groups (phenyl groups, etc.), bicyclic groups (naphthyl groups, biphenyl groups, etc.), tricyclic groups (fluorenyl groups, etc.), and benzyls. Examples thereof include an aralkyl group such as a group and a phenethyl group.
Examples of the aromatic heterocyclic group include heteroaryl groups such as a frill group and a thienyl group.
These aromatic hydrocarbon groups and aromatic heterocyclic groups may have an alkyl group as a substituent. The same applies to the alkyl group as described above.

In the above, the case of a monovalent group is illustrated as an aliphatic group or an aromatic group, but in the case of a divalent group, it is a group obtained by removing one hydrogen atom from the above monovalent group.

Examples of the halogen atom in the above formula include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

In the above formula, an alkoxy group (-O- alkyl group), an alkylthio group (the alkyl group -S-), dialkylamino group _((alkyl) 2 N-), an acyloxy group (an alkyl group - -O- group), Alkyl thio group (alkyl group-carbonyl group-S-), acyl amino group (alkyl group-carbonyl group-NH-), alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl group, alkyl group and aryl The group is the same as above.
The haloalkyl group in the above formula is an alkyl group substituted with one or more halogen atoms having a maximum possible number of substitutions or less. The same applies to the alkyl group and halogen atom.
The haloalkoxy group in the above formula is an alkoxy group substituted with one or more halogen atoms having a maximum possible number of substitutions or less. The same applies to the alkyl group and halogen atom.

Specific examples of the compound represented by the formula (a1-i) or the following formula (a1-ii) include the following structures.

In the compound represented by the formula (a1-i) or the formula (a1-ii), X ^1a is a sulfur atom and R ^1a is a linear or branched alkyl group having 1 or more and 3 or less carbon atoms. , R ^2a is preferably a chain aliphatic group having 1 or more and 18 or less carbon atoms substituted with one or more fluorine atoms.

Specific examples of the compound represented by the formula (a2-i) or the formula (a2-ii) include the following structures.

In the compound represented by the formula (a2-i) or the formula (a2-ii), R ^21a is a chain aliphatic group having 1 or more carbon atoms and 18 or less carbon atoms, and R ^22a is composed of one or more fluorine atoms. It is preferably a chain aliphatic group having 1 or more and 18 or less carbon atoms substituted.

Specific examples of the compound represented by the formula (a3-i) or the formula (a3-ii) include the following structures.

In the compound represented by the formula (a3-i) or the formula (a3-ii), R ^31a is a hydrogen atom, R ^32a is a chain aliphatic group having 1 to 18 carbon atoms, and R ^33a. Is preferably a chain aliphatic group having 1 or more and 18 or less carbon atoms substituted with one or more fluorine atoms.

A compound represented by the formula (a1-i) or the formula (a1-ii), a compound represented by the formula (a2-i) or the formula (a2-ii), or the formula (a3-i) or the formula (a3-i). The method for producing the compound represented by ii) is not particularly limited, and for example, it can be produced by the production method described in Patent Documents 3 to 5.

The acid generator (A) is a compound represented by the above formula (a1-i) or formula (a1-ii), a compound represented by the formula (a2-i) or formula (a2-ii), and a formula. It may contain other acid generators (hereinafter, also referred to as other acid generators) other than the compound represented by (a3-i) or the formula (a3-ii). The other acid generator is a compound that generates an acid by irradiation with active light or radiation, and is a compound that directly or indirectly generates an acid by light. As the other acid generator that may be contained in the acid generator (A), the acid generators of the first to fifth aspects described below are preferable.

As a first aspect of the other acid generator in the acid generator (A), a compound represented by the following formula (a101) can be mentioned.

In the above formula (a101), X ^101a represents a sulfur atom or an iodine atom having a valence of g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^101a is an ^{organic group bonded to X 101a} , and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, and the like. Represents an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, and R ^101a represents alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio. At least one selected from the group consisting of carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogens. It may be replaced with a seed. The number of R ^101a is g + h (g-1) + 1, and the R ^101a may be the same or different from each other. Also, directly with each other two or more ^{R 101a,} or _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 102a -, - CO -, - COO -, - CONH- , An alkylene group having 1 or more and 3 or less carbon atoms or a phenylene group may be bonded to form a ring structure containing ^{X 101a.} R ^102a is an alkyl group having 1 or less carbon atoms and 5 or more carbon atoms or an aryl group having 6 or less carbon atoms and 10 or more carbon atoms.

X ^102a has a structure represented by the following formula (a102).

In the above formula (a102), X ^104a contains an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms. Represented, X ^104a is composed of a group consisting of an alkyl having 1 to 8 carbon atoms, an alkoxy having 1 to 8 carbon atoms, an aryl, hydroxy, cyano, and nitro groups having 6 to 10 carbon atoms, and a halogen. It may be replaced with at least one selected. X ^105a is _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 102a -, - CO -, - COO -, - CONH-, carbon atom number of 1 to 3 alkylene Represents a group or a phenylene group. h represents the number of repeating units of the structure in parentheses. The h + 1 X ^104a and the h X ^105a may be the same or different, respectively. R ^102a is the same as the above definition.

X ^{103a- is a counterion of onium, and examples thereof} include a fluorinated alkylfluorophosphate anion represented by the following formula (a117) and a borate anion represented by the following formula (a118).

In the above formula (a117), R ^103a represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. j indicates the number thereof, and is an integer of 1 or more and 5 or less. The j R ^103a may be the same or different.

In the above formula (a118), R ^{104a to} R ^107a independently represent a fluorine atom or a phenyl group, and a part or all of the hydrogen atoms of the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group. It may be replaced with at least one of these.

Examples of the onium ion in the compound represented by the above formula (a101) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, and bis [4- (diphenylsulfonio) phenyl] sulfide. Bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-) Chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 −Thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-Benzoylphenylthio) phenyldiphenylsulfonium, diphenylphenylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl [4- (4-Biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4-acetophenylthio) phenyl] diphenylsulfonium, octadecylmethylphenacylsulfonium , Diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- Examples thereof include (2-hydroxytetradecyloxy) phenylphenyl iodonium, 4-isopropylphenyl (p-tolyl) iodonium, 4-isobutylphenyl (p-tolyl) iodonium, and the like.

Among the onium ions in the compound represented by the above formula (a101), preferable onium ions include sulfonium ions represented by the following formula (a119).

In the above formula (a119), R ^108a is independently composed of a hydrogen atom, an alkyl, a hydroxy, an alkoxy, an alkylcarbonyl, an alkylcarbonyloxy, an alkyloxycarbonyl, a halogen atom, and an aryl, an arylcarbonyl, which may have a substituent. Represents a group selected from the group. X ^102a represents the same meaning as ^{X 102a} in the formula (a101).

Specific examples of the sulfonium ion represented by the above formula (a119) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4-. (4-Benzoylphenylthio) phenyldiphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4) Examples thereof include −acetophenylthio) phenyl] diphenylsulfonium and diphenyl [4- (p-terphenylthio) phenyl] diphenylsulfonium.

In the fluorinated alkylfluorophosphate anion represented by the above formula (a117), R ^103a represents an alkyl group substituted with a fluorine atom, and the preferable number of carbon atoms is 1 or more and 8 or less, and the more preferable number of carbon atoms is 1 or more. It is 4 or less. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and further cyclopropyl, cyclobutyl and cyclopentyl. , Cycloalkyl group such as cyclohexyl, and the like, and the ratio of hydrogen atom of alkyl group substituted with fluorine atom is usually 80% or more, preferably 90% or more, more preferably 100%. When the substitution rate of the fluorine atom is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by the above formula (a101) decreases.

Particularly preferable R ^103a is a linear or branched perfluoroalkyl group having 1 or more and 4 or less carbon atoms and a fluorine atom substitution rate of 100%. Specific examples thereof include CF ₃ and CF ₃ CF. _{2, (CF 3) 2 CF} , CF 3 CF 2 CF 2, CF 3 CF 2 CF 2 CF 2, (CF 3) 2 CFCF 2, CF 3 CF 2 (CF 3) CF, is _{(CF 3)} 3 C Can be mentioned. The number j of R ^103a is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among these, [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , or [((CF 3) 2 CF) CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ is particularly preferable.

Specific preferred examples of the borate anion represented by the above formula (A 118), tetrakis (pentafluorophenyl) borate _{([B (C 6 F 5} ) 4] -), tetrakis [(trifluoromethyl) phenyl] borate ( [B (C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ), trifluoro (pentafluorophenyl) borate ([(C) ₆ F ₅ ) BF ₃ ] ^- ), tetrakis (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ^- ) and the like. Of these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferable.

The second aspect of the other acid generator in the acid generator (A) is 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl). ) -6- [2- (2-Frill) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl) -2-Frill) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) ) -6- [2- (3,5-diethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl]- s-Triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2 -(3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s -Triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styryl Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) )-1,3,5-Triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-frill) ethenyl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2 -[2- (3,5-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4 , 6-Bis (Trichloromethyl) -1,3,5-Triazine, 2- (3,4-Methylenedioxyphenyl) -4,6-Bis (Trichloromethyl) -1,3,5-Triazine, Tris ( Halogen-containing triazine compounds such as 1,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, and tris (2,3-dibromopropyl). Examples thereof include halogen-containing triazine compounds represented by the following formula (a103) such as isocyanurate.

In the above formula (a103), R ^109a , R ^110a , and R ^111a each independently represent an alkyl halide group.

In addition, as a third aspect of the other acid generator in the acid generator (A), α- (p-toluenesulfonyloxyimine) -phenylacetamite, α- (benzenesulfonyloxyimine) -2,4-dichlorophenyl Acetonitrile, α- (benzenesulfonyloxyimine) -2,6-dichlorophenylacetate, α- (2-chlorobenzenesulfonyloxyimine) -4-methoxyphenylacetamite, α- (ethylsulfonyloxyimine) -1-cyclopentenyl acetonitrile, In addition, a compound represented by the following formula (a104) containing an oxime sulfonate group can be mentioned.

In the above formula (a104), R ^112a represents a monovalent, divalent or trivalent organic group, and R ^113a is a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. Represents, and n represents the number of repeating units of the structure in parentheses.

In the above formula (a104), examples of the aromatic group include an aryl group such as a phenyl group and a naphthyl group, and a heteroaryl group such as a frill group and a thienyl group. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group on the ring. Further, R ^113a is particularly preferably an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. In particular, ^{a compound in which R 112a} is an aromatic group and R ^113a is an alkyl group having 1 or more and 4 or less carbon atoms is preferable.

As the acid generator represented by the above formula (a104), when n = 1, R ^112a is any of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and ^R113a is a compound having a methyl group, specifically. Specifically, α- (methylsulfonyloxyimino) -1-phenyl acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p-) Examples thereof include methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-iriden] (o-tolyl) acetonitrile and the like. When n = 2, the acid generator represented by the above formula (a104) specifically includes an acid generator represented by the following formula.

Further, as a fourth aspect of the other acid generator in the acid generator (A), an onium salt having a naphthalene ring in the cation portion can be mentioned. By "having a naphthalene ring", it means having a structure derived from naphthalene, and it means that the structure of at least two rings and their aromaticity are maintained. This naphthalene ring has substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and a linear or branched alkoxy group having 1 to 6 carbon atoms. May be good. The structure derived from the naphthalene ring may be a monovalent group (one free valence) or a divalent group (two free valences) or more, but it may be a monovalent group. Desirable (however, at this time, the free valence shall be counted except for the portion bonded to the above substituent). The number of naphthalene rings is preferably 1 or more and 3 or less.

As the cation portion of the onium salt having a naphthalene ring in such a cation portion, a structure represented by the following formula (a105) is preferable.

In the above formula (a105), ^{at least one of R 114a} , R ^115a , and R ^116a represents a group represented by the following formula (a106), and the rest are linear or branched with 1 to 6 carbon atoms. Represents an alkyl group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^114a , R ^115a , and R ^116a is a group represented by the following formula (a106), and the remaining two are independently linear or branched with 1 to 6 carbon atoms. It is an alkylene group of, and these ends may be bonded to form a cyclic.

In the above formula (a106), R ^117a and R ^118a are independently hydroxyl groups, linear or branched alkoxy groups having 1 to 6 carbon atoms, or linear or branched having 1 to 6 carbon atoms, respectively. Representing a branched alkyl group, R ^119a represents a linear or branched alkylene group having 1 to 6 carbon atoms which may have a single bond or a substituent. l and m each independently represent an integer of 0 or more and 2 or less, and l + m is 3 or less. However, ^{when there are a plurality of R 117a} , they may be the same or different from each other. Further, ^{when a plurality of R 118a} exist, they may be the same or different from each other.

Of the above R ^114a , R ^115a , and R ^116a , the number of groups represented by the above formula (a106) is preferably one from the viewpoint of compound stability, and the rest is directly formed with 1 or more and 6 or less carbon atoms. It is a chain or branched alkylene group, and these ends may be bonded to form a cyclic group. In this case, the two alkylene groups form a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 or more and 6 or less.

Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group and the like.

The substituents that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms, and a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms. Alkoxy group and the like can be mentioned.

Suitable examples of these cation portions include those represented by the following formulas (a107) and (a108), and a structure represented by the following formula (a108) is particularly preferable.

The cation portion may be an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable from the viewpoint of acid generation efficiency and the like.

Therefore, as an anion portion of an onium salt having a naphthalene ring in the cation portion, an anion capable of forming a sulfonium salt is desirable.

The anion portion of such an acid generator is a fluoroalkyl sulfonic acid ion or an aryl sulfonic acid ion in which a part or all of hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkyl sulfonic acid ion may be linear, branched or cyclic with 1 or more and 20 or less carbon atoms, and has 1 or more and 10 or less carbon atoms from the bulkiness of the generated acid and its diffusion distance. Is preferable. In particular, branched or annular ones are preferable because they have a short diffusion distance. Moreover, since it can be synthesized at low cost, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like can be mentioned as preferable ones.

Examples of the aryl group in the aryl sulfonic acid ion include an aryl group having 6 to 20 carbon atoms, an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having 6 or more and 10 or less carbon atoms is preferable because it can be synthesized at low cost. Specific examples of preferable ones include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group and the like.

In the above fluoroalkyl sulfonic acid ion or aryl sulfonic acid ion, the fluorination rate when a part or all of hydrogen atoms is fluorinated is preferably 10% or more and 100% or less, more preferably 50% or more and 100%. The following is particularly preferable, in which all hydrogen atoms are replaced with fluorine atoms because the strength of the acid becomes stronger. Specific examples thereof include trifluoromethanesulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, and perfluorobenzene sulfonate.

