JP2024025108A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition showing a wide flow margin, having no excessive reduction of film thickness after development, and capable of forming a pattern composed of dots with rectangular cross sections, a micro-lens formed of a cured product of the positive photosensitive resin composition, and a production method of the micro-lens using the positive photosensitive resin composition.

SOLUTION: In a positive photosensitive resin composition containing a resin (A) having an acid-dissociable, dissolution-inhibiting group and exhibiting increased solubility in an alkali under the action of an acid, a compound (B) having a functional group capable of crosslinking the resin (A), a photoacid generator (C), and a quencher (D), an onium salt-based photoacid generator as the photoacid generator (C) and a secondary aliphatic amine or a tertiary aliphatic amine as the quencher (D) are used.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention provides a positive photosensitive resin composition containing a structural unit with a specific structure, a microlens made of a cured product of the positive photosensitive resin composition, and a microlens using the positive photosensitive resin composition described above. The present invention relates to a method for manufacturing a lens.

Conventionally, solid-state imaging devices have been used in cameras, video cameras, and the like. A CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor is used as the solid-state image sensor. The image sensor is provided with a fine condensing lens (hereinafter referred to as a microlens) for the purpose of improving the light condensing efficiency.

As a method for forming such microlenses, a method called a thermal flow method is widely adopted industrially.
In the thermal flow method, a photoresist film is first formed on top of a CCD element or the like. A photoresist film is a film made of a photosensitive resin composition or the like. Thereafter, the photoresist film is exposed and developed to form a dot pattern made of resin on the element. The dot pattern consists of a plurality of dots located where microlenses are to be formed. Each dot constituting the dot pattern has a substantially cylindrical shape or a substantially truncated cone shape. By heating the dot pattern at a temperature higher than the glass transition point of the resin material that makes up the dots, the resin material that makes up the dots flows, and the shape of each dot changes into a hemispherical lens shape due to surface tension. In this way, a microlens pattern is formed (see, for example, Patent Document 1).

Furthermore, an etch-back method is known as one of the methods for manufacturing a microlens for a CCD or CMOS image sensor (Patent Documents 2 and 3). In this method, first, a microlens resin layer is formed on a color filter. Next, a lens pattern is formed on the microlens resin layer using a photosensitive resin composition by a method similar to the thermal flow method described above. A microlens is produced by etching back the lower microlens resin layer using the lens pattern thus formed as an etching mask and transferring the lens pattern shape to the microlens resin layer.

Japanese Patent Application Publication No. 2007-33518 Japanese Unexamined Patent Publication No. 1-10666 Japanese Patent Application Publication No. 6-112459

In the above-mentioned thermal flow method and etchback method, a positive photosensitive resin composition is often used from the viewpoint of thermal fluidity to form a microlens pattern or a mask pattern having a microlens shape. .
The dots used for the microlens pattern or the mask pattern with the shape of microlens by thermal flow are determined by the workability of forming the pattern of the microlens or the mask pattern with the shape of microlens, and the desired shape. A wide flow margin is required in terms of ease of forming a microlens pattern or a mask pattern having a microlens shape. Here, the flow margin is the width between the lowest temperature and the highest temperature at which a microlens pattern of a desired shape or a mask pattern having a microlens shape can be formed.
In addition, the dots provided with the microlens pattern by thermal flow or the mask pattern with the shape of the microlens form microlenses of the desired shape and size, so there is no excessive decrease in film thickness after development. In addition, the cross-sectional shape in the direction perpendicular to the substrate is required to be rectangular.
However, when using conventionally known positive photosensitive resin compositions, it is difficult to form a pattern consisting of dots with a wide flow margin, no excessive decrease in film thickness after development, and a rectangular cross section. be.

The present invention has been made in view of these conventional circumstances, and provides a positive film that exhibits a wide flow margin, does not cause an excessive decrease in film thickness after development, and is capable of forming a pattern consisting of dots with a rectangular cross section. The present invention aims to provide a microlens made of a cured product of a type photosensitive resin composition, the aforementioned positive type photosensitive resin composition, and a method for manufacturing a microlens using the aforementioned positive type photosensitive resin composition.

The present inventors have developed a resin (A) that has an acid-dissociable dissolution-inhibiting group and whose solubility in alkali increases due to the action of an acid, and a compound (B) that has a functional group that crosslinks the resin (A). In a positive photosensitive resin composition containing a photoacid generator (C) and a quencher (D), an onium salt-based photoacid generator as the photoacid generator (C) and a quencher (D). It has been discovered that the above problems can be solved by using a secondary aliphatic amine or a tertiary aliphatic amine as (), leading to the present invention. Specifically, the present invention provides the following.

（式（ａ１）中、Ｒ^ａ１は水素原子、アルキル基、ハロゲン原子、又はハロゲン化アルキル基を示し、Ｒ^ａ２は水素原子又はアルキル基を示し、ｐは１以上５以下の整数を示し、ｑは０以上４以下の整数を示す。）

（式（ａ２－１）～（ａ２－３）中、Ｒ^ａ３は水素原子、アルキル基、ハロゲン原子、又はハロゲン化アルキル基を示し、Ｒ^ａ４、Ｒ^ａ５及びＲ^ａ６は、それぞれ独立に、水素原子又はアルキル基を示し、Ｒ^ａ７はアルキル基又はシクロアルキル基を示し、Ｒ^ａ８は第三級炭素原子を有する有機基を示し、式（ａ２－２）、及び式（ａ２－３）中の、ＯとＲ^ａ８との間の結合は、酸素原子と前記第三級炭素原子との結合であり、ｒは１以上５以下の整数を示し、ｓ及びｔは、それぞれ独立に、０以上４以下の整数を示す。） A first aspect of the present invention is a resin (A) that has an acid-dissociable dissolution-inhibiting group and whose solubility in alkali increases by the action of an acid, and a compound (B) that has a functional group that crosslinks the resin (A). ), a photoacid generator (C), and a quencher (D), the positive photosensitive resin composition comprising:
Resin (A) includes resin (A1) and resin (A2),
The resin (A1) has a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2-1),
The resin (A2) has a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2-2) or (a2-3),
The photoacid generator (C) includes an onium salt-based photoacid generator,
The quencher (D) is a positive photosensitive resin composition containing one or more selected from secondary aliphatic amines and tertiary aliphatic amines.

(In formula (a1), R ^a1 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, R ^a2 represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 5, and q indicates an integer between 0 and 4.)

(In formulas (a2-1) to (a2-3), R ^a3 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, and R ^a4 , R ^a5 and R ^a6 each independently represent hydrogen represents an atom or an alkyl group, R ^a7 represents an alkyl group or a cycloalkyl group, R ^a8 represents an organic group having a tertiary carbon atom, and in formula (a2-2) and formula (a2-3), , the bond between O and R ^a8 is a bond between the oxygen atom and the tertiary carbon atom, r represents an integer of 1 to 5, and s and t each independently represent 0 to 4. (Indicates the following integer.)

A second aspect of the present invention is a microlens made of a cured product of the positive photosensitive resin composition according to the first aspect.

A third aspect of the present invention is to form a positive photosensitive resin composition layer using the positive photosensitive resin composition according to the first aspect;
Positionally selectively exposing the positive photosensitive resin composition layer;
Developing the exposed positive photosensitive resin composition layer;
This is a method for manufacturing a microlens, which includes heating a developed positive photosensitive resin composition layer to transform it into a microlens shape.

A fourth aspect of the present invention is to laminate a positive photosensitive resin composition layer on the lens material layer using the positive photosensitive resin composition according to the first aspect;
Positionally selectively exposing the positive photosensitive resin composition layer;
Developing the exposed positive photosensitive resin composition layer;
heating the developed positive photosensitive resin composition layer to form a mask layer having a microlens pattern;
The method of manufacturing a microlens includes dry etching a lens material layer and the mask layer to transfer the shape of a microlens pattern to the lens material layer.