Among these, preferred anion portions include those represented by the following formula (a109).

In the above formula (a109), R ^120a is a group represented by the following formulas (a110), (a111), and (a112).

In the above equation (a110), x represents an integer of 1 or more and 4 or less. Further, in the above formula (a111), R ^121a is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, or a linear or branched alkyl group having 1 or more and 6 or less carbon atoms. Represents an alkoxy group in the form, and y represents an integer of 1 or more and 3 or less. Among these, trifluoromethanesulfonate and perfluorobutane sulfonate are preferable from the viewpoint of safety.

Further, as the anion portion, those containing nitrogen represented by the following formulas (a113) and (a114) can also be used.

The formula (a113), (a114) in, X ^a represents a linear or branched alkylene group having at least one hydrogen atom is substituted with a fluorine atom, the number of carbon atoms of the alkylene group 2 to 6 It is preferably 3 or more and 5 or less, and most preferably the number of carbon atoms is 3. Further, Y ^a and Z ^a each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms of the alkyl group is 1 or more and 10 or less. It is preferably 1 or more and 7 or less, and more preferably 1 or more and 3 or less.

X ^a number of carbon atoms of the alkylene group, or Y ^a, soluble enough in organic solvents the number of carbon atoms in the alkyl group of Z ^a is less preferred because it is excellent.

Further, in the alkylene group of ^{X a or the alkyl group of Y a} and Z ^a , the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably all hydrogen atoms are fluorine. It is an atomically substituted perfluoroalkylene group or perfluoroalkyl group.

Preferred as an onium salt having a naphthalene ring in such a cation portion include compounds represented by the following formulas (a115) and (a116).

Further, as a fifth aspect of the other acid generator in the acid generator (A), bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, Bissulfonyldiazomethanes such as bis (2,4-dimethylphenylsulfonyl) diazomethane; p-toluenesulfonic acid 2-nitrobenzyl, p-toluenesulfonic acid 2,6-dinitrobenzyl, nitrobenzyltosylate, dinitrobenzyltosylate, Nitrobenzyl derivatives such as nitrobenzylsulfonate, nitrobenzylcarbonate, dinitrobenzylcarbonate; pyrogalloltrimesylate, pyrogalloltritosylate, benzyltosylate, benzylsulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxy Sulfonate esters such as succinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyphthalimide; N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -1,8-naphthylimide, Trifluoromethanesulfonic acid esters such as N- (trifluoromethylsulfonyloxy) -4-butyl-1,8-naphthalimide (where, compounds represented by the formula (a1-i) or the formula (a1-ii), Excludes compounds represented by the formula (a2-i) or the formula (a2-ii) and compounds represented by the formula (a3-i) or the formula (a3-ii)); diphenyliodonium. Hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluo Onium salts such as lomethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; benzointosylates such as benzointosylate and α-methylbenzointosylate; other diphenyliodonium salts, triphenylsulfonium salts , Phenyldiazonium salt, benzyl carbonate and the like.

The total content of the acid generator (A) is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 8% by mass or less, based on the total solid content of the photosensitive resin composition. It is preferably 0.05% by mass or more and 5% by mass or less.
Further, the compound represented by the above-mentioned formula (a1-i) or formula (a1-ii), the compound represented by the formula (a2-i) or the formula (a2-ii), and the formula (a3-i). Alternatively, the total amount of the compounds represented by the formula (a3-ii) is preferably 0.01% by mass or more and 10% by mass or less, and 0.03% by mass or more and 8% by mass or less, based on the total solid content of the photosensitive resin composition. The following is more preferable, and 0.05% by mass or more and 5% by mass or less is particularly preferable.
When the amount of the acid generator (A) used is in the above range, it is easy to prepare a photosensitive resin composition having better sensitivity, a uniform solution, and excellent storage stability.

<Resin (B)>
The resin (B) whose solubility in alkali is increased by the action of acid is not particularly limited, and any resin whose solubility in alkali is increased by the action of acid can be used. Examples of the resin (B) whose solubility in alkali is increased by the action of an acid include a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3).
The resin (B) preferably contains an acrylic resin (B3). The ratio of the acrylic resin contained in the resin (B) to the resin (B), that is, the ratio of the acrylic resin (B3) to the resin (B) is preferably 70% by mass or more.

[Novolak resin (B1)]
The novolak resin (B1) is a novolak resin having an acid dissociative dissolution inhibitory group.
As the novolak resin (B1), a resin containing a structural unit represented by the following formula (b1) can be used.

In the above formula (b1), R ^1b represents an acid dissociation dissolution inhibitor, and R ^2b and R ^3b independently represent a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms.

Examples of the ^{acid dissociative dissolution inhibitor group represented by R 1b} include a group represented by the following formulas (b2) and (b3), a linear, branched or cyclic alkyl having 1 to 6 carbon atoms. It is preferably a group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the above formulas (b2) and (b3), R ^4b and R ^5b each independently represent a hydrogen atom or a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, and R ^6b is carbon. Represents a linear, branched, or cyclic alkyl group having 1 or more and 10 or less atoms, and R ^7b represents a linear, branched, or cyclic alkyl group having 1 or more and 6 or less carbon atoms. Represents 0 or 1.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. .. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

Here, as the acid dissociative dissolution inhibitory group represented by the above formula (b2), specifically, a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, Examples thereof include isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. Specific examples of the acid dissociative dissolution inhibitory group represented by the above formula (b3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include groups having 1 or more and 6 or less carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]
The polyhydroxystyrene resin (B2) is a polyhydroxystyrene resin having an acid dissociative dissolution inhibitory group.
In the present specification, the "polyhydroxystyrene resin" is not particularly limited as long as it is a resin recognized by those skilled in the art as a polyhydroxystyrene resin in the technical field relating to the photosensitive resin composition. Typically, the polyhydroxystyrene resin has a total of 70 mol% or more of the hydroxystyrene structural unit, which is a structural unit derived from hydroxystyrene or a hydroxystyrene derivative, and the structural unit derived from styrene, and hydroxystyrene. It is a resin having a total of 50 mol% or more of the constituent units. The "hydroxystyrene derivative" is a compound in which a hydrogen atom bonded to a hydrogen atom of a hydroxy group of hydroxystyrene or a carbon atom at the α-position of hydroxystyrene is replaced with a hydrocarbon group which may have an oxygen atom. is there.
Examples of the acid dissociative dissolution inhibitory group include acid dissociative dissolution inhibitory groups similar to those exemplified in the above formulas (b2) and (b3).

As the polyhydroxystyrene resin (B2), a resin containing a structural unit represented by the following formula (b4) can be used.

In the above formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms, and R ^9b represents an acid dissociation dissolution inhibitory group.

The alkyl group having 1 or more and 6 or less carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 or more and 6 or less carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

As the ^{acid dissociative dissolution inhibitor represented by R 9b} , the same acid dissociative dissolution inhibitor as those exemplified in the above formulas (b2) and (b3) can be used.

Further, the resin containing the structural unit represented by the above formula (b4) as the polyhydroxystyrene resin (B2) contains another polymerizable compound as a structural unit for the purpose of appropriately controlling the physical and chemical properties. be able to. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-. Methacrylate derivatives having carboxy groups and ester bonds such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meta) acrylic acid alkyl esters such as (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, (Meta) acrylic acid aryl esters such as benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, Vinyl group-containing aromatic compounds such as α-methylhydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugate diolefins such as butadiene and isoprene; Nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylicamide; and the like can be mentioned.
When the polyhydroxystyrene resin (B2) contains a polymerizable compound other than the structural unit represented by the above formula (b4) as a structural unit, the structural unit derived from the other polymerizable compound is an acid. It may have a dissociative dissolution inhibitory group.

[Acrylic resin (B3)]
The acrylic resin (B3) is an acrylic resin having an acid dissociative dissolution inhibitory group.
The acrylic resin (B3) is not particularly limited as long as it is an acrylic resin whose solubility in an alkali is increased by the action of an acid and has been conventionally blended in various photosensitive resin compositions.

As used herein, the term "acrylic resin" is a resin containing 70 mol% or more of an acrylic structural unit, which is a structural unit derived from (meth) acrylic acid or a (meth) acrylic acid derivative.
Further, in the present specification, the "(meth) acrylic acid derivative" is a (meth) acrylic acid ester, (meth) acrylamide which may be an N-substituted product, and (meth) acrylonitrile.
In addition, in this specification, "(meth) acrylic" means both "acrylic" and "methacryl". "(Meta) acrylic rate" means both "acrylate" and "methacrylate".
The "acrylic resin" may contain 30 mol% or less of a structural unit derived from a monomer other than the (meth) acrylic acid and the (meth) acrylic acid derivative in the (meth) acrylic resin.

Acrylic resin (B3) is, for example, -SO 2 _- containing cyclic group, or preferably contains a structural unit (b-3) derived from an acrylate ester containing a lactone-containing cyclic group. In such a case, when forming a resist pattern, it is easy to form a resist pattern having a preferable cross-sectional shape.

(-SO ₂ -containing cyclic group)
Here, "- SO 2 _- containing cyclic group" means, -SO 2 _- within the ring skeleton thereof shows a cyclic group containing a ring containing, in particular, -SO 2 _- in the sulfur atom ( S) is a cyclic group forming a part of the cyclic skeleton of the cyclic group. _{A ring containing −SO 2} − in its ring skeleton is counted as the first ring, and if it is the ring alone, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. It is called. The −SO ₂ − containing cyclic group may be monocyclic or polycyclic.

-SO ₂ - containing cyclic group, in particular, -O-SO ₂ - within the ring skeleton cyclic group containing, i.e. -O-SO ₂ - -O-S- medium is a part of the ring skeleton It is preferably a cyclic group containing a sultone ring to be formed.

-SO ₂ - carbon atoms containing cyclic group preferably has 3 to 30, more preferably 4 to 20, more preferably 4 to 15, particularly preferably 4 to 12. The number of carbon atoms is the number of carbon atoms constituting the ring skeleton, and does not include the number of carbon atoms in the substituent.

The −SO ₂ -containing cyclic group may be a −SO ₂ -containing aliphatic cyclic group or a −SO ₂ -containing aromatic cyclic group. Preferably -SO ₂ - containing aliphatic cyclic group.

As the −SO ₂ − containing aliphatic cyclic group, a hydrogen atom is obtained from an aliphatic hydrocarbon ring in which a part of carbon atoms constituting the ring skeleton is _{substituted with −SO 2} − or −O−SO _{2 −.} Examples include groups excluding at least one. More specifically, a group in which at least one hydrogen atom is removed from the aliphatic hydrocarbon ring in which _{−CH 2} − constituting the ring skeleton is _{substituted with −SO 2 −, and the ring is composed of −CH 2} −. Examples thereof include a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which CH ₂ − is substituted with −O−SO _2−.

The number of carbon atoms in the alicyclic hydrocarbon ring is preferably 3 or more and 20 or less, and more preferably 3 or more and 12 or less. The alicyclic hydrocarbon ring may be a polycyclic type or a monocyclic type. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 or more and 6 or less carbon atoms is preferable. Examples of the monocycloalkane include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon ring is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 or more and 12 or less carbon atoms, and specifically, the polycycloalkane is adamantane or norbornane. , Isobornane, tricyclodecane, tetracyclododecane and the like.

The −SO ₂ − containing cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, an oxygen atom (= O), -COOR ", -OC (= O) R", a hydroxyalkyl group, a cyano group and the like. Can be mentioned.

As the alkyl group as the substituent, an alkyl group having 1 to 6 carbon atoms is preferable. The alkyl group is preferably linear or branched. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group and the like. Be done. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

As the alkoxy group as the substituent, an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specific examples thereof include a group in which an alkyl group mentioned as the above-mentioned alkyl group as a substituent is bonded to an oxygen atom (−O−).

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the alkyl halide group of the substituent include a group in which a part or all of the hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned halogen atom.

Examples of the alkyl halide group as the substituent include a group in which a part or all of the hydrogen atoms of the alkyl group mentioned as the alkyl group as the substituent are substituted with the above-mentioned halogen atom. As the alkyl halide group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

The R "in the above-mentioned -COOR" and -OC (= O) R "is a hydrogen atom or a linear, branched-chain or cyclic alkyl group having 1 to 15 carbon atoms.

When R "is a linear or branched alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or 2.

When R "is a cyclic alkyl group, the number of carbon atoms of the cyclic alkyl group is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and particularly preferably 5 or more and 10 or less. Specifically, a fluorine atom. , Or monocycloalkanes that may or may not be substituted with an alkyl fluorinated group, and polycycloalkanes such as bicycloalkanes, tricycloalkanes, tetracycloalkanes, etc., except for one or more hydrogen atoms. More specifically, one or more hydrogen atoms can be obtained from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantan, norbornan, isobornane, tricyclodecane, and tetracyclododecane. Excluded groups and the like can be mentioned.

As the hydroxyalkyl group as the substituent, a hydroxyalkyl group having 1 to 6 carbon atoms is preferable. Specifically, a group in which at least one hydrogen atom of the alkyl group mentioned as the alkyl group as the above-mentioned substituent is substituted with a hydroxyl group can be mentioned.

（式中、Ａ’は酸素原子若しくは硫黄原子を含んでいてもよい炭素原子数１以上５以下のアルキレン基、酸素原子又は硫黄原子であり、ｚは０以上２以下の整数であり、Ｒ^１０ｂはアルキル基、アルコキシ基、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基、又はシアノ基であり、Ｒ”は水素原子、又はアルキル基である。） -SO ₂ - containing cyclic group, and more specifically, include groups represented by the following formula (3-1) to (3-4).

(In the formula, A'is an alkylene group, an oxygen atom or a sulfur atom having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom, z is an integer of 0 or more and 2 or less, and R ^10b. Is an alkyl group, an alkoxy group, an alkyl halide group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group, or a cyano group, and R "is a hydrogen atom or an alkyl group.)

In the above formulas (3-1) to (3-4), A'is an alkylene group having 1 or more and 5 or less carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-). , Oxygen atom, or sulfur atom. The alkylene group having 1 or more and 5 or less carbon atoms in A'preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group in which -O- or -S- is interposed between the terminal or carbon atom of the above-mentioned alkylene group, for example, -O-. _{CH 2 -, - CH 2 -O} -CH 2 -, - S-CH 2 -, - CH 2 -S-CH 2 - , and the like. As A', an alkylene group having 1 or more and 5 or less carbon atoms or —O— is preferable, an alkylene group having 1 or more and 5 or less carbon atoms is more preferable, and a methylene group is most preferable.

z may be any of 0, 1, and 2, with 0 being most preferred. When z is 2, the plurality of R ^10b may be the same or different.

The alkyl group, alkoxy group, alkyl halide group, -COOR ", -OC (= O) R", and hydroxyalkyl group in R ^10b _{may each have a -SO 2} -containing cyclic group. Examples of the alkyl group, alkoxy group, alkyl halide group, -COOR ", -OC (= O) R", and hydroxyalkyl group mentioned as substituents are the same as those described above.

Specific cyclic groups represented by the above formulas (3-1) to (3-4) will be illustrated below. In addition, "Ac" in the formula indicates an acetyl group.

The -SO ₂ - containing cyclic group, among the above, preferably a group represented by the formula (3-1) described above, the aforementioned chemical formula (3-1-1), (3-1-18) , (3-3-1), and (3-4-1), at least one selected from the group consisting of groups represented by any of (3-4-1) is more preferable, and the above-mentioned chemical formula (3-1-1) is used. The group represented is most preferred.

(Lactone-containing cyclic group)
The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing −OC (= O) − in its cyclic skeleton. The lactone ring is counted as the first ring, and when it has only a lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

As the lactone cyclic group in the structural unit (b-3), any one can be used without particular limitation. Specifically, the lactone-containing monocyclic group is a group obtained by removing one hydrogen atom from a 4- to 6-membered ring lactone, for example, a group obtained by removing one hydrogen atom from β-propionolactone, or γ-butyrolactone. Examples thereof include a group from which one hydrogen atom has been removed, a group from which one hydrogen atom has been removed from δ-valerolactone, and the like. Examples of the lactone-containing polycyclic group include a bicycloalkane having a lactone ring, a tricycloalkane, and a tetracycloalkane from which one hydrogen atom has been removed.

As the structural unit (b-3), -SO 2 - containing cyclic group, or a lactone-containing cyclic structure other parts as long as it has a group is not particularly limited, and bonded to the α-position carbon atom -SO 2 a structural unit is a hydrogen atom are derived substituted from even an acrylate ester with a substituent _- structural unit containing an containing cyclic group (b-3-S), and α-position carbon atom It is selected from the group consisting of a structural unit (b-3-L) derived from an acrylic acid ester in which the hydrogen atom bonded to is optionally substituted with a substituent and containing a lactone-containing cyclic group. At least one structural unit is preferred.

[Constituent unit (b-3-S)]
More specifically, as an example of the structural unit (b-3-S), a structural unit represented by the following formula (b-S1) can be mentioned.

（式中、Ｒは水素原子、炭素原子数１以上５以下のアルキル基、又は炭素原子数１以上５以下のハロゲン化アルキル基であり、Ｒ^１１ｂは−ＳＯ_２−含有環式基であり、Ｒ^１２ｂは単結合、又は２価の連結基である。）

(Wherein, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, R ^11b represents a -SO 2 _- containing cyclic group, R ^12b is a single bond or a divalent linking group.)

In the formula (b-S1), R is the same as described above.
R ^11b is, -SO ₂ mentioned above - is similar to the containing cyclic group.
R ^12b may be either a single bond or a divalent linking group.

The ^{divalent linking group in R 12b} is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom and the like are preferable.

-Divalent hydrocarbon group which may have a substituent The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Saturated hydrocarbon groups are usually preferred. More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, and the like.

The number of carbon atoms of the linear or branched aliphatic hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and further preferably 1 or more and 5 or less.

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], a trimethylene group _{[- (CH 2) 3 -} ], a tetramethylene group _{[- (CH 2) 4 -} ] , Pentamethylene group [-(CH ₂ ) _5- ] and the like.

As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferable. Specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH) ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkylmethylene groups; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )- , -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ CH ₃ ) _2- CH _2-, etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH ₂ −, −CH ₂ CH (CH ₃ ) CH ₂ − and other alkyl methylene groups; −CH (CH ₃ ) CH ₂ CH ₂ CH ₂ −, −CH ₂ CH (CH ₃ ) CH ₂ CH ₂ − Alkyl alkylene groups such as alkyl tetramethylene groups and the like can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) for substituting a hydrogen atom. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxo group (= O).

As the aliphatic hydrocarbon group containing a ring in the above structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (two hydrogen atoms are removed from the aliphatic hydrocarbon ring). Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group in a linear or branched chain. Examples thereof include a group intervening in the middle of the aliphatic hydrocarbon group. Examples of the above-mentioned linear or branched-chain aliphatic hydrocarbon group include the same as those described above.

The number of carbon atoms of the cyclic aliphatic hydrocarbon group is preferably 3 or more and 20 or less, and more preferably 3 or more and 12 or less.

The cyclic aliphatic hydrocarbon group may be a polycyclic type or a monocyclic type. As the monocyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The number of carbon atoms of the monocycloalkane is preferably 3 or more and 6 or less. Specific examples thereof include cyclopentane and cyclohexane. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable. The number of carbon atoms of the polycycloalkane is preferably 7 or more and 12 or less. Specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) that substitutes for a hydrogen atom. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, an oxo group (= O) and the like.

As the alkyl group as the substituent, an alkyl group having 1 or more carbon atoms and 5 or less carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are more preferable.

The alkoxy group as the substituent is preferably an alkoxy group having 1 or more and 5 or less carbon atoms, and is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

Examples of the halogen atom as the above-mentioned substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the alkyl halide group as the above-mentioned substituent include a group in which a part or all of the hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned halogen atom.

The cyclic aliphatic hydrocarbon group may have a part of carbon atoms constituting its ring structure substituted with -O- or -S-. The substituent containing a hetero atom, -O -, - C (= O) -O -, - S -, - S (= O) 2 -, - S (= O) 2 -O- are preferred.

The aromatic hydrocarbon group as the divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring, and may have a substituent. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 or more and 30 or less, more preferably 5 or more and 20 or less, further preferably 6 or more and 15 or less, and particularly preferably 6 or more and 12 or less. However, the number of carbon atoms does not include the number of carbon atoms of the substituent.

Specifically, the aromatic ring is an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, and phenanthrene; an aromatic heterocycle in which a part of carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom; And so on. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

Specifically, as an aromatic hydrocarbon group as a divalent hydrocarbon group, a group obtained by removing two hydrogen atoms from the above aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); A group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); a group obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocycle (for example, a group obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocycle). A group in which one of the hydrogen atoms of an aryl group or heteroaryl group is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, 2- A group obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as a naphthylethyl group); and the like.

The number of carbon atoms of the above aryl group or alkylene group bonded to the heteroaryl group is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, and particularly preferably 1.

In the above aromatic hydrocarbon group, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, an oxo group (= O) and the like.

As the alkyl group as the substituent, an alkyl group having 1 or more carbon atoms and 5 or less carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group are more preferable.

As the alkoxy group as the above-mentioned substituent, an alkoxy group having 1 or more and 5 or less carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Is preferable, and a methoxy group and an ethoxy group are more preferable.

Examples of the halogen atom as the above-mentioned substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the alkyl halide group as the above-mentioned substituent include a group in which a part or all of the hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned halogen atom.

-Divalent linking group containing a hetero atom The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, and is, for example, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. And so on.

Specific examples of the divalent linking group containing a heteroatom include -O-, -C (= O)-, -C (= O) -O-, -OC (= O) -O-, _{-S -, - S (= O} ) 2 -, - S (= O) 2 -O -, - NH -, - NH-C (= O) -, - NH-C (= NH) -, = N Examples thereof include a non-hydrocarbon-based linking group such as −, and a combination of at least one of these non-hydrocarbon-based linking groups and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include those similar to the divalent hydrocarbon group which may have the above-mentioned substituent, and a linear or branched aliphatic hydrocarbon group is preferable. ..

Of the above, H in -NH-, -NH-, and -NH-C (= NH)- in -C (= O) -NH- is substituted with a substituent such as an alkyl group or an acyl group, respectively. It may have been done. The number of carbon atoms of the substituent is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

As the ^{divalent linking group in R 12b,} a divalent linking group containing a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a heteroatom is particularly preferable.

When the ^{divalent linking group in R 12b} is a linear or branched alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and 1 or more and 4 or less. Is particularly preferable, and 1 or more and 3 or less are most preferable. Specifically, in the description of the above-mentioned "divalent hydrocarbon group which may have a substituent" as the divalent linking group, it is mentioned as a linear or branched aliphatic hydrocarbon group. Examples thereof include a linear alkylene group and a branched alkylene group.

When the ^{divalent linking group in R 12b} is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group may have a "substituent" as the above-mentioned divalent linking group. In the description of "divalent hydrocarbon group", the same group as the cyclic aliphatic hydrocarbon group mentioned as "aliphatic hydrocarbon group containing a ring in the structure" can be mentioned.

As the cyclic aliphatic hydrocarbon group, a group in which two or more hydrogen atoms are removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane is particularly preferable.

When the ^{divalent linking group in R 12b} is a divalent linking group containing a hetero atom, -O-, -C (= O) -O-, -C (= O) are preferable as the linking group. )-, -OC (= O) -O-, -C (= O) -NH-, -NH- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S (= O) _2- , -S (= O) _2- O-, general formula -Y ^1b -O-Y ^2b -,-[Y ^1b- C (= O) -O] _{m '} Groups represented by −Y ^2b − or −Y ^1b −OC (= O) −Y ^2b − [Even if Y ^1b and Y ^{2b in the} formula each have independent substituents. It is a good divalent hydrocarbon group, where O is an oxygen atom and m'is an integer greater than or equal to 0 and less than or equal to 3. ] Etc. can be mentioned.

When the ^{divalent linking group in R 12b} is -NH-, the hydrogen atom in -NH- may be substituted with a substituent such as an alkyl group or an acyl group. The number of carbon atoms of the substituent (alkyl group, acyl group, etc.) is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

Wherein ^{-Y 1b -O-Y 2b -,} - [Y 1b -C (= O) -O] m '-Y 2b -, or ^{-Y 1b -O-C (= O} ) -Y 2b - in, Y ^1b and Y ^2b are divalent hydrocarbon groups that may independently have substituents. Examples of the divalent hydrocarbon group include the same as the “divalent hydrocarbon group which may have a substituent” mentioned in the explanation as the divalent linking group.

As Y ^1b , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 or more carbon atoms and 5 or less carbon atoms is more preferable, and a methylene group and ethylene are preferable. Groups are particularly preferred.

As Y ^2b , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group, and an alkylmethylene group are more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

Formula ^{- [Y 1b -C (= O} ) -O] m '-Y 2b - In the group represented by, m' is an integer of 0 to 3, preferably 0 to 2 integer 0 or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula − [Y ^1b −C (= O) −O] _{m ′} −Y ^2b − is represented by the formula −Y ^1b −C (= O) −O−Y ^2b−. Groups are particularly preferred. Among them, the formula _{- (CH 2) a '-C} (= O) -O- (CH 2) b' - a group represented by are preferred. In the formula, a'is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, still more preferably 1 or 2, and most preferably 1. b'is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, still more preferably 1 or 2, and most preferably 1.

Regarding the divalent linking group in R ^{12b, as} the divalent linking group containing a hetero atom, an organic group consisting of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group is preferable. Among them, a linear group having an oxygen atom as a hetero atom, for example, a group containing an ether bond or an ester bond is preferable, and the above-mentioned formulas −Y ^1b −O−Y ^2b− , − [Y ^1b− C (=). ^{_{O) -O] m '-Y 2b}} -, or ^{-Y 1b -O-C (= O} ) -Y 2b - more preferably a group represented by the previously described formula ^{- [Y 1b -C (= O} ) -O] _{m '-Y} ^2b -, or ^{-Y 1b -O-C (= O} ) -Y 2b - is particularly desirable.

As the ^{divalent linking group in R 12b,} those containing an alkylene group or an ester bond (-C (= O) -O-) are preferable.

The alkylene group is preferably a linear or branched alkylene group. Preferable examples of the linear aliphatic hydrocarbon group include methylene group [−CH ₂ −], ethylene group [− (CH ₂ ) ₂ −], trimethylene group [− (CH ₂ ) ₃ −], a tetramethylene group _{[- (CH 2) 4 -} ], and a pentamethylene group _{[- (CH 2) 5 -} ] , and the like. Preferable examples of this branched alkylene group are -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , -C (CH ₃ ) (CH _2). Alkylene methylene groups such as _{CH 3} )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2- ; -CH (CH 3} ) CH _2- , -CH ( _{CH 3) CH (CH 3)} -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3) 2 -CH 2 - alkyl ethylene such as Group; -CH (CH ₃ ) CH ₂ CH ₂ −, −CH ₂ CH (CH ₃ ) CH ₂ − and other alkyl methylene groups; −CH (CH ₃ ) CH ₂ CH ₂ CH ₂ −, −CH ₂ CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as _{CH 2} CH _2-.

As the divalent linking group containing an ester bond, in particular, the formula: -R ^13b- C (= O) -O- [in the formula, R ^13b is a divalent linking group. ] Is preferred. That is, the structural unit (b-3-S) is preferably a structural unit represented by the following formula (b-S1-1).

（式中、Ｒ、及びＲ^１１ｂはそれぞれ前記と同様であり、Ｒ^１３ｂは２価の連結基である。）

(In the formula, R and R ^11b are the same as described above, and R ^13b is a divalent linking group.)

The R ^13b is not particularly limited, and examples thereof include the same as the divalent linking group in ^{R 12b described above.}
As the ^{divalent linking group of R 13b,} a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, or a divalent linking group containing a hetero atom is preferable, and the divalent linking group is linear. Alternatively, a branched alkylene group or a divalent linking group containing an oxygen atom as a hetero atom is preferable.

As the linear alkylene group, a methylene group or an ethylene group is preferable, and a methylene group is particularly preferable. As the branched alkylene group, an alkylmethylene group or an alkylethylene group is preferable, and -CH (CH ₃ )-, -C (CH ₃ ) _2- , or -C (CH ₃ ) ₂ CH _2- is particularly preferable. preferable.

As the divalent linking group containing an oxygen atom, an ether bond or a divalent linking group containing an ester bond is preferable, and the above-mentioned −Y ^1b −O−Y ^2b− , − [Y ^1b− C (= O) ^{_{) -O] m '-Y 2b -}} , or ^{-Y 1b -O-C (= O} ) -Y 2b - is more preferable. Y ^1b and Y ^2b are divalent hydrocarbon groups that may independently have substituents, and m'is an integer of 0 or more and 3 or less. Of these, −Y ^1b −OC (= O) −Y ^2b − is preferable, and the _{group represented by − (CH 2} ) _c −OC (= O) − (CH ₂ ) _d − is particularly preferable. .. c is an integer of 1 or more and 5 or less, preferably 1 or 2. d is an integer of 1 or more and 5 or less, preferably 1 or 2.