According to the present invention, a positive photosensitive resin composition exhibiting a wide flow margin, no excessive decrease in film thickness after development, and capable of forming a pattern consisting of dots with a rectangular cross section by photolithography; A microlens made of a cured product of the positive photosensitive composition and a method for manufacturing a microlens using the above-described positive photosensitive resin composition can be provided.

The present invention will be described below based on embodiments. Note that in this specification, (meth)acrylate is a general term for acrylate and methacrylate.

≪Positive photosensitive resin composition≫
The positive photosensitive resin composition includes a resin (A) having an acid-dissociable dissolution-inhibiting group and whose solubility in alkali increases by the action of an acid, and a compound (A) having a functional group that crosslinks the resin (A). B), a photoacid generator (C), and a quencher (D). Hereinafter, the resin (A) having an acid-dissociable dissolution-inhibiting group and whose solubility in alkali increases by the action of an acid will also be referred to as "resin (A)." Hereinafter, the compound (B) having a functional group that crosslinks the resin (A) will also be referred to as "compound (B)." Hereinafter, each component contained in the positive photosensitive resin composition will be explained in detail.

<Resin (A)>
The resin (A), which has an acid-dissociable dissolution-inhibiting group and whose solubility in alkali increases by the action of an acid, is one of the resins that can be used as a base resin in a so-called chemically amplified positive photosensitive resin composition. You can choose from.
Specifically, a resin having a structural unit derived from hydroxystyrene having an acid-dissociable dissolution-inhibiting group or a resin having a structural unit derived from (meth)acrylate having an acid-dissociable dissolution-inhibiting group can be used. Typically, the resin (A) has an alkali-soluble group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group.
Among these resins, a resin containing a structural unit derived from hydroxystyrene having an acid-dissociable dissolution-inhibiting group is preferable as the resin (A) because of its easy availability, excellent thermal flow properties, and the like.
As the resin (A), the above-mentioned resins can be used alone or in combination of two or more.

It is preferable that the resin (A) includes a resin (A1) described later and a resin (A2) described later. By using resin (A1) and resin (A2) as resin (A), a pattern consisting of dots with a rectangular cross section is formed, which exhibits a wide flow margin and does not cause excessive decrease in film thickness after development. It is easy to obtain a positive photosensitive resin composition. Resin (A) may contain resins other than resin (A1) and resin (A2) as long as the desired purpose is not impaired.

The resin (A1) has a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2-1). The resin (A2) has a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2-2) or the following formula (a2-3).
Hereinafter, the structural unit represented by formula (a1) will also be referred to as "structural unit (a1)." The structural unit represented by formula (a2-1) is also referred to as "constituent unit (a2-1)." The structural unit represented by formula (a2-2) is also referred to as "constituent unit (a2-2)." The structural unit represented by formula (a2-3) is also referred to as "constituent unit (a2-3)."

（式（ａ１）中、Ｒ^ａ１は水素原子、アルキル基、ハロゲン原子、又はハロゲン化アルキル基を示し、Ｒ^ａ２は水素原子又はアルキル基を示し、ｐは１以上５以下の整数を示し、ｑは０以上４以下の整数を示す。）

(In formula (a1), R ^a1 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, R ^a2 represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 5, and q indicates an integer between 0 and 4.)

（式（ａ２－１）～（ａ２－３）中、Ｒ^ａ３は水素原子、アルキル基、ハロゲン原子、又はハロゲン化アルキル基を示し、Ｒ^ａ４、Ｒ^ａ５及びＲ^ａ６は、それぞれ独立に、水素原子又はアルキル基を示し、Ｒ^ａ７はアルキル基又はシクロアルキル基を示し、Ｒ^ａ８は第三級炭素原子を有する有機基を示し、式（ａ２－２）、及び式（ａ２－３）中の、ＯとＲ^ａ８との間の結合は、酸素原子と前記第三級炭素原子との結合であり、ｒは１以上５以下の整数を示し、ｓ及びｔは、それぞれ独立に、０以上４以下の整数を示す。）

(In formulas (a2-1) to (a2-3), R ^a3 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, and R ^a4 , R ^a5 and R ^a6 each independently represent hydrogen represents an atom or an alkyl group, R ^a7 represents an alkyl group or a cycloalkyl group, R ^a8 represents an organic group having a tertiary carbon atom, and in formula (a2-2) and formula (a2-3), , the bond between O and R ^a8 is a bond between the oxygen atom and the tertiary carbon atom, r represents an integer of 1 to 5, and s and t each independently represent 0 to 4. (Indicates the following integer.)

In formula (a1), formula (a2-1), formula (a2-2), and formula (a2-3), R ^a1 and R ^a3 are a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group represents.
The number of carbon atoms in the alkyl groups as R ^a1 and R ^a3 is not particularly limited. The number of carbon atoms in the alkyl group as R ^a1 and R ^a3 is preferably 1 or more and 5 or less. The alkyl groups as R ^a1 and R ^a3 may be linear or branched. Specific examples of alkyl groups as R ^a1 and R ^a3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, and a neopentyl group. Methyl group is preferred industrially.
Specific examples of the halogen atom as R ^a1 and R ^a3 or the halogen atom in the alkyl halide include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atoms are preferred. The halogenated alkyl group is preferably a group in which some or all of the hydrogen atoms in the above-mentioned alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. The halogenated alkyl group may be linear or branched. Preferred specific examples of the halogenated alkyl group include fluorinated alkyl groups such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl, and nonafluorobutyl.
As R ^a1 and R ^a3 , a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable.

The number of carbon atoms in the alkyl group as R ^a2 and R ^a4 is preferably 1 or more and 5 or less. Preferred examples of alkyl groups as R ^a2 and R ^a4 are the same as preferred examples of alkyl groups as R ^a1 and R ^a3 .

q, s, and t are each independently an integer of 0 to 4. Among these, q, s, and t are preferably 0 or 1, and particularly preferably 0 from an industrial standpoint.

In formula (a1), when q is 1, the substitution position of R ^a2 is o relative to the position of the carbon atom bonded to the carbon atom bonded to R ^a1 on the benzene ring in formula (a1). It may be any of the -, m-, and p-positions.
When q is an integer of 2 or more and 4 or less, R ^a2 can be bonded to any position on the benzene ring in formula (a1).

In formula (a2-1) and formula (a2-3), when t is 1, the substitution position of R ^a4 is on the benzene ring in formula (a2-1) and formula (a2-3). , R ^a3 may be at o-position, m-position, or p-position relative to the carbon atom bonded to the carbon atom bonded to R a3.
When t is an integer of 2 or more and 4 or less, R ^a4 can be bonded to any position on the benzene ring in formula (a2-1) and formula (a2-3).

In formula (a1), p is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1.
In formulas (a2-1) and (a2-3), s is an integer of 0 to 4, preferably 0 to 3, and more preferably 0 or 1.
When p is 1 or s is 1, the substitution position of the hydroxyl group in formula (a1), formula (a2-1), and formula (a2-3) is ), or o-position, m-position, p-position with respect to the position of the carbon atom bonded to the carbon atom bonded to R ^a1 or R ^a3 on the benzene ring in formula (a2-3). Either may be used, and the p-position is preferable.
In formula (a1), p is an integer of 2 or more and 5 or less, or in formula (a2-1) and formula (a2-3), when s is an integer of 2 or more and 4 or less, the hydroxyl group has the formula It can be bonded to any position on the benzene ring in (a1), formula (a2-1), and formula (a2-3).

In formulas (a2-1) and (a2-3), r is an integer of 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1.
When r is 1, a group represented by -C(R ^a5 )(R ^a6 )OR ^a7 in formula (a2-1) and formula (a2-3), or -O-CO-O-R ^a8 The substitution position of the group represented by is o with respect to the position of the carbon atom bonded to the carbon atom bonded to R ^a3 on the benzene ring in formula (a2-1) or formula (a2-3). It may be any of the -, m-, and p-positions.
In formulas (a2-1) and (a2-3), when r is an integer of 2 or more and 5 or less, a group represented by -C(R ^a5 )(R ^a6 )OR ^a7 , or -O- The group represented by CO-O-R ^a8 can be bonded to any position on the benzene ring in formula (a2-1) and formula (a2-3).