As the structural unit (b-3-S), a structural unit represented by the following formula (b-S1-11) or (b-S1-12) is particularly preferable, and the structural unit (b-S1-12) is used. The structural unit represented is more preferable.

（式中、Ｒ、Ａ’、Ｒ^１０ｂ、ｚ、及びＲ^１３ｂはそれぞれ前記と同じである。）

(In the formula, R, A', R ^10b , z, and R ^13b are the same as described above, respectively.)

In the formula (b-S1-11), A'preferably is a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

As R ^13b , a linear or branched alkylene group or a divalent linking group containing an oxygen atom is preferable. The ^{linear or branched alkylene group and the divalent linking group containing an oxygen atom in R 13b} include the above-mentioned linear or branched alkylene group and a divalent linking group containing an oxygen atom, respectively. The same can be mentioned.

As the structural unit represented by the formula (b-S1-12), the structural unit represented by the following formula (b-S1-12a) or (b-S1-12b) is particularly preferable.

（式中、Ｒ、及びＡ’はそれぞれ前記と同じであり、ｃ〜ｅはそれぞれ独立に１以上３以下の整数である。）

(In the formula, R and A'are the same as above, and c to e are independently integers of 1 or more and 3 or less.)

[Constituent unit (b-3-L)]
Examples of the structural unit (b-3-L) include those in which R ^11b in the above formula (b-S1) is replaced with a lactone-containing cyclic group, and more specifically, the following formula (b-S1) is used. Examples thereof include structural units represented by b-L1) to (b-L5).

（式中、Ｒは水素原子、炭素原子数１以上５以下のアルキル基、又は炭素原子数１以上５以下のハロゲン化アルキル基であり；Ｒ’はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基、又はシアノ基であり、Ｒ”は水素原子、又はアルキル基であり；Ｒ^１２ｂは単結合、又は２価の連結基であり、ｓ”は０以上２以下の整数であり；Ａ”は酸素原子若しくは硫黄原子を含んでいてもよい炭素原子数１以上５以下のアルキレン基、酸素原子、又は硫黄原子であり；ｒは０又は１である。）

(In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms; R'is an independent hydrogen atom, alkyl group, and alkoxy group, respectively. , Alkyl halide group, hydroxyl group, -COOR ", -OC (= O) R", hydroxyalkyl group, or cyano group, where R "is a hydrogen atom or alkyl group; R ^12b is a single bond or It is a divalent linking group, where s "is an integer of 0 or more and 2 or less; A" is an alkylene group, oxygen atom, or sulfur having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom. It is an atom; r is 0 or 1.)

R in the formulas (b-L1) to (b-L5) is the same as described above.
The alkyl group in R ', alkoxy group, halogenated alkyl group, -COOR ", - OC (= O) R", The hydroxyalkyl group, respectively, -SO ₂ - may have the containing cyclic group Examples of the substituents include an alkyl group, an alkoxy group, an alkyl halide group, -COOR ", -OC (= O) R", and a hydroxyalkyl group similar to those described above.

R'is preferably a hydrogen atom in consideration of industrial availability and the like.
The alkyl group in "R" may be linear, branched or cyclic.
When R "is a linear or branched alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.
When R "is a cyclic alkyl group, the number of carbon atoms is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and most preferably 5 or more and 10 or less. Specifically, one or more polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, which may or may not be substituted with a fluorine atom or an alkyl fluorinated group. Examples thereof include groups excluding hydrogen atoms. Specifically, one or more monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantan, norbornan, isobornane, tricyclodecane, and tetracyclododecane. Examples include groups excluding hydrogen atoms.
Examples of A ″ include those similar to A ′ in the above formula (3-1). A ″ is an alkylene group having 1 or more carbon atoms and 5 or less carbon atoms, an oxygen atom (−O−), or a sulfur atom. It is preferably (-S-), and more preferably an alkylene group having 1 or more and 5 or less carbon atoms, or -O-. As the alkylene group having 1 or more and 5 or less carbon atoms, a methylene group or a dimethylmethylene group is more preferable, and a methylene group is most preferable.

R ^12b is the same as ^{R 12b} in the above-mentioned formula (b-S1).
In the formula (b-L1), s "is preferably 1 or 2.
Hereinafter, specific examples of the structural units represented by the above-mentioned formulas (b-L1) to (b-L3) will be illustrated. In each of the following formulas, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

As the structural unit (b-3-L), at least one selected from the group consisting of the structural units represented by the above-mentioned formulas (b-L1) to (b-L5) is preferable, and the structural unit (b-3-L) is preferably at least one type. ) To (b-L3), at least one selected from the group consisting of the structural units represented by the above formulas (b-L1) or (b-L3) is more preferable. At least one selected from the group is particularly preferred.
Among them, the above-mentioned formulas (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2). At least one selected from the group consisting of the structural units represented by -14), (b-L3-1), and (b-L3-5) is preferable.

式（ｂ−Ｌ６）及び（ｂ−Ｌ７）中、Ｒ及びＲ^１２ｂは前述と同様である。 Further, as the structural unit (b-3-L), the structural unit represented by the following formulas (b-L6) to (b-L7) is also preferable.

In the formulas (b-L6) and (b-L7), R and R ^12b are the same as described above.

Further, the acrylic resin (B3) is a structural unit represented by the following formulas (b5) to (b7) having an acid dissociative group as a structural unit that enhances the solubility of the acrylic resin (B3) in alkali by the action of an acid. including.

In the above formulas (b5) to (b7), R ^14b and R ^{18b to} R ^23b are independently hydrogen atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, fluorine atoms, or fluorine atoms, respectively. Represents a linear or branched fluorinated alkyl group ^{having 1 or more and 6 or less carbon atoms, and R 15b to} R ^17b are independently linear or branched alkyl groups having 1 or more and 6 or less carbon atoms. Represents a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms or an aliphatic cyclic group having 5 to 20 carbon atoms, and each independently has a linear chain having 1 to 6 carbon atoms. Represents a linear or branched alkyl group or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, and R ^16b and R ^17b are bonded to each other, and both are bonded carbon atoms. May form a hydrocarbon ring having 5 or more and 20 or less carbon atoms, Y ^b represents an aliphatic cyclic group or an alkyl group which may have a substituent, and p is 0 or more and 4 or less. It represents an integer and q represents 0 or 1.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Can be mentioned. The fluorinated alkyl group is one in which a part or all of the hydrogen atom of the alkyl group is replaced by a fluorine atom.
Specific examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, a group obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Can be mentioned. In particular, a group obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have a substituent) is preferable.

When the R ^16b and R ^17b do not bond with each other to form a hydrocarbon ring, the R ^15b , R ^16b , and R ^17b have high contrast and good resolution, depth of focus, and the like. It is preferably a linear or branched alkyl group having a number of 2 or more and 4 or less. The R ^19b , R ^20b , R ^22b , and R ^23b are preferably hydrogen atoms or methyl groups.

The R ^16b and R ^17b may form an aliphatic cyclic group having 5 or more and 20 or less carbon atoms together with the carbon atom to which both are bonded. Specific examples of such an aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group is mentioned. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Further, ^{when the aliphatic cyclic group formed by R 16b} and R ^17b has a substituent on its ring skeleton, examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, and an oxygen atom (= O). ), And linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (= O) is particularly preferable.

The Y ^b is an aliphatic cyclic group or an alkyl group, and examples thereof include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. .. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The basis etc. can be mentioned. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferable.

Further, when ^{the aliphatic cyclic group of Y b} has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxy group, a cyano group and an oxygen atom (= O). Examples thereof include a linear or branched alkyl group having 1 or more and 4 or less carbon atoms. As the polar group, an oxygen atom (= O) is particularly preferable.

When Y ^b is an alkyl group, it is preferably a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, preferably 6 or more and 15 or less. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, and a 1-isopropoxy. Ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -Ethoxy-1-methylethyl group and the like can be mentioned.

As a preferable specific example of the structural unit represented by the above formula (b5), those represented by the following formulas (b5-1) to (b5-33) can be mentioned.

In the above formulas (b5-1) to (b5-33), R ^24b represents a hydrogen atom or a methyl group.

As a preferable specific example of the structural unit represented by the above formula (b6), those represented by the following formulas (b6-1) to (b6-26) can be mentioned.

In the above formulas (b6-1) to (b6-26), R ^24b represents a hydrogen atom or a methyl group.

As a preferable specific example of the structural unit represented by the above formula (b7), those represented by the following formulas (b7-1) to (b7-15) can be mentioned.

In the above formulas (b7-1) to (b7-15), R ^24b represents a hydrogen atom or a methyl group.

Among the structural units represented by the formulas (b5) to (b7) described above, the structural unit represented by the formula (b6) is preferable from the viewpoint of easy synthesis and relatively high sensitivity. Further, among the structural units represented by the formula (b6), a structural unit in which Y ^b is an alkyl group is preferable, and a structural unit in which ^{one or both of R 19b} and R ^20b is an alkyl group is preferable.

Further, the acrylic resin (B3) is a resin composed of a copolymer containing the structural units represented by the above formulas (b5) to (b7) and the structural units derived from the polymerizable compound having an ether bond. Is preferable.

Examples of the polymerizable compound having an ether bond include a radically polymerizable compound such as a (meth) acrylic acid derivative having an ether bond and an ester bond, and specific examples thereof include 2-methoxyethyl (meth) acrylate. , 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Examples thereof include acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or methoxytriethylene glycol (meth) acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Further, the acrylic resin (B3) can contain other polymerizable compounds as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic polymerizable compounds.

Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Methacrylic acid derivatives having carboxy groups and ester bonds such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) (Meta) acrylic acid alkyl esters such as acrylates and cyclohexyl (meth) acrylates; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylates and 2-hydroxypropyl (meth) acrylates; phenyl ( (Meta) acrylic acid aryl esters such as meta) acrylates and benzyl (meth) acrylates; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene , Hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other vinyl group-containing aromatic compounds; vinyl acetate and other vinyl group-containing aliphatic compounds; butadiene, isoprene and other conjugated diolefins; Binitrile group-containing polymerizable compounds such as bnitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylicamide; and the like can be mentioned.

As described above, the acrylic resin (B3) may contain a structural unit derived from a polymerizable compound having a carboxy group, such as the above-mentioned monocarboxylic acids and dicarboxylic acids. However, the acrylic resin (B3) does not substantially contain a structural unit derived from a polymerizable compound having a carboxy group because it is easy to form a resist pattern including a non-resist portion having a rectangular shape having a good cross-sectional shape. Is preferable. Specifically, the ratio of the structural units derived from the polymerizable compound having a carboxy group in the acrylic resin (B3) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 5% by mass or less. preferable.
In the acrylic resin (B3), the acrylic resin containing a relatively large amount of the structural unit derived from the polymerizable compound having a carboxy group contains or does not contain a small amount of the structural unit derived from the polymerizable compound having a carboxy group. It is preferably used in combination with an acrylic resin.

Examples of the polymerizable compound include (meth) acrylic acid esters having an acid-non-dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds, and the like. As the acid non-dissociable aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group and the like are particularly preferable in terms of being easily available industrially. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of the (meth) acrylic acid esters having an acid-non-dissociative aliphatic polycyclic group include those having the structures of the following formulas (b8-1) to (b8-5). it can.

In the above formulas (b8-1) to (b8-5), R ^25b represents a hydrogen atom or a methyl group.

Acrylic resin (B3) is, -SO ₂ - containing cyclic group, or containing a structural unit containing a lactone-containing cyclic group (b-3), the structural units in the acrylic resin (B3) (b-3) The content is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 10% by mass or more and 50% by mass or less, and most preferably 10% by mass or more and 30% by mass or less. When the photosensitive resin composition contains a structural unit (b-3) in an amount within the above range, it is easy to achieve both good developability and good pattern shape.

Further, the acrylic resin (B3) preferably contains 5% by mass or more of the structural units represented by the above formulas (b5) to (b7), more preferably 10% by mass or more, and 10% by mass or more. It is particularly preferable to contain 50% by mass or less.

The acrylic resin (B3) preferably contains a structural unit derived from the above-mentioned polymerizable compound having an ether bond. The content of the structural unit derived from the polymerizable compound having an ether bond in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.

The acrylic resin (B3) preferably contains a structural unit derived from the (meth) acrylic acid esters having the above-mentioned acid non-dissociative aliphatic polycyclic group. The content of the structural unit derived from the (meth) acrylic acid ester having an acid-non-dissociable aliphatic polycyclic group in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less. More preferably, it is by mass% or more and 30% by mass or less.

The polystyrene-equivalent mass average molecular weight (hereinafter, also referred to as “mass average molecular weight”) of the resin (B) described above by GPC (gel permeation chromatography) is preferably 10,000 or more and 600,000 or less, more preferably 20,000. It is more than 400,000 or less, more preferably 30,000 or more and 300,000 or less, and particularly preferably 40,000 or more and 300,000 or less. By setting such a mass average molecular weight, it is possible to maintain sufficient strength of the photosensitive resin layer without lowering the peelability from the substrate, and further prevent profile swelling and cracks during plating. be able to.

The dispersity of the resin (B) is preferably 1.05 or more. Here, the degree of dispersion is a value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting such a dispersion degree, it is possible to further avoid the problems of stress resistance to the desired plating and the tendency of the metal layer obtained by the plating treatment to swell.

The content of the resin (B) is preferably 5% by mass or more and 98% by mass or less, and more preferably 5% by mass or more and 85% by mass or less, based on the total solid content of the photosensitive resin composition.

<Phenolic hydroxyl group-containing low molecular weight compound (C)>
The photosensitive resin composition preferably contains a phenolic hydroxyl group-containing low molecular weight compound (C).
The phenolic hydroxyl group means a hydroxyl group (OH) directly bonded to the benzene ring. Since the phenolic hydroxyl group-containing low molecular weight compound (C) has a phenolic hydroxyl group, it is an alkali-soluble compound. The alkali-soluble compound means a compound that dissolves in a 2.38% by mass TMAH aqueous solution.
The low molecular weight compound is a compound that is not a polymer, for example, a compound having a molecular weight of 1500 or less.

The phenolic hydroxyl group-containing low molecular weight compound (C) can increase the dissolution rate of the exposed portion and improve the sensitivity.

The type of the phenolic hydroxyl group-containing low molecular weight compound (C) is not particularly limited as long as it does not impair the object of the present invention. As the phenolic hydroxyl group-containing low molecular weight compound (C), a compound having two or more phenolic hydroxyl groups is preferable. Specific examples of the phenolic hydroxyl group-containing low molecular weight compound (C) include the following compounds.