In the acid-dissociable, dissolution-inhibiting group represented by -C(R ^a5 )(R ^a6 )OR ^a7 in formula (a2-1), R ^a5 and R ^a6 each independently represent a hydrogen atom or an alkyl group. . R ^a7 represents an alkyl group or a cycloalkyl group. At least two of R ^a5 , R ^a6 , and R ^a7 may be bonded to each other to form a ring.

In formula (a2-2) or formula (a2-3), R ^a8 represents an organic group having a tertiary carbon atom. The bond between O and R ^a8 in formulas (a2-2) and (a2-3) is a bond between an oxygen atom and the tertiary carbon atom.

The number of carbon atoms in the alkyl group as R ^a5 or R ^a6 is preferably 1 or more and 6 or less. The alkyl group as R ^a5 or R ^a6 may be linear or branched.
The number of carbon atoms in the alkyl group as R ^a7 is preferably 1 or more and 10 or less. The alkyl group as R ^a7 may be linear or branched.
The number of carbon atoms in the cycloalkyl group as R ^a7 is preferably 3 or more and 10 or less, for example.

Specific examples of the alkyl group as R ^a5 , R ^a6 , or R ^a7 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, and the like.
Specific examples of the cycloalkyl group as R ^a7 include a cyclopentyl group and a cyclohexyl group.

Specific examples of the acid dissociable dissolution inhibiting group represented by -C(R ^a5 )(R ^a6 )OR ^a7 in formula (a2-1) include 1-methoxyethyl group, 1-ethoxyethyl group, 1- n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxypropyl group, 1 -ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, and 1-ethoxy-1-methylethyl group.

R ^a8 in formula (a2-2) is an organic group having a tertiary carbon atom. As such an organic group, a group represented by -C(R ^A1 )(R ^A2 )(R ^A3 ) is preferable.
R ^A1 , R ^A2 , and R ^A3 are each independently an alkyl group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, or an aliphatic group having 5 to 20 carbon atoms. It is a cyclic group.
Specific examples of alkyl groups as R ^A1 , R ^A2 , and R ^A3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. , n-pentyl group, isopentyl group, neopentyl group, and n-hexyl group.
The fluorinated alkyl groups as R ^A1 , R ^A2 , and R ^A3 are groups in which some or all of the hydrogen atoms of the above alkyl group are substituted with fluorine atoms.
Specific examples of aliphatic cyclic groups as R ^A1 , R ^A2 , and R ^A3 include polycycloalkanes from which one or more hydrogen atoms have been removed, such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. The following groups are mentioned. Specifically, groups 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.

Specific examples of the group represented by -C(R ^A1 )(R ^A2 )(R ^A3 ) include the following groups. Among the groups listed below, tert-butyl group is preferred.

In formula (a2-3), a specific example of the acid-dissociable, dissolution-inhibiting group represented by -COOR ^a8 includes a tert-butoxycarbonyl group.

The resin (A1) may contain one or more types of structural units (a1). The resin (A1) may contain one or more types of structural units (a2-1).
The sum of the ratio of the structural unit (a1) and the ratio of the structural unit (a2-1) in the resin (A1) is 10 mol% or more and 100 mol based on the number of moles of all the structural units that constitute the resin (A1). % or less, more preferably 25 mol% or more and 100 mol% or less, even more preferably 35 mol% or more and 100 mol% or less, particularly preferably 50 mol% or more and 100 mol% or less, and most preferably 100 mol%. When the above ratio is within the above range, it is easy to obtain a positive photosensitive resin composition that exhibits a wide flow margin, does not have an excessive decrease in film thickness after development, and can form a pattern consisting of dots having a rectangular cross section. .

The ratio of the number of moles of the structural unit (a2-1) to the total number of moles of the structural unit (a1) and the number of moles of the structural unit (a2-1) is preferably 10 mol% or more and 60 mol% or less, More preferably 20 mol% or more and 40 mol% or less. This ratio is the protection rate of hydroxyl groups derived from hydroxystyrene. When the protection rate is within the above range, it is easy to obtain a positive photosensitive resin composition that exhibits a wide flow margin, does not have an excessive decrease in film thickness after development, and can form a pattern consisting of dots having a rectangular cross section. .

The ratio of the number of moles of the structural unit (a2-1) to the number of moles of all the structural units constituting the resin (A) is preferably 10 mol% or more and 50 mol% or less, more preferably 15 mol% or more and 40 mol% or less. preferable.

The resin (A2) may contain one or more types of structural units (a1). The resin (A2) may contain one or more types of structural units (a2-2). The resin (A2) may contain one or more types of structural units (a2-3).
The sum of the ratio of the structural unit (a1), the ratio of the structural unit (a2-2), and the ratio of the structural unit (a2-3) in the resin (A2) is the sum of the ratio of the structural unit (a2-3) in the resin (A2). Based on the number of moles, preferably 10 mol% or more and 100 mol% or less, more preferably 30 mol% or more and 100 mol% or less, even more preferably 50 mol% or more and 100 mol% or less, particularly 70 mol% or more and 100 mol% or less. Preferably, 100 mol% is most preferred. When the above ratio is within the above range, it is easy to obtain a positive photosensitive resin composition that exhibits a wide flow margin, does not have an excessive decrease in film thickness after development, and can form a pattern consisting of dots having a rectangular cross section. .

Among the total number of moles of the structural unit (a1), the number of moles of the structural unit (a2-2), and the number of moles of the structural unit (a2-3), the structural unit (a2-2) or (a2-3) The ratio (that is, the protection rate of (meth)acrylate or the protection rate of hydroxystyrene) is preferably 10 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 40 mol% or less. When the protection rate of hydroxystyrene is within the above range, the resulting positive photosensitive resin composition exhibits a wide flow margin, does not have an excessive decrease in film thickness after development, and is composed of dots with a rectangular cross section. It is easy to obtain a positive photosensitive resin composition that can form a pattern.

The ratio of the structural unit (a2-2) and/or the structural unit (a2-3) to the number of moles of all the structural units constituting the resin (A) is preferably 2 mol% or more and 30 mol% or less, and 6 mol%. The content is more preferably 25 mol% or less.

The resin (A1) may contain other structural units other than the structural unit (a1) and the structural unit (a2-1). The resin (A2) may contain other structural units other than the structural unit (a1), the structural unit (a2-2), and the structural unit (a2-3).

Examples of other monomers providing other structural units include (meth)acrylic esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and maleimides. These compounds can be used alone or in combination of two or more.

Examples of (meth)acrylic acid esters include linear or branched chains such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and tert-octyl (meth)acrylate. alkyl (meth)acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, Examples include furfuryl (meth)acrylate; glycidyl (meth)acrylate; and (meth)acrylic acid ester having a group having an alicyclic skeleton.
In the (meth)acrylic acid ester having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Examples of (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, and N,N-aryl(meth)acrylamide. , N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, and the like.

Examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; etc.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxy Aliphatic vinyl ethers such as ethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4 -Vinyl aryl ethers such as dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether; and the like.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene. , ethoxymethylstyrene, acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo; Halostyrenes such as styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and the like.

Examples of maleimides include carbon atoms such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, Nn-pentylmaleimide, and Nn-hexylmaleimide. Maleimide N-substituted with an alkyl group having 1 to 10 atoms; N-substituted with an alicyclic group having 3 to 20 carbon atoms such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, etc. Maleimide: N-arylmaleimide substituted with an aryl group having 6 to 20 carbon atoms such as N-phenylmaleimide, N-α-naphthylmaleimide, N-β-naphthylmaleimide; N-benzylmaleimide, N-phenethyl N-substituted N-aralkylmaleimide with an aralkyl group having 7 to 20 carbon atoms such as maleimide can be mentioned.

<Other resin (A3)>
In addition to the resin (A1) and the resin (A2), the resin (A) may further contain a resin (A3) other than the resins (A1) and (A2). The other resin (A3) is not particularly limited as long as the desired effect is not impaired. As the other resin (A3), various resins conventionally blended into positive photosensitive resin compositions that can be developed with an alkaline developer can be used without particular limitation.

In order to easily obtain the desired effect, the total ratio of the mass of the resin (A1) and the mass of the resin (A2) to the mass of the resin (A) is preferably 50% by mass or more and 100% by mass or less, More preferably, it is 80% by mass or more and 100% by mass or less, and most preferably 100% by mass.
When resin (A) contains resins (A1) and (A2) in such proportions, the resulting positive photosensitive resin composition exhibits a wide flow margin and does not have an excessive decrease in film thickness after development. , it is easy to obtain a positive photosensitive resin composition that can form a pattern consisting of dots having a rectangular cross section.

In addition, the mass ratio of resins (A1) and (A2) in resin (A) is preferably 30:70 to 95:5, more preferably 35:75 to 90:10, and more preferably 40:60 to 80:20. is even more preferable.

The weight average molecular weight (Mw) of the resin (A) is preferably 5,000 or more and 30,000 or less. The same applies to the mass average molecular weights of resin (A1) and resin (A2). When the weight average molecular weight is within the above range, the positive photosensitive resin composition exhibits a wide flow margin, does not excessively reduce the film thickness after development, and can form a pattern consisting of dots having a rectangular cross section. Easy to obtain. In addition, in this specification, the weight average molecular weight is the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC).

The content of the resin (A) in the positive photosensitive resin composition may be adjusted depending on the thickness of the resist film to be formed.

<Compound (B)>
The positive photosensitive resin composition contains compound (B). Compound (B) has a functional group that crosslinks the resin (A).
Examples of this functional group include groups that can react with groups exhibiting proton-donating properties such as phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups that the resin (A) may have. Specific examples of the crosslinkable functional group possessed by the compound (B) include functional groups such as a vinyloxy group, an isocyanate group, a thioisocyanate group, an epoxy group, and an oxetanyl group. Compounds having such a crosslinkable functional group or derivatives of these compounds can be used as the compound (B).
Among compounds having these functional groups and derivatives of these compounds, from the viewpoint of high reactivity with resin (A), high availability, high chemical resistance after crosslinking, etc. Compounds having a vinyloxy group, isocyanate group, alkoxymethyl group, or methylol group in the molecule or derivatives of these compounds are preferred.
Typically, compound (B) preferably has two or more such crosslinkable functional groups in the molecule.

A preferable example of the compound (B) is a compound (B1) having at least two vinyloxy groups.
In compound (B1), the vinyloxy group is bonded to a carbon atom. By containing such a compound, the positive photosensitive resin composition exhibits a wide flow margin, prevents excessive reduction in film thickness after development, and is capable of forming a pattern consisting of dots with a rectangular cross section. Easy to obtain resin composition. Compound (B1) can be used alone or in combination of two or more.
Compound (B1) acts as a crosslinking agent for resin (A). It is thought that the above effects are obtained as a result of resin (A) being crosslinked by compound (B1). It is presumed that the flow margin widens due to further progress of crosslinking with the resin (A) during post-baking.

Specific examples of compound (B1) include polyfunctional vinyl ether compounds listed in numerous publications such as JP-A-6-148889 and JP-A-6-230574. Compound (B1) can be arbitrarily selected from these and used. In particular, considering the resist profile shape caused by thermal crosslinking and acid decomposition, and the contrast characteristics between exposed and unexposed areas, some or all of the hydroxyl groups of the alcohol represented by the following formula (b1) are A compound in which the hydrogen atom in the hydroxyl group is substituted with a vinyl group is preferred.
R ^b -(OH) _b (b1)
In formula (b1), R ^b is a b-valent aliphatic hydrocarbon group. The structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. The aliphatic hydrocarbon group may have a substituent. The hydrocarbon chain in the aliphatic hydrocarbon group may be interrupted by an oxygen atom (ether bond). b represents 2, 3, or 4.

Specific examples of the compound (B) having a vinyloxy group derived from a polyol represented by formula (b1) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butanediol divinyl ether, and tetramethylene glycol divinyl ether. , neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, 1,6-hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol Examples include trivinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and the like.

As the compound (B1), a compound represented by the following formula (b2) is also preferable.
In formula (b2), R ^b1 is an alkylene group having 1 or more and 10 or less carbon atoms, or a group represented by the following formula (b2-1). The alkylene group as R ^b1 may be linear or branched. The alkylene group as R ^b1 may have a substituent. The alkylene group as R ^b1 may contain an oxygen atom (ether bond). However, in the compound represented by formula (b2), the vinyloxy group is bonded to the carbon atom in R ^b1 .
In formula (b2-1), R ^b2 is an alkylene group having 1 or more and 10 or less carbon atoms. The alkylene group as R ^b2 may be linear or branched. The alkylene group as R ^b2 may have a substituent. The alkylene group as R ^b2 may contain an oxygen atom (ether bond).
In formula (b2-1), R ^b3 is a cyclohexane-1,4-diyl group, a cyclohexane-1,3-diyl group, or a cyclohexane-1,2-diyl group.
In formula (b1-1), c is each independently 0 or 1.
CH ₂ =CH-O-R ^b1 -O-CH=CH ₂ (b2)
-(R ^b2 ) _c -R ^b3 -(R ^b2 ) _c - (b2-1)

R ^b1 is -(CH ₂ ) ₄ -, -(C ₂ H ₄ OC ₂ H ₄ )-, -(C ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ )-, and formula (b2-1) A group represented by formula (b2-1) is preferable, and a group represented by formula (b2-1) is more preferable. The group represented by formula (b2-1) is preferably a group represented by formula (b2-1), in which R ^b2 is a methylene group and c is 1.
As the compound represented by formula (b2), 1,4-cyclohexanedimethanol divinyl ether is preferred. 1,4-Cyclohexane dimethanol divinyl ether is also referred to as CHDVE.

The content of the compound (B) in the positive photosensitive resin composition is a positive type that exhibits a wide flow margin, does not cause an excessive decrease in film thickness after development, and can form a pattern consisting of dots with a rectangular cross section. Since it is easy to obtain a photosensitive resin composition, the content is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the resin (A).

<Photoacid generator (C)>
The photoacid generator (C) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or radiation. The photoacid generator (C) can be used alone or in combination of two or more. The photoacid generator (C) essentially contains an onium salt photoacid generator (C).

As the photoacid generator (C), photoacid generators according to the first to fifth embodiments described below are preferable. Preferred examples of the photoacid generator (C) will be described below as first to fifth embodiments.
Note that among the photoacid generators according to the first to fifth aspects, the photoacid generator according to the first aspect and the photoacid generator according to the fourth aspect are onium salt-based photoacid generators. .

A first embodiment of the photoacid generator (C) includes a compound represented by the following formula (c1).

In the above formula (c1), X ^1c represents a sulfur atom or an iodine atom with a valence of g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1c is an organic group bonded to X ^1c , such as 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, Represents an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, and R ^1c is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio At least one group selected from the group consisting of carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen. May be substituted with a species. The number of R ^1c is g+h(g-1)+1, and R ^1c may be the same or different from each other. In addition, two or more R ^1c are directly connected to each other, or -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2c -, -CO-, -COO-, -CONH- , an alkylene group having 1 to 3 carbon atoms, or a phenylene group to form a ring structure containing X ^1c . R ^2c is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ^2c has a structure represented by the following formula (c2).

In the above formula (c2), X ^4c represents 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 X ^4c is from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, hydroxy, cyano, nitro, and halogen. It may be substituted with at least one selected member. X ^5c is -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2c -, -CO-, -COO-, -CONH-, alkylene having 1 to 3 carbon atoms group, or a phenylene group. h represents the number of repeating units of the structure in parentheses. h+1 X ^4cs and h X ^5cs may be the same or different. R ^2c is the same as defined above.