Further, as the phenolic hydroxyl group-containing low molecular weight compound (C), polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone; tris (4-hydroshikiphenyl). ) Methan, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3) , 5-Dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxy Phenolmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2) , 5-Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3 , 4-Dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5) -Cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy) -2-Methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, 4,4'-[(3,4-dihydroxyphenyl) ) Methylene] bis (2-cyclohexyl-5-methylphenol) and other trisphenol-type compounds; 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis ( Linear trinuclear phenolic compounds such as 2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol; 1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5 − Cycloxyphol Enyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl)- 4-Hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) ) -4-Hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-) Diethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2 -Hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [4-Hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis Linear tetranuclear phenolic compounds such as [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane; 2,4-bis [2-hydroxy-3- (4) -Hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,6-cyclohexyl Bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol and other linear pentanuclear phenol compounds and other linear polyphenol compounds; bis (2) , 3,4-Trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- (2,3,4-trihydroxy) Phenyl) -2- (2', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2', 4'-dihydroxyphenyl) propane, 2- (4) -Hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3'-fluoro-4'-hydroxyphenyl) propane, 2- (2, 4-Benzyl Loxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-tri) Bisphenol-type compounds such as hydroxyphenyl) -2- (4'-hydroxy-3', 5'-dimethylphenyl) propane; 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1 , 1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, etc., polynuclear branched compounds; condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane, bisphenol A, pyrogallol monomethyl Examples thereof include ether, pyrogallol-1,3-dimethylether and the like. These can be used alone or in combination of two or more.

When the photosensitive resin composition contains the phenolic hydroxyl group-containing low molecular weight compound (C), the content of the phenolic hydroxyl group-containing low molecular weight compound (C) is 100 parts by mass based on the total amount of the resins contained in the photosensitive resin composition. , 1 part by mass or more and 20 parts by mass or less is preferable, and 3 parts by mass or more and 15 parts by mass or less is more preferable.

<Alkali-soluble resin (D)>
The photosensitive resin composition preferably further contains an alkali-soluble resin (D) in order to improve alkali solubility. Here, the alkali-soluble resin is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) to form a resin film having a thickness of 1 μm on a substrate and 2.38% by mass of TMAH (water). (Tetramethylammonium oxide) means a solution that dissolves in 0.01 μm or more when immersed in an aqueous solution for 1 minute, and does not correspond to the above-mentioned component (B) (typically, alkali solubility is also achieved by the action of an acid). Refers to a resin that does not substantially fluctuate.) The alkali-soluble resin (D) is preferably at least one resin selected from the group consisting of novolak resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3).

[Novolak resin (D1)]
The novolak resin is obtained, for example, by adding and condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes under an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-Xylenol, 2,4-Xylenol, 2,5-Xylenol, 2,6-Xylenol, 3,4-Xylenol, 3,5-Xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples thereof include trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, fluoroxylenol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.
Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like.
The catalyst at the time of the addition condensation reaction is not particularly limited, but for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

The flexibility of the novolak resin can be further improved by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using bulky aldehydes. Is.

The mass average molecular weight of the novolak resin (D1) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 1500 or more and 50,000 or less.

[Polyhydroxystyrene resin (D2)]
Examples of the hydroxystyrene compound (hydroxystyrene, hydroxystyrene derivative) constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and the like.
Further, the polyhydroxystyrene resin (D2) is preferably a copolymer with the styrene resin. Examples of the styrene-based compound constituting such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene and the like.

The mass average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 1500 or more and 50,000 or less.

[Acrylic resin (D3)]
The acrylic resin (D3) preferably contains a structural unit derived from a polymerizable compound having an ether bond and a structural unit derived from a polymerizable compound having a carboxy group.

Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, and phenoxypolyethylene glycol ( Examples thereof include (meth) acrylic acid derivatives having ether bonds and ester bonds such as meta) acrylates, methoxypolypropylene glycol (meth) acrylates, and tetrahydrofurfuryl (meth) acrylates. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxytriethylene glycol acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Examples of the polymerizable compound having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Examples of compounds having a carboxy group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; and the like can be exemplified. The polymerizable compound having a carboxy group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

The mass average molecular weight of the acrylic resin (D3) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 50,000 or more and 800,000 or less.

The content of the alkali-soluble resin (D) is preferably 3 parts by mass or more and 70 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less, when the total solid content of the photosensitive resin composition is 100 parts by mass. .. By setting the content of the alkali-soluble resin (D) in the above range, the alkali solubility can be easily improved.

<Sulfur-containing compound (E)>
Since the photosensitive resin composition is used for pattern formation on a metal substrate, it is preferable that the photosensitive resin composition contains a sulfur-containing compound (E). The sulfur-containing compound (E) is a compound containing a sulfur atom that can coordinate with a metal. Regarding a compound capable of producing two or more tautomers, when at least one tautomer contains a sulfur atom that coordinates with the metal constituting the surface of the metal substrate, the compound is a sulfur-containing compound. Applicable.
When a resist pattern used as a plating mold is formed on a surface made of a metal such as Cu, defects in cross-sectional shape such as footing are likely to occur. However, when the photosensitive resin composition contains the sulfur-containing compound (E), it is easy to suppress the occurrence of cross-sectional shape defects such as footing even when a resist pattern is formed on the metal surface of the substrate. Note that "footing" is a phenomenon in which the width of the bottom is narrower than the width of the top in the non-resist portion because the resist portion projects toward the non-resist portion near the contact surface between the substrate surface and the resist pattern. Is.

Sulfur atoms that can coordinate with a metal include, for example, a mercapto group (-SH), a thiocarboxy group (-CO-SH), a dithiocarboxy group (-CS-SH), and a thiocarbonyl group (-CS-). Etc. are included in sulfur-containing compounds.
It is preferable that the sulfur-containing compound has a mercapto group because it is easy to coordinate with a metal and has an excellent effect of suppressing footing.

（式中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に水素原子又はアルキル基を示し、Ｒ^ｅ３は単結合又はアルキレン基を示し、Ｒ^ｅ４は炭素以外の原子を含んでいてもよいｕ価の脂肪族基を示し、ｕは２以上４以下の整数を示す。） A preferable example of the sulfur-containing compound having a mercapto group is a compound represented by the following formula (e1).

(In the formula, R ^e1 and R ^e2 each independently represent a hydrogen atom or an alkyl group, R ^e3 represents a single bond or an alkylene group, and R ^e4 is a u-valent fat which may contain an atom other than carbon. Indicates a family group, and u indicates an integer of 2 or more and 4 or less.)

When R ^e1 and R ^e2 are alkyl groups, the alkyl group may be linear or branched chain, and is preferably linear. When R ^e1 and R ^e2 are alkyl groups, the number of carbon atoms of the alkyl group is not particularly limited as long as the object of the present invention is not impaired. The number of carbon atoms of the alkyl group is preferably 1 or more and 4 or less, particularly preferably 1 or 2, and most preferably 1. As ^{a combination of R e1} and R ^e2 , one is preferably a hydrogen atom and the other is an alkyl group, and one is particularly preferably a hydrogen atom and the other is a methyl group.

When ^Re3 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When ^Re3 is an alkylene group, the number of carbon atoms of the alkylene group is not particularly limited as long as it does not impair the object of the present invention. The number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or 2, and most preferably 1.

^Re4 is an aliphatic group having a divalent value or more and a tetravalence or less, which may contain an atom other than carbon. ^Examples of the atom other than carbon that Re4 may contain include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Structure of the aliphatic group is an R ^e4 may be linear, may be branched, may be cyclic, may be a structure combining these structures.

（式（ｅ２）中、Ｒ^ｅ４及びｕは、式（ｅ１）と同意である。） Among the compounds represented by the formula (e1), the compound represented by the following formula (e2) is more preferable.

(In equation (e2), ^Re4 and u agree with equation (e1).)

Among the compounds represented by the above formula (e2), the following compounds are preferable.

（式（ｅ３−Ｌ１）〜（ｅ３−Ｌ７）中、Ｒ’、ｓ”、Ａ”、及びｒは、アクリル樹脂（Ｂ３）について前述した、式（ｂ−Ｌ１）〜（ｂ−Ｌ７）と同様である。） Compounds represented by the following formulas (e3-L1) to (e3-L7) are also mentioned as preferable examples of sulfur-containing compounds having a mercapto group.

(In the formulas (e3-L1) to (e3-L7), R', s", A ", and r are the same as the formulas (b-L1) to (b-L7) described above for the acrylic resin (B3). The same is true.)

Preferable specific examples of the mercapto compounds represented by the above formulas (e3-L1) to (e3-L7) include the following compounds.

（式（ｅ３−１）〜（ｅ３−４）中の略号の定義については、アクリル樹脂（Ｂ３）に関して前述した、式（３−１）〜（３−４）について前述した通りである。） Compounds represented by the following formulas (e3-1) to (e3-4) are also mentioned as preferable examples of sulfur-containing compounds having a mercapto group.

(The definitions of the abbreviations in the formulas (e3-1) to (e3-4) are as described above for the acrylic resin (B3) and the formulas (3-1) to (3-4) described above.)

Preferable specific examples of the mercapto compounds represented by the above formulas (e3-1) to (e3-4) include the following compounds.

（式（ｅ４）において、Ｒ^ｅ５は、水酸基、炭素原子数１以上４以下のアルキル基、炭素原子数１以上４以下のアルコキシ基、炭素数１以上４以下のアルキルチオ基、炭素数１以上４以下のヒドロキシアルキル基、炭素数１以上４以下のメルカプトアルキル基、炭素数１以上４以下のハロゲン化アルキル基及びハロゲン原子からなる群より選択される基であり、ｎ１は０以上３以下の整数であり、ｎ０は０以上３以下の整数であり、ｎ１が２又は３である場合、Ｒ^ｅ５は同一であっても異なっていてもよい。） Moreover, as a preferable example of the compound having a mercapto group, the compound represented by the following formula (e4) can be mentioned.

(In the formula (e4), R ^e5 is a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. It is a group selected from the group consisting of the following hydroxyalkyl groups, mercaptoalkyl groups having 1 to 4 carbon atoms, alkyl halide groups having 1 to 4 carbon atoms and halogen atoms, and n1 is an integer of 0 to 3 carbon atoms. When n0 is an integer of 0 or more and 3 or less and n1 is 2 or 3, ^Re5 may be the same or different.)

Specific example of R ^e5 is an alkyl group which may have a hydroxyl group or less carbon atoms having 1 to 4 include a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl Groups, sec-butyl groups, and tert-butyl groups can be mentioned. Among these alkyl groups, a methyl group, a hydroxymethyl group, and an ethyl group are preferable.

^{Specific examples of the case where Re5} is an alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group and a sec-butyloxy group. Groups and tert-butyloxy groups can be mentioned. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

Specific example of R ^e5 is an alkylthio group having 1 to 4 carbon atoms include methylthio group, ethylthio group, n- propylthio group, isopropylthio group, n- butylthio group, isobutylthio, sec- butylthio , And the tert-butylthio group. Among these alkylthio groups, a methylthio group and an ethylthio group are preferable, and a methylthio group is more preferable.

^{Specific examples of the case where Re5} is a hydroxyalkyl group having 1 or more carbon atoms and 4 or less carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxy-n-propyl group, and 4 -Hydroxy-n-butyl group and the like can be mentioned. Among these hydroxyalkyl groups, a hydroxymethyl group, a 2-hydroxyethyl group, and a 1-hydroxyethyl group are preferable, and a hydroxymethyl group is more preferable.

^{Specific examples of the case where Re5} is a mercaptoalkyl group having 1 or more carbon atoms and 4 or less carbon atoms include a mercaptomethyl group, a 2-mercaptoethyl group, a 1-mercaptoethyl group, a 3-mercapto-n-propyl group, and 4 -Mercapto-n-butyl group and the like can be mentioned. Among these mercaptoalkyl groups, a mercaptomethyl group, a 2-mercaptoethyl group, and a 1-mercaptoethyl group are preferable, and a mercaptomethyl group is more preferable.

When ^Re5 is an alkyl halide group having 1 or more and 4 or less carbon atoms, examples of the halogen atom contained in the alkyl halide group include fluorine, chlorine, bromine, and iodine. Specific example of R ^e5 is a halogenated alkyl group having 1 to 4 carbon atoms are chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, a difluoromethyl group, Trichloromethyl group, tribromomethyl group, trifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, 1,2-dichloroethyl group, 2,2-difluoroethyl group, 1-chloro- Examples thereof include 2-fluoroethyl group, 3-chloro-n-propyl group, 3-bromo-n-propyl group, 3-fluoro-n-propyl group, 4-chloro-n-butyl group and the like. Among these alkyl halide groups, chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trichloromethyl group, tribromomethyl group, and trifluoromethyl group Is preferable, and a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a trifluoromethyl group are more preferable.

^{Specific examples of the case where Re5} is a halogen atom include fluorine, chlorine, bromine, and iodine.

In the formula (e4), n1 is an integer of 0 or more and 3 or less, and 1 is more preferable. When n1 is 2 or 3, the plurality of ^Re5s may be the same or different.

In the compound represented by the formula (e4), ^{the substitution position of Re5} on the benzene ring is not particularly limited. The substitution position of ^Re5 on the benzene ring is preferably the meta position or the para position with respect to the bond position _{of − (CH 2} ) _{n0 −SH.}

Examples of the compound represented by formula (e4), as R ^e5, alkyl group, hydroxyalkyl group, and a group selected from the group consisting of mercaptoalkyl group, a compound having at least one is preferable, as R ^e5, alkyl A compound having one group selected from the group consisting of a group, a hydroxyalkyl group, and a mercaptoalkyl group is more preferable. When the compound represented by the formula (e4) has one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as ^{Re5, an alkyl group, a hydroxyalkyl group, or a mercaptoalkyl group is used.} The substitution position of the group on the benzene ring is preferably in the meta position or the para position with respect to the bond position of _{− (CH 2} ) _{n0 −SH, and more preferably in the para position.}

In the formula (e4), n0 is an integer of 0 or more and 3 or less. Since the compound can be easily prepared and obtained, n0 is preferably 0 or 1, and more preferably 0.