X ^3c- is a counter ion of onium, and is a fluorinated alkylfluorophosphate anion represented by the following formula (c17) or a borate anion represented by the following formula (c18), and a hydrogen atom in which some or all of the hydrogen atoms are fluorine Examples include fluoroalkylsulfonate ions or arylsulfonate ions.

In the above formula (c17), R ^3c represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. j indicates the number and is an integer from 1 to 5. The j R ^3cs may be the same or different.

In the above formula (c18), R ^4c to R ^7c each independently represent a fluorine atom or a phenyl group, and some or all of the hydrogen atoms of the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group. may be substituted with at least one species.

Onium ions in the compound represented by formula (c1) above include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, (4-methoxyphenyl)diphenylsulfonium), 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-dihydroanthracen-2-yldi-p-tolylsulfonium , 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio ] Phenyldi-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, diphenylphenacylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 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-(2-hydroxytetradecyloxy) ) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, or 4-isobutylphenyl (p-tolyl) iodonium, and the like.

Among the onium ions in the compound represented by the above formula (c1), preferred onium ions include sulfonium ions represented by the following formula (c19).

In the above formula (c19), R ^8c is each independently a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, a halogen atom, aryl which may have a substituent, or arylcarbonyl. represents a group selected from the group consisting of: X ^2c represents the same meaning as X ^2c in the above formula (c1).

Specific examples of the sulfonium ion represented by the above formula (c19) 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 -acetophenylthio)phenyl]diphenylsulfonium and diphenyl[4-(p-terphenylthio)phenyl]diphenylsulfonium.

In the fluorinated alkylfluorophosphate anion represented by the above formula (c17), R ^3c represents an alkyl group substituted with a fluorine atom, and the number of carbon atoms is preferably 1 or more and 8 or less, and more preferably 1 or more. 4 or less. Specific examples of alkyl groups 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 cyclopropyl, cyclobutyl, and cyclopentyl. , cycloalkyl groups such as cyclohexyl, etc., and the proportion of hydrogen atoms in the alkyl group substituted with fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by the above formula (c1) decreases.

Particularly preferred R ^3c is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%; specific examples include CF ₃ , CF ₃ CF _{2 ,} ( _{CF3 ) 2CF} , _{CF3CF2CF2 , CF3CF2CF2CF2 ,} ( _CF3 ) _{2CFCF2 , CF3CF2} ( _CF3 ) _CF ,( _{CF3 ) 3C} is Can be mentioned. The number j of R ^3c is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, 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 CFCF ₂ ) ₂ PF ₄ ] ^- is particularly preferred.

Preferred specific examples of the borate anion represented by the above formula (c18) include 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. Among these, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferred.

The alkyl group in the fluoroalkyl sulfonate ion may be linear, branched, or cyclic, having 1 to 20 carbon atoms, and should have 1 to 10 carbon atoms in view of the bulk of the generated acid and its diffusion distance. is preferred. In particular, branched or cyclic alkyl groups are preferred because they have a short diffusion distance. Furthermore, since they can be synthesized at low cost, methyl, ethyl, propyl, butyl, octyl, and the like are preferred.

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

In the above fluoroalkylsulfonate ion or arylsulfonate ion, when some or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100%. In particular, those in which all hydrogen atoms are replaced with fluorine atoms are preferred because the strength of the acid becomes stronger. Specific examples of such substances include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate, and the like.

Among these, preferred anion moieties include those represented by the following formula (c9).

In the above formula (c9), R ^20c is a group represented by the following formulas (c10), (c11), and (c12).

In the above formula (c10), x represents an integer of 1 or more and 4 or less. In the above formula (c11), R ^21c is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms. y represents an integer of 1 or more and 3 or less. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

The second embodiment of the photoacid generator (C) includes 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(2-furyl)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-furyl) 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)styrylphenyl-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-furyl)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(1 , 3-dibromopropyl)-1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine, and tris(2,3-dibromopropyl) isocyanate. Examples include halogen-containing triazine compounds represented by the following formula (c3) such as nurate.

In the above formula (c3), R ^9c , R ^10c , and R ^11c each independently represent a halogenated alkyl group.

Further, the third embodiment of the photoacid generator (C) includes α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-( benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and oxime sulfonate groups. Examples include a compound represented by the following formula (c4).

In the above formula (c4), R ^12c represents a monovalent, divalent, or trivalent organic group, and R ^13c represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. , and n represents the number of repeating units of the structure in parentheses.

In the above formula (c4), the aromatic group refers to a group of compounds that exhibit physical and chemical properties specific to aromatic compounds, such as aryl groups such as phenyl group and naphthyl group, furyl group, and thienyl group. Examples include heteroaryl groups such as groups. These may have one or more suitable substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, or a nitro group. Further, R ^13c is particularly preferably an alkyl group having 1 or more and 6 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a butyl group. Particularly preferred are compounds in which R ^12c is an aromatic group and R ^13c is an alkyl group having 1 to 4 carbon atoms.

As the acid generator represented by the above formula (c4), when n=1, a compound in which R ^12c is a phenyl group, methylphenyl group, or methoxyphenyl group, and R ^13c is a methyl group; Specifically, α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p- Examples include methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](o-tolyl)acetonitrile, and the like. When n=2, specific examples of the acid generator represented by the above formula (c4) include acid generators represented by the following formula.

Further, a fourth embodiment of the photoacid generator (C) includes an onium salt having a naphthalene ring in the cation moiety. "Having a naphthalene ring" means having a structure derived from naphthalene, and means that the structure of at least two rings and their aromaticity are maintained. This naphthalene ring has a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Good too. 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 is not possible to be a monovalent group. Desirable (however, in this case, free valences shall be counted excluding the moiety bonded to the above substituent). The number of naphthalene rings is preferably 1 or more and 3 or less.

The cation moiety of such an onium salt having a naphthalene ring in the cation moiety preferably has a structure represented by the following formula (c5).

In the above formula (c5), at least one of R ^14c , R ^15c , and R ^16c represents a group represented by the following formula (c6), and the rest are linear or branched groups having 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 ^14c , R ^15c , and R ^16c is a group represented by the following formula (c6), and the remaining two are each independently a linear or branched group having 1 to 6 carbon atoms. is an alkylene group, and these terminals may be bonded to form a ring.

In the above formula (c6), R ^17c and R ^18c each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. R 19c represents a branched alkyl group, and R ^19c represents a linear or branched alkylene group having 1 or more and 6 or less 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 a plurality of R ^17cs exist, they may be the same or different from each other. Furthermore, when a plurality of R ^18cs exist, they may be the same or different from each other.

Among the above R ^14c , R ^15c , and R ^16c , the number of groups represented by the above formula (c6) is preferably one from the viewpoint of stability of the compound, and the remaining are straight groups having 1 to 6 carbon atoms. It is a chain or branched alkylene group, and the terminals thereof may be bonded to form a ring. In this case, the above two alkylene groups constitute a 3- to 9-membered ring including the sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 or more and 6 or less.

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

In addition, as substituents that the phenyl group may have, linear or branched alkoxy groups having 1 to 6 carbon atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, Examples include groups.

Examples of cations suitable for these cation moieties include cations represented by the following formulas (c7) and (c8), with the structure represented by the following formula (c8) being particularly preferred.

Such a cation moiety may be an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable from the viewpoint of acid generation efficiency.

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

The anion moiety of such an acid generator is a fluoroalkylsulfonic acid ion or an arylsulfonic acid ion in which some or all of the hydrogen atoms are fluorinated. Such an anion moiety is the same as the fluoroalkylsulfonate ion or arylsulfonate ion in which some or all of the hydrogen atoms are fluorinated, as described in the first embodiment.

Furthermore, as the anion part, nitrogen-containing anion parts represented by the following formulas (c13) and (c14) can also be used.

In the above formulas (c13) and (c14), X ^c represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms. The number of carbon atoms is preferably 3 or more and 5 or less, most preferably 3. Further, Y ^c and Z ^c 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 in the alkyl group is 1 or more and 10 or less. , preferably 1 or more and 7 or less, more preferably 1 or more and 3 or less.

The smaller the number of carbon atoms in the alkylene group of X ^c or the number of carbon atoms in the alkyl group of Y ^c or Z ^c , the better the solubility in organic solvents.

Further, in the alkylene group of X ^c or the alkyl group of Y ^c or Z ^c , the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength becomes, which is preferable. The proportion 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 atoms. It is a perfluoroalkylene group or a perfluoroalkyl group substituted with atoms.

Preferred compounds as such onium salts having a naphthalene ring in the cation moiety include compounds represented by the following formulas (c15) and (c16).

Further, the fifth embodiment of the photoacid generator (C) includes bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4 -dimethylphenylsulfonyl) diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, Nitrobenzyl derivatives such as nitrobenzyl carbonate and dinitrobenzyl carbonate; pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenyl Sulfonic acid esters such as sulfonyloxymaleimide and N-methylsulfonyloxyphthalimide; N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(trifluoro Trifluoromethanesulfonic acid esters such as methylsulfonyloxy)-4-butyl-1,8-naphthalimide and N-(trifluoromethylsulfonyloxy)-4-butylthio-1,8-naphthalimide; diphenyliodonium hexafluorophos Fart, (4-methoxyphenyl) phenyl iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate , (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate, and other onium salts; benzointosylate, α-methylbenzointosylate, and other benzointosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium Examples include salt, benzyl carbonate, and the like.

The content of the photoacid generator (C) in the positive photosensitive resin composition is not particularly limited as long as it does not impede the object of the present invention. The content of the photoacid generator (C) is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, based on 100 parts by mass of the resin (A).

The amount of the onium salt photoacid generator used in the first aspect or the fourth aspect is preferably 1 equivalent or more and 10 equivalents or less, more preferably 2 equivalents or more and 8 equivalents or less, relative to the quencher (D) described below. , more preferably 3 equivalents or more and 7 equivalents or less.

<Quencher (D)>
The positive photosensitive resin composition may contain a quencher (D). The quencher (D) contains one or more selected from secondary aliphatic amines and tertiary aliphatic amines. Here, an aliphatic amine is an amine having one or more aliphatic groups. The number of carbon atoms in the aliphatic group that the aliphatic amine has is preferably 1 or more and 20 or less.

Examples of aliphatic amines include ammonia (NH ₃ ) in which at least one hydrogen atom is substituted with an alkyl group having 20 or less carbon atoms, and ammonia (NH ₃ ) in which at least one hydrogen atom is substituted with a hydroxyalkyl group. Included are group-substituted alkanolamines and cyclic amines.

Preferred specific examples of secondary aliphatic amines include dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine, diethanolamine, and diisopropanolamine. , and dialkanolamines such as di-n-octanolamine.
Preferred specific examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine. amines, trialkylamines such as tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine, triethanolamine, tri-n-octanolamine, stearyldiethanolamine, and lauryl Examples include alkanolamines such as diethanolamine.
Additionally, tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy) ) ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, and tris[2-{2-(2-hydroxyethoxy)ethoxy}ethylamine etc. are also preferable as tertiary aliphatic amines.

The secondary aliphatic amine and tertiary aliphatic amine may be cyclic amines. Examples of the cyclic secondary aliphatic amine include piperidine and piperazine. Examples of the cyclic tertiary aliphatic amine include N-methylpiperidine, N-ethylpiperidine, N-methylpiperazine, N-ethylpiperazine, N,N'-dimethylpiperazine, and N,N'-diethylpiperazine. Can be mentioned.

These quenchers (D) may be used alone or in combination of two or more. The amount of quencher contained in the positive photosensitive resin composition is 0.01 parts by mass or more and 5.0 parts by mass or less, preferably 0.05 parts by mass or more and 3.0 parts by mass or less, based on 100 parts by mass of the resin (A). It is 0 parts by mass or less, more preferably 0.10 parts by mass or more and 1.0 parts by mass or less.

<Organic solvent (S)>
The positive photosensitive resin composition may contain an organic solvent (S). By containing the organic solvent (S) in the positive photosensitive resin composition, the coating properties of the positive photosensitive resin composition and the positive photosensitive resin composition formed using the positive photosensitive resin composition are improved. It is easy to adjust the thickness of the material layer. The organic solvent (S) can be used alone or in combination of two or more.

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, and dipropylene glycol monoacetate, and polyhydric alcohols such as their monomethyl ethers (e.g., propylene glycol monomethyl ether acetate), monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether, and their Derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxy acetate, methoxypropion Methyl acid, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3 -Esters such as methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; and the like.

In the positive photosensitive resin composition, the content of the organic solvent (S) is preferably 50 parts by mass or more and 3000 parts by mass or less, and 100 parts by mass or more and 2000 parts by mass based on 100 parts by mass of component (A). It is more preferable that the amount is less than 100%. When the content is within the above range, the coating properties of the positive photosensitive resin composition are likely to improve, and the thickness of the positive photosensitive resin composition layer formed using the positive photosensitive resin composition can be reduced. Adjustment is easy.

<Other ingredients>
The positive photosensitive resin composition may contain various additives in addition to the above-mentioned components as long as the desired effects are not impaired. The additive may be appropriately selected from various additives conventionally blended into positive photosensitive resin compositions. Specific examples of other components include polyvinyl resin, surfactant, and acid or acid anhydride.

The positive photosensitive resin composition may contain a polyvinyl resin in order to improve the plasticity of the formed film. Specific examples of polyvinyl resins include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinylethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof. can be mentioned.

The positive photosensitive resin composition may contain an adhesion aid in order to improve adhesion to the support.

The positive photosensitive resin composition may contain a surfactant in order to improve coating properties, antifoaming properties, leveling properties, and the like. Specific examples of surfactants include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all manufactured by DIC), and Florado FC. -135, Florado FC-170C, Florado FC-430, Florado FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone), Polyfox PF-136A, Polyfox PF-156A, Polyfox Examples include commercially available fluorine-based surfactants such as PF-151N, Polyfox PF-636, Polyfox PF-656, and Polyfox PF-6520 (all manufactured by OMNOVA Solutions), but are not limited to these. do not have.

The positive photosensitive resin composition may contain an acid or an acid anhydride in order to finely adjust the solubility in a developer.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxy monocarboxylic acids such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic 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 acids, polyhydric carboxylic acids such as butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, anhydride Succinic acid, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, himic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, Acid anhydrides such as cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate anhydride, glycerin tris trimellitate anhydride; etc. can.

<Method for producing positive photosensitive resin composition>
The above positive photosensitive resin composition can be prepared by mixing and stirring the above components in a conventional manner. If necessary, dispersion and mixing may be performed using a dispersing machine such as a dissolver, homogenizer, or three-roll mill. Furthermore, after mixing, the mixture may be further filtered using a mesh, membrane filter, or the like.

≪Production method of microlens≫
Hereinafter, a method for manufacturing a microlens using the above-mentioned positive photosensitive resin composition will be explained.
The manufacturing method for microlenses is as follows:
Forming a positive photosensitive resin composition layer using the above-mentioned positive photosensitive resin composition;
Positionally selectively exposing the positive photosensitive resin composition layer;
Developing the exposed positive photosensitive resin composition layer;
A method for manufacturing a microlens includes heating a developed positive photosensitive resin composition layer to transform it into a microlens shape.
This method will also be referred to as the first method below.