Specific examples of the compound represented by the formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4- (methylthio) benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, and the like. 4-ethoxybenzene thiol, 4-isopropyloxybenzene thiol, 4-tert-butoxybenzene thiol, 3,4-dimethoxybenzene thiol, 3,4,5-trimethoxybenzene thiol, 4-ethylbenzene thiol, 4-isopropylbenzene thiol , 4-n-butylbenzene thiol, 4-tert-butylbenzene thiol, 3-ethylbenzene thiol, 3-isopropylbenzene thiol, 3-n-butylbenzene thiol, 3-tert-butylbenzene thiol, 3,5-dimethylbenzene Thiol, 3,4-dimethylbenzene thiol, 3-tert-butyl-4-methylbenzene thiol, 3-tert-4-methylbenzene thiol, 3-tert-butyl-5-methylbenzene thiol, 4-tert-butyl- 3-Methylbenzene thiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol, 4- (mercaptomethyl) phenol, 3- (mercaptomethyl) phenol, 1,4-di (mercaptomethyl) phenol, 1,3-di (Mercaptomethyl) Phenol, 4-fluorobenzene thiol, 3-fluorobenzene thiol, 4-chlorobenzene thiol, 3-chlorobenzene thiol, 4-bromobenzene thiol, 4-iodobenzene thiol, 3-bromobenzene thiol, 3,4- Dichlorobenzene thiol, 3,5-dichlorobenzene thiol, 3,4-difluorobenzene thiol, 3,5-difluorobenzene thiol, 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3, 5-Di-tert-butyl-4-methoxybenzenethiool, 4-bromo-3-methylbenzenethiool, 4- (trifluoromethyl) benzenethiool, 3- (trifluoromethyl) benzenethiool, 3,5-bis ( Examples thereof include trifluoromethyl) benzene thiol, 4-methyl thiobenzene thiol, 4-ethyl thiobenzene thiol, 4-n-butyl thiobenzene thiol, 4-tert-butyl thiobenzene thiol and the like.

Examples of the sulfur-containing compound having a mercapto group include a tally mutant of a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group and a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group. Be done.
Suitable specific examples of the nitrogen-containing aromatic heterocycle include imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2, 3-triazine, 1,2,4-triazine, 1,3,5-triazine, indol, indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinolin, cinnoline, phthalazine, quinazoline, quinoxalin, And 1,8-naphthylidine.

Suitable specific examples of the nitrogen-containing heterocyclic compound suitable as the sulfur-containing compound and the tautomer of the nitrogen-containing heterocyclic compound include the following compounds.

When the photosensitive resin composition contains the sulfur-containing compound (E), the amount used is 0.01 part by mass with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D). 5 parts by mass or more is preferable, 0.02 parts by mass or more and 3 parts by mass or less is more preferable, and 0.05 parts by mass or more and 2 parts by mass or less is particularly preferable.

<Acid diffusion inhibitor (F)>
The photosensitive resin composition preferably further contains an acid diffusion inhibitor (F) in order to improve the shape of the resist pattern used as a template, the retention stability of the photosensitive resin film, and the like. As the acid diffusion inhibitor (F), a nitrogen-containing compound (F1) is preferable, and if necessary, an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof (F2) can be contained.

[Nitrogen-containing compound (F1)]
Examples of the nitrogen-containing compound (F1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine and n-hexylamine. , N-Heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N, N, N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propion Amide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole , 4-Methylimidazole, 8-oxyquinolin, aclysine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholin, 4-methylmorpholin, piperazin, 1,4-dimethyl Piperazine, 1,4-diazabicyclo [2.2.2] octane, pyridine and the like can be mentioned. These may be used alone or in combination of two or more.

In addition, Adekastab LA-52, Adekastab LA-57, Adekastab LA-63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-81, Adekastab LA-82, and Adekastab LA. Commercially available hindered amine compounds such as -87 (all manufactured by ADEKA) and 4-hydroxy-1,2,2,6,6-pentamethylpiperidine derivatives, 2,6-diphenylpyridine, and 2,6- Pyridine in which the 2,6-positions such as di-tert-butylpyridine are substituted with a substituent such as a hydrocarbon group can also be used as the nitrogen-containing compound (F1).

The nitrogen-containing compound (F1) is usually used in a range of 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D), and is 0 parts by mass or more. It is particularly preferable to use it in the range of 3 parts by mass or less.

[Organic carboxylic acid, or phosphorus oxo acid or derivative thereof (F2)]
Of the organic carboxylic acid, or the oxo acid of phosphorus or a derivative thereof (F2), the organic carboxylic acid is specifically malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like. , Particularly salicylic acid is preferred.

Phosphonic oxo acids or derivatives thereof include phosphoric acids such as phosphoric acid, di-n-butyl ester of phosphoric acid, diphenyl ester of phosphoric acid and derivatives such as their esters; phosphonic acid, dimethyl phosphonic acid ester, phosphonic acid- Phosphonates such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives such as their esters; such as phosphinic acid such as phosphinic acid, phenylphosphinic acid and their esters. Derivatives; etc. Of these, phosphonic acid is particularly preferable. These may be used alone or in combination of two or more.

The organic carboxylic acid, or the oxo acid of phosphorus or a derivative thereof (F2) is usually 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D). It is used in a range, and it is particularly preferable to use it in a range of 0 parts by mass or more and 3 parts by mass or less.

Further, in order to form and stabilize the salt, it is preferable to use the same amount of the organic carboxylic acid, or the oxo acid of phosphorus or its derivative (F2) as that of the nitrogen-containing compound (F1).

<Organic solvent (S)>
The photosensitive resin composition preferably contains an organic solvent (S). The type of the organic solvent (S) is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected from the organic solvents conventionally used in positive photosensitive resin compositions. ..

Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, and propylene glycol monoacetate. , Dipropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether and other polyvalent alcohols and derivatives thereof; cyclic ethers such as dioxane; ethyl acetate, lactic acid Methyl, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate , Ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and other esters; toluene , Aromatic hydrocarbons such as xylene; and the like. These may be used alone or in combination of two or more.

The content of the organic solvent (S) is not particularly limited as long as it does not impair the object of the present invention. When the photosensitive resin composition is used in a thick film application in which the thickness of the photosensitive resin layer obtained by a spin coating method or the like is 5 μm or more, the solid content concentration of the photosensitive resin composition is 30% by mass or more 70. It is preferable to use the organic solvent (S) in the range of mass% or less.

<Other ingredients>
The photosensitive resin composition may further contain a polyvinyl resin in order to improve the plasticity. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinylmethyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof. Can be mentioned. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

Further, the photosensitive resin composition may further contain an adhesion aid in order to improve the adhesiveness between the mold formed by using the photosensitive resin composition and the metal substrate.

Further, the photosensitive resin composition may further contain a surfactant in order to improve coatability, defoaming property, leveling property and the like. As the surfactant, for example, a fluorine-based surfactant or a silicone-based surfactant is preferably used.
Specific examples of fluorine-based surfactants include BM-1000 and BM-1100 (all manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, and Megafuck F183 (all manufactured by Dainippon Ink and Chemicals). , Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M Ltd.), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S- Commercially available fluorine-based surfactants such as 141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) However, the present invention is not limited to these.
Examples of silicone-based surfactants include unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and aralkyl-based silicone-based surfactants. A reactive silicone-based surfactant or the like can be preferably used.
As the silicone-based surfactant, a commercially available silicone-based surfactant can be used. Specific examples of commercially available silicone-based surfactants include Painted M (manufactured by Toray Dow Corning), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyester-modified silicone-based). Surfactants, manufactured by Clariant, BYK-310 (polyester-modified silicone-based surfactants, manufactured by Big Chemie) and the like.

In addition, the photosensitive resin composition may further contain an acid, an acid anhydride, or a high boiling point solvent in order to finely adjust the solubility in a developing solution.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutylic acid, n-valeric acid, isovaleric acid, benzoic acid and cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxymonocarboxylic acids such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycaterous acid, 3-hydroxycaterous acid, 4-hydroxycaterous acid, 5-hydroxyisophthalic acid, syringic acid, etc. Acids; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid Polyvalent carboxylic acids such as acids, butanetetracarboxylic acids, trimellitic acids, pyromellitic acids, cyclopentanetetracarboxylic acids, butanetetracarboxylic acids, 1,2,5,8-naphthalenetetracarboxylic acids; itaconic anhydride, anhydrous Succinic acid, citraconic acid anhydride, dodecenyl succinic acid anhydride, tricarbanyl anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic acid anhydride, Acid anhydrides such as cyclopentanetetracarboxylic acid dianhydride, phthalic acid anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bis anhydride trimellitate, glycerintris anhydride trimeritate; it can.

Specific examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and benzyl. Ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, capricic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate , Propylene carbonate, phenylcellosolveacetate and the like.

In addition, the photosensitive resin composition may further contain a sensitizer in order to improve the sensitivity. In the present specification, the sensitizer is defined as a compound other than the phenolic hydroxyl group-containing low molecular weight compound (C).

The photosensitive resin composition contains the resin (B) as an essential component as the resin, and if necessary, contains a resin other than the resin (B) such as the alkali-soluble resin (D). In the specification of the present application and claims, the "resin" is a polymer compound having a mass average molecular weight of more than 1500, which is a polymer obtained by polymerizing a monomer compound. The mass average molecular weight is a polystyrene-equivalent mass average molecular weight by GPC (gel permeation chromatography).
In the photosensitive resin composition, the ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is 70% by mass or more. The ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is preferably 80% by mass or more, and more preferably 90% by mass or more.
The acrylic resin may be either the resin (B) or a resin other than the resin (B), but it is preferable that the resin (B) contains an acrylic resin. The ratio of the acrylic resin contained in the resin (B) to the resin (B) is preferably 70% by mass or more.

The "resin other than the resin (B)" is a resin other than the resin (B) contained in the photosensitive resin composition, and for example, the above-mentioned alkali-soluble resin (D), a polyvinyl resin as a plasticizer, and the like can be used. It corresponds to "resin other than resin (B)".
The "total of the resin (B) and the resin other than the resin (B)" is the total amount of the resins contained in the photosensitive resin composition. For example, when the resin contained in the photosensitive resin composition is only the resin (B), the "total of the resin (B) and the resin other than the resin (B)" is only the "resin (B)". is there. When the resin contained in the photosensitive resin composition is the resin (B) and the above-mentioned alkali-soluble resin (D), the "total of the resin (B) and the resin other than the resin (B)" is ". It is the total of the resin (B) and the alkali-soluble resin (D). When the resin contained in the photosensitive resin composition is a resin other than the resin (B), the above-mentioned alkali-soluble resin (D), and the resin (B) and the alkali-soluble resin (D), "resin". "The total of (B) and the resin other than the resin (B)" is the total of the resin (B), the alkali-soluble resin (D), and the resin other than the resin (B) and the alkali-soluble resin (D). is there.

As described above, a chemically amplified positive photosensitive resin composition containing an acid generator (A) that generates an acid by irradiation with active light or radiation and a resin (B) whose solubility in an alkali is increased by the action of the acid. By setting the content of the acrylic resin in the product to a specific range with respect to the total of the resin (B) and the resin other than the resin (B), which contains a specific acid generator, as shown in Examples described later, h It is a chemically amplified positive photosensitive resin composition that can be applied to linear exposure and can easily form a resist pattern having excellent plating solution resistance and crack resistance. Moreover, the cross-sectional shape of the resist pattern is also good.
As described above, the photosensitive resin composition of the present invention, which is applicable to h-line exposure and easily forms a resist pattern having excellent plating solution resistance and crack resistance, is obtained by plating a metal on a substrate having a metal surface. It is used to make a mold for forming a plated model by embedding.

Since the photosensitive resin composition has the above-mentioned specific composition, it can be applied to exposure by h-line. Therefore, the photosensitive resin composition can be preferably applied, for example, to the production of a mold for forming a plated model on a panel-level substrate, which generally has a larger area than a wafer.
When the area of the substrate is large, the plating conditions may be harsher than when the area of the substrate is small. When the area of the substrate is large, the stress applied to the substrate, the mold, the plated object, and the like tends to increase. For panel-level substrates, the shape of the main surface to which the photosensitive resin composition is applied is often rectangular. When the shape of the panel is rectangular, the stress is more likely to vary than when it is circular. Therefore, when a substrate having a large area or a rectangular substrate is applied, the photosensitive resin composition is further required to have plating solution resistance and crack resistance.
Since the photosensitive resin composition is applicable to h-line exposure and has excellent plating solution resistance and crack resistance, it is a substrate having a large area or a rectangular substrate, and is plated on a substrate having a metal surface. It can be particularly preferably used as a chemically amplified positive photosensitive resin composition used for producing a mold for forming a plated molded product by embedding a metal.

<Method for preparing chemically amplified positive photosensitive resin composition>
The chemically amplified positive photosensitive resin composition is prepared by mixing and stirring each of the above components by a usual method. Examples of the device that can be used when mixing and stirring each of the above components include a dissolver, a homogenizer, and a three-roll mill. After uniformly mixing each of the above components, the obtained mixture may be further filtered using a mesh, a membrane filter or the like.

≪Photosensitive dry film≫
The photosensitive dry film has a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer is made of the above-mentioned photosensitive resin composition.

As the base film, one having light transmittance is preferable. Specific examples thereof include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc., and polyethylene terephthalate (PET) film is preferable because it has an excellent balance between light transmission and breaking strength.

A photosensitive dry film is produced by applying the above-mentioned photosensitive resin composition on a base film to form a photosensitive resin layer.
When forming the photosensitive resin layer on the base film, an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, or the like is used, and the film thickness after drying on the base film is preferably 0. The photosensitive resin composition is applied and dried so as to be 5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less.

The photosensitive dry film may further have a protective film on the photosensitive resin layer. Examples of this protective film include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film and the like.

<< Manufacturing method of patterned resist film and substrate with mold >>
The method for forming a patterned resist film on the substrate using the photosensitive resin composition described above is not particularly limited. Such a patterned resist film is used as a mold for forming a plated model.
The preferred method is
A laminating step of laminating a photosensitive resin layer made of a photosensitive resin composition on a substrate, and
An exposure process in which the photosensitive resin layer is exposed by regioselectively irradiating active light rays or radiation,
A developing process that develops the photosensitive resin layer after exposure,
Examples thereof include a method for producing a patterned resist film including.
The method for manufacturing a substrate with a mold provided with a mold for forming a plated object includes a step of laminating a photosensitive resin layer on the metal surface of a substrate having a metal surface, and in the developing step, plating molding by development. It is the same as the method for producing a patterned resist film, except that a mold for forming an object is produced.

As the substrate on which the photosensitive resin layer is laminated, a substrate having a metal surface is used. As the metal species constituting the metal surface, copper, gold, and aluminum are preferable, and copper is more preferable.