Other microlens manufacturing methods include:
Forming a positive photosensitive resin composition layer using the above-mentioned positive photosensitive resin composition;
Positionally selectively exposing the positive photosensitive resin composition layer;
Developing the exposed positive photosensitive resin composition layer;
A method for manufacturing a microlens includes heating a developed positive photosensitive resin composition layer to transform it into a microlens shape.
This method will also be referred to as the second method below.

<First method>
In the first method, first, a positive photosensitive resin composition layer is formed using the above-described positive photosensitive resin composition. The method of forming the positive photosensitive resin composition layer is not particularly limited. Examples of methods for forming the positive photosensitive resin composition layer include coating, pasting of a dry film, and the like. Coating is preferred as a lamination method.

A positive photosensitive resin composition layer is usually formed on a base material. As a base material, an image element including a photodiode (organic photodiode, inorganic photodiode, etc.), a silicon wafer provided with a color filter layer, etc., a substrate such as a silicon wafer further formed with an antireflection film if necessary, etc. can be mentioned.

The method of applying the positive photosensitive resin composition is not particularly limited. For example, a positive photosensitive resin composition can be coated using a contact transfer coating device such as a roll coater, reverse coater, bar coater, or slit coater, or a non-contact coating device such as a spinner (rotary coating device) or curtain flow coater. A positive-working photosensitive resin composition layer can be formed by applying a material to a desired thickness.

When forming a positive photosensitive resin composition layer, the coating film made of the positive photosensitive resin composition is appropriately subjected to heat treatment (pre-bake (post-apply bake (PAB) treatment) to form a coating film. The solvent inside may be removed.
The conditions for the above-mentioned heat treatment vary depending on the type of each component in the positive photosensitive resin composition layer, the blending ratio, the coating film thickness, etc. The heating temperature is, for example, preferably 60°C or more and 150°C or less, more preferably 70°C or more and 140°C or less. The heating time is, for example, preferably 0.5 minutes or more and 60 minutes or less, more preferably 1 minute or more and 50 minutes or less.
The thickness of the positive photosensitive resin composition layer is preferably in the range of 100 nm or more and 4.0 μm or less, more preferably 200 nm or more and 1.0 μm or less.

The positive photosensitive resin composition layer formed as described above is selectively exposed to light so that dots are formed at positions where microlenses are to be formed. Position-selective exposure can be performed, for example, via a desired mask pattern. The wavelength of the light beam used for exposure is not particularly limited. Exposure can be performed using radiation such as KrF excimer laser, ArF excimer laser, F2 excimer laser, EUV (extreme ultraviolet light), VUV (vacuum ultraviolet light), EB (electron beam), X-rays, soft X-rays, and the like.

After exposure, the positive photosensitive resin composition layer is subjected to PEB (post-exposure bake) treatment (post-exposure heat treatment), if necessary. Conditions for the PEB treatment vary depending on the type of each component in the positive photosensitive resin composition, blending ratio, coating film thickness, etc. For example, the heating temperature is preferably 60°C or higher and 150°C or lower, more preferably 70°C or higher and 140°C or lower. The heating time is, for example, preferably 0.5 minutes or more and 60 minutes or less, more preferably 1 minute or more and 50 minutes or less.

Next, the exposed positive photosensitive resin composition layer is developed. This dissolves and removes unnecessary parts.

Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3. An aqueous solution of an alkali such as 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 aqueous solution of the above-mentioned alkali can also be used as the developer. As the developer, a tetramethylammonium hydroxide aqueous solution having a concentration of 0.1% by mass or more and 10% by mass or less is preferred.

The development time varies depending on the composition of the positive photosensitive resin composition, the thickness of the positive photosensitive resin composition layer, etc., but is usually 1 minute or more and 30 minutes or less. The developing method may be any of a piling method, a dipping method, a paddle method, a spray developing method, and the like.

The developed positive photosensitive resin composition layer is washed with running water or the like, if necessary, and then dried. In this way, a dot pattern is formed.
A convex lens-shaped microlens is formed by heating the dots constituting the dot pattern of the positive photosensitive resin composition layer after development into a microlens shape.
Heating conditions vary depending on the type of each component in the positive photosensitive resin composition, blending ratio, coating film thickness, etc. For example, the heating temperature is preferably 130°C or higher and 170°C or lower, more preferably 140°C or higher and 160°C or lower. The heating time is, for example, preferably 1 minute or more and 30 minutes or less, more preferably 3 minutes or more and 10 minutes or less.
The microlens thus formed is made of a cured product of the above-mentioned positive photosensitive resin composition.

<Second method>
In the second method, first, a positive photosensitive resin composition layer is laminated on the lens material layer using a positive photosensitive resin composition. The lamination method is not particularly limited. Examples of the lamination method include coating, dry film attachment, and the like. Coating is preferred as a lamination method.
A lens material layer is typically formed on a substrate. As a base material, an image element including a photodiode (organic photodiode, inorganic photodiode, etc.), a silicon wafer provided with a color filter layer, etc., a substrate such as a silicon wafer further formed with an antireflection film if necessary, etc. can be mentioned.

The method for applying the positive photosensitive resin composition onto the lens material layer is the same as the application method described for the first method.

When forming a positive photosensitive resin composition layer, the coating film made of the positive photosensitive resin composition is appropriately subjected to heat treatment (pre-bake (post-apply bake (PAB) treatment) to form a coating film. The solvent inside may be removed.
The conditions for the heat treatment described above are the same as those described for the first method.
The thickness of the positive photosensitive resin composition layer is preferably in the range of 100 nm or more and 4.0 μm or less, more preferably 200 nm or more and 1.0 μm or less.

The positive photosensitive resin composition layer formed as described above is positionally selectively exposed so that dots are formed at positions corresponding to positions where microlenses are formed on the lens material layer. . Position-selective exposure is performed in the same manner as the exposure in the first method.

After exposure, the positive photosensitive resin composition layer is subjected to PEB (post-exposure bake) treatment (post-exposure heat treatment), if necessary. The conditions for PEB processing are the same as those for the first method.

Next, the positive photosensitive resin composition layer is exposed to light and developed in the same manner as in the first method. A mask layer having a convex lens-shaped microlens pattern is formed by heating the dots constituting the dot pattern of the positive photosensitive resin composition layer after development into a microlens shape.

By etching the lens material layer together with the mask, a microlens with the shape of the mask transferred thereto is formed.
The etching method is preferably dry etching. Dry etching is not particularly limited, and includes, for example, dry etching using plasma (oxygen, argon, _CF4 , etc.), corona discharge, and the like.

（式（ａ１）中、Ｒ^ａ１は水素原子、アルキル基、ハロゲン原子、又はハロゲン化アルキル基を示し、Ｒ^ａ２は水素原子又はアルキル基を示し、ｐは１以上５以下の整数を示し、ｑは０以上４以下の整数を示す。）