The photosensitive resin layer is laminated on the substrate as follows, for example. That is, a liquid photosensitive resin composition is applied onto the substrate, and the solvent is removed by heating to form a photosensitive resin layer having a desired film thickness. The thickness of the photosensitive resin layer is not particularly limited as long as the resist pattern used as a mold can be formed with a desired film thickness. The film thickness of the photosensitive resin layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 100 μm or less.

As a method for applying the photosensitive resin composition on the substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like can be adopted. It is preferable to prebake the photosensitive resin layer. The prebaking conditions vary depending on the type, blending ratio, coating film thickness, etc. of each component in the photosensitive resin composition, but are usually 70 ° C. or higher and 200 ° C. or lower, preferably 80 ° C. or higher and 150 ° C. or lower, for 2 minutes or longer. It takes about 120 minutes or less.

The photosensitive resin layer formed as described above is selectively irradiated with active light or radiation, for example, ultraviolet rays having a wavelength of 300 nm or more and 500 nm or less or visible light through a mask having a predetermined pattern (exposure). Will be done. The active light beam or radiation to be irradiated is preferably one containing light (h line) having a wavelength of 405 nm, and examples thereof include broadband light of a mercury lamp including h line, bandpassed h line single light, and gh line.
The compound represented by the formula (a1-i) or the formula (a1-ii) as the acid generator (A), the compound represented by the formula (a2-i) or the formula (a2-ii), and the formula ( The resin (B) and the resin include at least one selected from the compounds represented by a3-i) or the formula (a3-ii) and the resin (B) whose solubility in an alkali is increased by the action of an acid. By using the chemically amplified positive photosensitive resin composition in which the ratio of the acrylic resin to the total of the resins other than (B) is 70% by mass or more, h-rays applicable to a large-area panel-level package can be obtained. When applied, a resist pattern having excellent plating solution resistance and crack resistance can be formed.

As the radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. Further, the radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion rays and the like. Dose of radiation varies depending on the film thickness and the like of the composition of the photosensitive resin composition and a photosensitive resin layer, for example, in the case of ultra-high pressure mercury lamp used is 100 mJ / cm ² or more 10000 mJ / cm ² or less. Further, the radiation includes a light beam that activates the acid generator (A) in order to generate an acid.

After the exposure, the photosensitive resin layer is heated by a known method to promote the diffusion of the acid, and the alkali solubility of the photosensitive resin layer is changed in the exposed portion of the photosensitive resin film. ..

Next, the exposed photosensitive resin layer is developed according to a conventionally known method, and unnecessary portions are dissolved and removed to form a predetermined resist pattern or a mold for forming a plated object. At this time, an alkaline aqueous solution is used as the developing solution.

Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, and the like. Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5 An aqueous solution of an alkali such as −diazabicyclo [4,3,0] -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above-mentioned aqueous solution of alkalis can also be used as a developing solution.

The developing time varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive resin layer, and the like, but is usually between 1 minute and 30 minutes or less. The developing method may be any of a liquid filling method, a dipping method, a paddle method, a spray developing method and the like.

After development, it is washed with running water for 30 seconds or more and 90 seconds or less, and dried using an air gun, an oven, or the like. In this way, a resist pattern patterned in a desired shape is formed on the metal surface of the substrate having the metal surface. Further, in this way, a substrate with a mold having a resist pattern serving as a mold can be manufactured on the metal surface of the substrate having a metal surface.

The film thickness of the resist pattern (patterned resist film) formed by using the photosensitive resin composition is not particularly limited, and can be applied to either a thick film or a thin film. The photosensitive resin composition is preferably used for forming a thick-film resist pattern. Specifically, the film thickness of the resist pattern formed by using the photosensitive resin composition is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, and even more preferably 0.5 μm or more and 200 μm or less. , 0.5 μm or more and 150 μm or less is particularly preferable.
The upper limit of the film thickness may be, for example, 100 μm or less. The lower limit of the film thickness may be, for example, 1 μm or more, or 3 μm or more.

≪Manufacturing method of plated objects≫
By embedding a conductor such as metal by plating in the non-resist portion (the portion removed by the developer) in the mold of the substrate with a mold formed by the above method, for example, connection terminals such as bumps and metal posts can be formed. , Cu rewiring can be formed. The plating treatment method is not particularly limited, and various conventionally known methods can be adopted. As the plating solution, solder plating, copper plating, gold plating, and nickel plating solution are particularly preferably used. Finally, the remaining mold is removed using a stripping solution or the like according to a conventional method. Since the resist pattern obtained by the above method has excellent resistance to the plating solution, changes in the shape of the resist pattern before and after the plating treatment are suppressed. Therefore, it is possible to obtain a plated model having a desired shape.

When manufacturing a plated model, it may be preferable to perform an ashing treatment on the exposed metal surface in the non-patterned portion of the resist pattern used as a mold for forming the plated model.
Specifically, for example, it is a case where a plated model is formed by using a pattern formed by using a photosensitive resin composition containing a sulfur-containing compound (E) as a template. In this case, the adhesion of the plated model to the metal surface may be easily impaired. This defect is remarkable when the sulfur-containing compound (E) represented by the above formula (e1) or the sulfur-containing compound (E) represented by the formula (e4) is used.
However, when the above ashing treatment is performed, even if the pattern formed by using the photosensitive resin composition containing the sulfur-containing compound (E) is used as a template, a plated molded product that adheres well to the metal surface is formed. Cheap.
When a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group is used as the sulfur-containing compound (E), the above-mentioned problem regarding the adhesion of the plated model is almost nonexistent or mild. Therefore, when a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group is used as the sulfur-containing compound (E), a plated model having good adhesion to the metal surface is formed without ashing. Cheap.

The ashing treatment is not particularly limited as long as it is a method that does not damage the resist pattern, which is a mold for forming a plated model, to the extent that a plated model having a desired shape cannot be formed.
A method using oxygen plasma can be mentioned as a preferable ashing treatment method. In order to ash the metal surface on the substrate with oxygen plasma, oxygen plasma may be generated using a known oxygen plasma generator, and the oxygen plasma may be irradiated to the metal surface on the substrate.

As the gas used for generating oxygen plasma, various gases conventionally used for plasma treatment can be mixed with oxygen as long as the object of the present invention is not impaired. Examples of such a gas include nitrogen gas, hydrogen gas, CF ₄ gas and the like.
The ashing condition using oxygen plasma is not particularly limited as long as the object of the present invention is not impaired, but the treatment time is, for example, in the range of 10 seconds or more and 20 minutes or less, preferably in the range of 20 seconds or more and 18 minutes or less. , More preferably in the range of 30 seconds or more and 15 minutes or less.
By setting the treatment time by oxygen plasma in the above range, it becomes easy to exert the effect of improving the adhesion of the plated model without causing a change in the shape of the resist pattern.

According to the above method, the h-line applicable to a large-area panel level package can be applied, and a resist pattern having excellent plating solution resistance and crack resistance can be used as a mold for forming a plated model. , Not only at the wafer level but also at the large area panel level, and even if a substrate having a non-circular shape, for example, a rectangular main surface, is applied as well as a circular shape, a plated molded product having a desired shape can be obtained. Can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Preparation Example 1]
(Synthesis of mercapto compound E1)
In Preparation Example 1, a mercapto compound T2 having the following structure was synthesized as the sulfur-containing compound (E).

15.00 g of 7-oxanorborna-5-ene-2,3-dicarboxylic acid anhydride and 150.00 g of tetrahydrofuran were added to the flask and stirred. Then, 7.64 g of thioacetic acid (AcSH) was added to the flask, and the mixture was stirred at room temperature for 3.5 hours. Then, the reaction solution was concentrated to obtain 22.11 g of 5-acetylthio-7-oxanorbornane-2,3-dicarboxylic acid anhydride.
After adding 22.11 g of 5-acetylthio-7-oxanorbornane-2,3-dicarboxylic acid anhydride and 30.11 g of an aqueous sodium hydroxide solution having a concentration of 10% by mass into the flask, the contents of the flask at room temperature. Was stirred for 2 hours. Next, hydrochloric acid (80.00 g) having a concentration of 20% by mass was added into the flask to acidify the reaction solution. Then, extraction with 200 g of ethyl acetate was carried out four times to obtain an extract containing the mercapto compound T2. To the residue recovered by concentrating the extract, 25.11 g of tetrahydrofuran (THF) was added and dissolved. Heptane was added dropwise to the obtained THF solution to precipitate the mercapto compound T2, and the precipitated mercapto compound T2 was recovered by filtration. ^{The measurement results of 1} H-NMR of the mercapto compound T2 are described below.
^{1 1} H-NMR (DMSO-d6): δ12.10 (s, 2H), 4.72 (d, 1H), 4.43 (s, 1H), 3.10 (t, 1H), 3.01 ( d, 1H), 2.85 (d, 1H), 2.75 (d, 1H), 2.10 (t, 1H), 1.40 (m, 1H)

[Examples 1 to 19 and Comparative Examples 1 to 5]
In Examples 1 to 19 and Comparative Examples 1 to 5, the compounds PAG1 and PAG2 of the following formulas were used as the acid generator (A).

In Examples 1 to 19 and Comparative Examples 1 to 5, the following Acryl-1 to Acryl-11, PHS-1 and PHS- are used as resins (resins (B)) whose solubility in alkali is increased by the action of an acid. 2 was used. The number in the lower right of the parentheses in each structural unit in the following structural formula represents the content (mol%) of the structural unit in each resin. Acryl-1 to Acryl-11 are acrylic resins (B3) because they contain 70 mol% or more of acrylic constituent units, which are constituent units derived from (meth) acrylic acid or (meth) acrylic acid derivatives. Further, PHS-1 and PHS-2 are polyhydroxystyrene resins (B2).
The mass average molecular weight Mw of Acryl-1 to Acryl-7 is 40,000. Resin-8 to Resin-11 are resins having the same structural unit and composition ratio as Resin-l but different in mass average molecular weight. Resin-8 has a mass average molecular weight of 10,000 and Resin-9 has a mass average molecular weight. Is 20,000, the mass average molecular weight of Resin-10 is 80,000, and the mass average molecular weight of Resin-11 is 120,000. The dispersity (Mw / Mn) of Acryl-1 to Acryl-11 was 2.6.
The mass average molecular weight Mw of PHS-1 was 10,000, and the dispersity (Mw / Mn) was 2.1. The mass average molecular weight Mw of PHS-2 was 11,500, and the dispersity (Mw / Mn) was 1.08.

As the phenolic hydroxyl group-containing low molecular weight compound (C), the following compound C1 was used.

As the alkali-soluble resin (D), the following PHS-3 (polyhydroxystyrene resin) and Novolac-1 (novolak resin (m-cresol monocondensate)) were used. The number in the lower right of the parentheses in each structural unit in the following structural formula represents the content (mol%) of the structural unit in each resin. The mass average molecular weight (Mw) of PHS-3 is 2500, and the dispersity (Mw / Mn) is 2.4. The mass average molecular weight (Mw) of Novolac-1 is 8000.

The following sulfur-containing compounds T1 to T3 were used as the sulfur-containing compound (E).

The following Amine-1 to Amine-3 were used as the acid diffusion inhibitor (F).
Amine-1: ADEKA STAB LA-63P (manufactured by ADEKA)
Amine-2: Diphenylpyridine Amine-3: Triphenylpyridine

Acid generator (A), resin (B), phenolic hydroxyl group-containing low molecular weight compound (C), alkali-soluble resin (D), and sulfur-containing, respectively, of the types and amounts shown in Tables 1 and 2, respectively. The compound (E), the acid diffusion inhibitor (F), and the surfactant (BYK310, manufactured by Big Chemie) are dissolved in 3-methoxybutyl acetate (MA) to make the photosensitivity of each Example and Comparative Example. A resin composition was obtained. The surfactant (BYK310, manufactured by Big Chemie) was added so as to be 0.05 parts by mass with respect to the total amount of the resin (B) and the alkali-soluble resin (D). The photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 5 were prepared so that the solid content concentration was 40% by mass. Further, the photosensitive resin composition of Example 19 was prepared so that the solid content concentration was 53% by mass. Further, the ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is shown in the “Acrylic resin ratio (% mass)” column of Tables 1 and 2.

Using the obtained photosensitive resin composition, a resist pattern was formed according to the following method, and the shape and crack resistance of the resist pattern and the shape after immersion in the copper sulfate plating solution were evaluated. Examples 1 to 18 and Comparative Examples 1 to 5 were evaluated at a film thickness of 7 μm. On the other hand, Example 19 was evaluated at a film thickness of 55 μm. The evaluation results are shown in Tables 1 and 2.

(Formation of evaluation resist pattern with a film thickness of 7 μm)
A substrate provided with a copper layer by sputtering on the surface of a glass substrate having a diameter of 500 mm was prepared, and the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 5 were applied onto the copper layer of this substrate. , A photosensitive resin layer having a film thickness of 7 μm was formed. The photosensitive resin layer was then prebaked at 130 ° C. for 5 minutes. After prebaking, a mask with a line-and-space pattern with a line width of 2 μm and a space width of 2 μm and an exposure device Prisma GHI5452 (manufactured by Ultratech) equipped with an i-line cut filter can be used to form a pattern of a predetermined size. At an exposure amount of 1.2 times the exposure amount, pattern exposure was performed with gh lines until a space of 2.5 μm was formed. The substrate was then placed on a hot plate and heated at 90 ° C. for 1.5 minutes after exposure (PEB). Then, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is added dropwise to the exposed photosensitive resin layer, and then the mixture is allowed to stand at 23 ° C. for 30 seconds. Was repeated twice in total. Then, after washing (rinsing) the surface of the resist pattern with running water, nitrogen blow was performed to obtain a resist pattern.

(Formation of evaluation resist pattern at film thickness 55 μm)
A substrate provided with a copper layer by sputtering on the surface of a glass substrate having a diameter of 500 mm is prepared, and the photosensitive resin composition of Example 19 is applied onto the copper layer of this substrate to obtain a photosensitive resin layer having a film thickness of 55 μm. Was formed. Then, the photosensitive resin layer was prebaked at 100 ° C. for 5 minutes. After prebaking, a pattern of a predetermined size can be formed by using a square pattern mask capable of forming a rectangular opening of 30 μm × 30 μm and an exposure device Prisma GHI5452 (manufactured by Ultratech) equipped with an i-line cut filter. At an exposure amount of 1.2 times the minimum exposure amount, pattern exposure was performed with gh lines until a rectangular opening having a side of 35 μm was formed. Then, the substrate was placed on a hot plate and heated (PEB) after exposure at 100 ° C. for 3 minutes. Then, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is added dropwise to the exposed photosensitive resin layer, and then the mixture is allowed to stand at 23 ° C. for 60 seconds. Was repeated 4 times in total. Then, after washing (rinsing) the surface of the resist pattern with running water, nitrogen blow was performed to obtain a resist pattern.

[Evaluation of resist pattern shape]
The cross-sectional shape of the resist pattern was observed with a scanning electron microscope to evaluate the cross-sectional shape of the pattern. Specifically, when the width of the surface (top) of the resist pattern opposite to the surface in contact with the substrate is Wt and the pattern width Wm of the intermediate portion in the thickness direction of the resist pattern cross section is set, Wm is Wt. When it was within ± 10%, it was evaluated as ◯, and when Wm was outside the range of ± 10% of Wt, it was evaluated as ×. In all the examples, the pattern width of the intermediate portion of the resist pattern cross section in the thickness direction was substantially the same as the width of the surface (bottom) of the resist pattern cross section in contact with the substrate.

[Evaluation of crack resistance of resist pattern]
The substrate on which the resist pattern was formed was subjected to a thermal shock test using a thermal shock device (TSA-103EL manufactured by Espec) at 60 ° C. for 5 minutes and -5 ° C. for 5 minutes as one cycle, and the resist pattern was subjected to a magnification of 10 with an optical microscope. Observing 10 places at double, the case where cracks are observed in the first cycle is evaluated as x, the case where cracks are observed for the first time in the second cycle is evaluated as Δ, and the case where cracks are observed for the first time in the third cycle ○ Evaluation was made when no cracks were observed until the 4th cycle.

[Evaluation of resist pattern plating solution resistance]
The resist pattern was immersed in a copper sulfate plating solution (UTB-W30 manufactured by Ishihara Chemical Co., Ltd.) at 28 ° C. together with the substrate. After immersion, the cross-sectional shape of the resist pattern was observed with a scanning electron microscope to evaluate the cross-sectional shape of the pattern.
Specifically, the case where the shape of the resist pattern did not change before and after the immersion for 30 minutes was evaluated as ◎, and the shape of the resist pattern did not change after the immersion for 15 minutes, but the resist was not observed after the immersion for 30 minutes. The case where the pattern was dissolved in the plating solution was evaluated as ◯, and the case where the resist pattern was dissolved in the plating solution after immersion for 15 minutes was evaluated as x.

According to Examples 1 to 19, the compound represented by the formula (a1-i) or the formula (a1-ii) as the acid generator (A) that generates an acid by irradiation with active light or radiation, the formula (a2). -I) or at least one selected from the compound represented by the formula (a2-ii) and the compound represented by the formula (a3-i) or the formula (a3-ii), and an alkali due to the action of the acid. A positive photosensitive resin composition containing a resin (B) having increased solubility in a resin (B) and having an acrylic resin ratio of 70% by mass or more based on the total of the resin (B) and a resin other than the resin (B). It can be seen that the resist pattern can be formed by h-line exposure, and the formed resist pattern is excellent in plating solution resistance and crack resistance. Further, it can be seen that the cross-sectional shape of the resist pattern is good.

On the other hand, according to Comparative Examples 1 to 5, the positive photosensitive resin composition contains the formula (a1-i) or the formula (a2-i) as the acid generator (A), but the proportion of the acrylic resin is high. When it is less than 70% by mass, it can be seen that the plating solution resistance and crack resistance of the resist pattern are inferior to those of Examples 1 to 19.

Claims (21)

Acid generator (A), which is used to prepare a mold for forming a plated model by embedding metal on a substrate having a metal surface by plating, and generates acid by irradiation with active light or radiation. A chemically amplified positive photosensitive resin composition containing a resin (B) whose solubility in an alkali is increased by the action of an acid.
The acid generator (A) has the following formula (a1-i) or the following formula (a1-ii):

(In the formula (a1-i) and the formula (a1-ii), X ^1a is an oxygen atom or a sulfur atom.
R ^1a is an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;
-S-, -C (= O) -S-, _{-O-S (= O) 2-} , -OC (= O) -O-, -C (= O) -NH-, -C ( = ^{O) -NR 10a} -, and -C ^{(= O)} -NR ^10a comprises at least one moiety selected from the group consisting of ^{R 11a,} which may be substituted by one or more halogen atoms, carbon atoms Aliphatic groups of number 2 or more and 18 or less;
The following formula (a11):

Group represented by;
The following formula (a12):

Group represented by; and the following formula (a13):

Selected from the group consisting of the groups represented by
In the formula (a11), R ^3a is a single bond, or -O-, -S-, -C (= O) -O-, -C (= O) -S-, -OS (= O). ) _2- , -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , and An aliphatic group having 1 to 20 carbon atoms and which may contain at least one moiety selected from the group consisting of −C (= O) −NR ^10a−.
Ar is a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group and an aryl group. , An aromatic group which may have one or more substituents selected from the group consisting of an alkylaryl group, a cyano group, and a nitro group.
In the formula (a12), R ^4a and R ^5a are independently aliphatic groups having 1 or more and 5 or less carbon atoms.
Y ^1a is an oxygen atom,
R ^6a is an aliphatic group having 1 or more and 10 or less carbon atoms.
R ^7a is -O-, -S-, -C (= O) -S-, -O-S (= O) _2- , -OC (= O) -O-, -C (= O). ) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C (= O) -NR An aliphatic group having 1 to 18 carbon atoms and containing at least one moiety selected from the group consisting of ^10a R ^11a.
In the above formula (a13), R ^8a is −O−, −S−, −C (= O) −S−, −OS (= O) _2- , −OC (= O) −O. -, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , and -OC (= O) -NR ^10a- An aliphatic group having 2 to 18 carbon atoms, which may contain at least one moiety selected from the group.
Y ^2a is an oxygen atom
R ^9a is −O−, −S−, −C (= O) −O−, −C (= O) −S−, −OS (= O) _{2-, −OC (= O).} ) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -O-C (= O) -NR ^10a- , And -C (= O) -NR ^10a R ^11a , which is an aliphatic group having 1 to 18 carbon atoms and containing at least one moiety selected from the group.
R ^10a and R ^11a are aliphatic groups having 1 or more and 10 or less carbon atoms, respectively, and in -C (= O) -NR ^10a R ^11a , R ^10a and R ^11a are different even if they are the same as each other. And may be bonded to each other to form an alicyclic group.
R ^2a is an aliphatic group having 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms;
-O-, -S-, -C (= O) -O-, -C (= O) -S-, -O-S (= O) _2- , -O-C (= O) -O- , -C (= O) -NH-, -OC (= O) -NH-, -C (=
^{O) -NR 10a -, - O} -C (= O) -NR 10a -, and -C ^{(= O)} comprising at least one moiety selected from the group consisting of -NR ^{10a R 11a,} one or more Aliphatic groups with 3 to 18 carbon atoms, which may be substituted with halogen atoms;
Halogen atom, aliphatic group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl An aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of groups, cyano groups, and nitro groups; as well as halogen atoms, aliphatic groups, haloalkyl groups, Consists of an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group. Selected from the group Selected from the group consisting of alkyl groups substituted with aromatic groups having 4 or more and 18 or less carbon atoms, which may have one or more substituents. )
Compound represented by:
The following formula (a2-i) or the following formula (a2-ii):

(In formulas (a2-i) to (a2-ii), R ^21a is a hydrogen atom;
Aliphatic groups with 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms; or -O-, -S-, -C (= O)-, -C (= O)- O-, -C (= O) -S-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C ( ^{= O) -NR 10a -, -} O-C (= O) -NR 10a -, and -C ^{(= O)} may contain at least one moiety selected from the group consisting of -NR ^{10a R 11a} An aliphatic group having 2 to 18 carbon atoms, which may be substituted with one or more halogen atoms.
R ^22a is an aliphatic group having 2 to 18 carbon atoms which may be substituted with _{-CH 3} , -CH ₂ F, -CHF ₂ , -CF _{3, or one or more halogen atoms;}
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C (= O) ) -NR ^10a R ^11a contains at least one moiety selected from the group and may be substituted with one or more halogen atoms, an aliphatic group having 2 to 18 carbon atoms;
Halogen atom, aliphatic group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl An aromatic group having 4 to 18 carbon atoms which may have one or more substituents selected from the group consisting of a group, a cyano group, and a nitro group; as well as a halogen atom, an aliphatic group, a haloalkyl group, and an alkoxy. Group consisting of group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl group, cyano group, and nitro group. Selected from the group consisting of alkyl groups substituted with aromatic groups having 4 or more and 18 or less carbon atoms which may have one or more substituents.
However, when R ^22a is −CF ₃ , R ^21a is a hydrogen atom;
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C (= O) ) -NR ^10a An aliphatic group having 2 or more and 18 or less carbon atoms, which may contain at least one moiety selected from the group consisting of R ^{11a and may be substituted with one or more halogen atoms;}
-CH ₂ CH (CH ₃ ) ₂ , -CH ₂ CH = CH CH ₃ or -CH ₂ CH ₂ CH = CH ₂ ;
The following formula (a21):

Group represented by; and the following formula (a22):

A group selected from the group consisting of the groups represented by
R ^10a and R ^11a are aliphatic groups having 1 or more and 10 or less carbon atoms, respectively, and in -C (= O) -NR ^10a R ^11a , R ^10a and R ^11a are different even if they are the same as each other. And may be bonded to each other to form an alicyclic group.
In the formula (a21), R ^23a is an aliphatic group having 4 or more and 18 or less carbon atoms.
In the formula (a22), R ^24a is a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms, and na is an integer of 1 to 5. )
The compound represented by; and the following formula (a3-i) or the following formula (a3-ii):

In formulas a3-i to (a3-ii), R ^31a and R ^32a are independently hydrogen atoms;
Cyano group;
Aliphatic groups with 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms;
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -CN,- One or more including at least one portion selected from the group consisting of C (= O) -NH-, -C (= O) -NR ^10a- , and -C (= O) -NR ^10a R ^11a. An aliphatic group having 1 to 18 carbon atoms which may be substituted with a halogen atom; and a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, A carbon having one or more substituents selected from the group consisting of an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group. A group selected from the group consisting of aromatic groups having 4 or more and 18 or less atoms.
R ^31a and R ^32a may be the same or different from each other, and may be bonded to each other to form an alicyclic group or a heterocyclic group.
R ^33a is an aliphatic group having 1 to 18 carbon atoms, which may be substituted with one or more halogen atoms;
-O-, -S-, -C (= O)-, -C (= O) -O-, -C (= O) -S-, -OC (= O) -O-, -CN , -C (= O) -NH-, -OC (= O) -NH-, -C (= O) -NR ^10a- , -OC (= O) -NR ^10a- , and -C An aliphatic group having at least one moiety selected from the group consisting of (= O) -NR ^{10a R 11a and optionally substituted with one or more halogen atoms;} Halogen atom, aliphatic group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, dialkylamino group, acyloxy group, acylthio group, acylamino group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, aryl group, alkylaryl Selected from the group consisting of groups consisting of groups, cyano groups, and nitro groups, selected from the group consisting of aromatic groups having 4 or more and 18 or less carbon atoms which may have one or more substituents.
R ^10a and R ^11a are aliphatic groups having 1 or more and 10 or less carbon atoms, respectively, and in -C (= O) -NR ^10a R ^11a , R ^10a and R ^11a are different even if they are the same as each other. They may be bonded to each other to form an alicyclic group. )
Containing at least one selected from the compounds represented by
Contains acrylic resin, which is a resin containing 70 mol% or more of acrylic constituent units, which are constituent units derived from (meth) acrylic acid or (meth) acrylic acid derivatives.
A chemically amplified positive photosensitive resin composition in which the ratio of the acrylic resin to the total of the resin (B) and a resin other than the resin (B) is 70% by mass or more. The acid generator (A) comprises a compound represented by the formula (a1-i), the formula (a1-ii), the formula (a2-i) or the formula (a2-ii). The chemically amplified positive photosensitive resin composition according to 1. The chemically amplified positive photosensitive resin composition according to claim 1 or 2, wherein the resin (B) contains the acrylic resin. The chemically amplified positive photosensitive resin composition according to claim 3, wherein the ratio of the acrylic resin contained in the resin (B) to the resin (B) is 70% by mass or more. The chemically amplified positive photosensitive resin composition according to any one of claims 1 to 4, further comprising an alkali-soluble resin (D). The chemically amplified positive photosensitive resin composition according to claim 5, wherein the alkali-soluble resin (D) contains a novolak resin (D1). The chemically amplified positive photosensitive resin composition according to claim 5 or 6, wherein the alkali-soluble resin (D) contains a polyhydroxystyrene resin (D2). The chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7, further comprising a phenolic hydroxyl group-containing low molecular weight compound (C). The chemically amplified positive photosensitive resin composition according to any one of claims 1 to 8, further comprising a sulfur-containing compound (E) containing a sulfur atom that can coordinate with a metal. The chemically amplified positive photosensitive resin composition according to any one of claims 1 to 9, which is used for h-line exposure. The chemically amplified positive photosensitive resin composition according to any one of claims 1 to 10, wherein the main surface of the substrate having the metal surface is rectangular. The chemically amplified positive photosensitive according to any one of claims 1 to 11, which has a base film and a photosensitive resin layer formed on the surface of the base film. A photosensitive dry film made of a resin composition. Production of a photosensitive dry film, which comprises applying the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 11 on a base film to form a photosensitive resin layer. Method. A laminating step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 11 on a substrate.
An exposure step of exposing the photosensitive resin layer by irradiating the photosensitive resin layer with active rays or radiation in a regioselective manner.
A method for producing a patterned resist film, which comprises a developing step of developing the photosensitive resin layer after exposure. The method for producing a patterned resist film according to claim 14, wherein the active light beam or the radiation is h-ray. The method for producing a patterned resist film according to claim 14 or 15, wherein the patterned resist film has a thickness of 1 μm or more. A laminating step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 11 on a substrate having a metal surface.
An exposure step of exposing the photosensitive resin layer by irradiating the photosensitive resin layer with active rays or radiation in a regioselective manner.
A method for manufacturing a substrate with a mold, which comprises a developing step of developing the photosensitive resin layer after exposure to prepare a mold for forming a plated molded product. The method for manufacturing a substrate with a mold according to claim 17, wherein the active light beam or the radiation is h-ray. The method for producing a substrate with a mold according to claim 17 or 18, wherein the thickness of the mold is 1 μm or more. The method for manufacturing a substrate with a mold according to any one of claims 17 to 19, wherein the main surface of the substrate having a metal surface is rectangular. Plating molding including a plating step of plating the molded substrate manufactured by the method for manufacturing a molded substrate according to any one of claims 17 to 20 to form a plated molded product in the mold. Manufacturing method of things.