（式（ａ２－１）～（ａ２－３）中、Ｒ^ａ３は水素原子、アルキル基、ハロゲン原子、又はハロゲン化アルキル基を示し、Ｒ^ａ４、Ｒ^ａ５及びＲ^ａ６は、それぞれ独立に、水素原子又はアルキル基を示し、Ｒ^ａ７はアルキル基又はシクロアルキル基を示し、Ｒ^ａ８は第三級炭素原子を有する有機基を示し、式（ａ２－２）、及び式（ａ２－３）中の、ＯとＲ^ａ８との間の結合は、酸素原子と前記第三級炭素原子との結合であり、ｒは１以上５以下の整数を示し、ｓ及びｔは、それぞれ独立に、０以上４以下の整数を示す。）
（２）光酸発生剤（Ｃ）が、下記式（ｃ９）：
Ｒ^２０ｃＳＯ_３ ^－・・・（ｃ９）
（式（ｃ９）中、Ｒ^２０ｃは炭素原子数１以上４位以下の直鎖又は分岐状のフッ素化アルキル基を表す。）
で表されるアニオン部を有するオニウム塩系光酸発生剤を含む、（１）に記載のポジ型感光性樹脂組成物。
（３）樹脂（Ａ）を構成する全構成単位に対する、式（ａ２－１）で表される構成単位の比率が、１０モル％以上３５モル％以下であり、
樹脂（Ａ）を構成する全構成単位に対する、式（ａ２－２）で表される構成単位、及び／又は式（ａ２－３）で表される構成単位の比率が、２モル％以上１５モル％以下である（１）又は（２）に記載のポジ型感光性樹脂組成物。
（４）ポジ型感光性樹脂組成物における光酸発生剤（Ｃ）に含まれるオニウム塩系光酸発生剤の含有量が、クエンチャー（Ｄ）に対し２当量以上１０当量以下である（１）～（３）のいずれか１つに記載のポジ型感光性樹脂組成物。
（５）（１）～（４）のいずれか１つに記載のポジ型感光性組成物の硬化物からなるマイクロレンズ。
（６）えのいずれか１つに記載のポジ型感光性樹脂組成物を用いてポジ型感光性樹脂組成物層を形成することと、
ポジ型感光性樹脂組成物層を位置選択的に露光することと、
露光された前記ポジ型感光性樹脂組成物層を現像することと、
現像後のポジ型感光性樹脂組成物層を加熱する加熱して、マイクロレンズ形状に変形させと、を含むマイクロレンズパターンの製造方法。
（７）レンズ材料層上に、（１）～（４）のいずれか１つに記載のポジ型感光性樹脂組成物を用いてポジ型感光性樹脂組成物層を積層するポジ型感光性樹脂組成物層積層工程と、
ポジ型感光性樹脂組成物層を位置選択的に露光することと、
露光されたポジ型感光性樹脂組成物層を現像することと、
現像後のポジ型感光性樹脂組成物層を加熱して、マイクロレンズパターンを有するマスク層を形成することと、
レンズ材料層及び前記マスク層をドライエッチングして、レンズ材料層に前記マイクロレンズパターンの形状を転写することと、を含むマイクロレンズの製造方法。 As mentioned above, the following (1) to (6) are provided by the present inventor.
(1) A resin (A) that has an acid-dissociable dissolution-inhibiting group and whose solubility in alkali increases by the action of an acid, a compound (B) that has a functional group that crosslinks the resin (A), and a photoacid generator. A positive photosensitive resin composition containing an agent (C) and a quencher (D),
Resin (A) includes resin (A1) and resin (A2),
The resin (A1) has a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2-1),
The resin (A2) has a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2-2) or (a2-3),
The photoacid generator (C) includes an onium salt-based photoacid generator,
The quencher (D) is a positive photosensitive resin composition containing one or more selected from secondary aliphatic amines and tertiary aliphatic amines.

(In formula (a1), R ^a1 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, R ^a2 represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 5, and q indicates an integer between 0 and 4.)

(In formulas (a2-1) to (a2-3), R ^a3 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, and R ^a4 , R ^a5 and R ^a6 each independently represent hydrogen represents an atom or an alkyl group, R ^a7 represents an alkyl group or a cycloalkyl group, R ^a8 represents an organic group having a tertiary carbon atom, and in formula (a2-2) and formula (a2-3), , the bond between O and R ^a8 is a bond between the oxygen atom and the tertiary carbon atom, r represents an integer of 1 to 5, and s and t each independently represent 0 to 4. (Indicates the following integer.)
(2) The photoacid generator (C) has the following formula (c9):
R ^20c SO ₃ ^--- (c9)
(In formula (c9), R ^20c represents a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms.)
The positive photosensitive resin composition according to (1), comprising an onium salt photoacid generator having an anion moiety represented by:
(3) The ratio of the structural unit represented by formula (a2-1) to all the structural units constituting the resin (A) is 10 mol% or more and 35 mol% or less,
The ratio of the structural unit represented by formula (a2-2) and/or the structural unit represented by formula (a2-3) to all the structural units constituting the resin (A) is 2 mol% or more and 15 mol % or less, the positive photosensitive resin composition according to (1) or (2).
(4) The content of the onium salt photoacid generator contained in the photoacid generator (C) in the positive photosensitive resin composition is 2 equivalents or more and 10 equivalents or less with respect to the quencher (D) (1 ) to (3). The positive photosensitive resin composition according to any one of (3).
(5) A microlens made of a cured product of the positive photosensitive composition according to any one of (1) to (4).
(6) forming a positive photosensitive resin composition layer using the positive photosensitive resin composition according to any one of the above;
Positionally selectively exposing the positive photosensitive resin composition layer;
Developing the exposed positive photosensitive resin composition layer;
A method for producing a microlens pattern, comprising: heating a positive photosensitive resin composition layer after development to transform it into a microlens shape.
(7) A positive photosensitive resin in which a positive photosensitive resin composition layer is laminated on the lens material layer using the positive photosensitive resin composition according to any one of (1) to (4). composition layer lamination step;
Positionally selectively exposing the positive photosensitive resin composition layer;
Developing the exposed positive photosensitive resin composition layer;
heating the developed positive photosensitive resin composition layer to form a mask layer having a microlens pattern;
A method for manufacturing a microlens, comprising dry etching a lens material layer and the mask layer to transfer the shape of the microlens pattern to the lens material layer.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The invention is not limited to these examples.

[Preparation of positive photosensitive resin composition]
Resin (A), compound (B), photoacid generator (C), and quencher (D) of the type and amount shown in Table 1 are uniformly dissolved in an organic solvent (S), and a positive-working photosensitive resin is prepared. A composition was prepared. The numerical values in parentheses in Table 1 represent the blending amount (unit: parts by mass) of each component. In addition, in Table 1, the ratio of the blending amount of the onium salt photoacid generator (C-1) among the photoacid generators (C) to all the blending amounts of the quencher (D) is It is expressed as an equivalent ratio as the amount of onium salt photoacid generator (C-1) to be blended to all the amounts of D).

Each component listed in Table 1 will be explained below.

<Resin (A)>
The following resins A-1 to A-3 were used as resins corresponding to the resin (A1) or resin (A2) described above. In each of the following formulas representing resins A-1 to A-3, the subscripts (x, y, and z) attached to each repeating unit represent the ratio of each repeating unit to all repeating units contained in the resin ( (mol%).

A-1: Resin represented by the following formula (weight average molecular weight 20000, x=65, y=35)

A-2: Resin represented by the following formula (weight average molecular weight 20000, x=75, y=25)

A-3: Resin represented by the following formula (weight average molecular weight 10000, x=65, y=25, z=10)

<Compound (B)>
B-1: Compound represented by the following formula

<Photoacid generator (C)>
As the photoacid generator (C), the following C-1 to C-3 were used.

C-1: Compound represented by the following formula

C-2: Compound represented by the following formula

C-3: Compound represented by the following formula

As the quencher (D), the following D-1 to D-3 were used.
D-1: Triethylamine D-2: Triethanolamine D-3: 2,6-di-tert-butylpyridine

As the organic solvent (S), the following S-1 was used.
S-1: Propylene glycol monomethyl ether acetate

Using the obtained positive photosensitive resin compositions of Examples and Comparative Examples, the items listed in Table 3 were evaluated according to the following methods.

<Formation of dot pattern>
Using a spinner, the positive photosensitive resin compositions of each Example and each Comparative Example were applied onto a Si substrate on which an antireflection film and an acrylic transparent flattening film were formed to form a coating film. was formed. The coating film was prebaked on a hot plate at 100° C. for 90 seconds to dry the coating film, thereby forming a positive photosensitive resin composition layer with a thickness of 300 nm.
Next, using a KrF exposure device NSR-S203B (manufactured by Nikon, NA=0.68, S=0.75), it was exposed through a mask for forming a dot pattern with a dot diameter of 0.35 μm and a distance between dots of 0.23 μm. The positive photosensitive resin composition layer was irradiated with a KrF excimer laser (wavelength: 248 nm). The exposure amount was 50 mJ/ ^cm2 .
Thereafter, the positive photosensitive resin composition layer was subjected to PEB treatment at 110° C. for 90 seconds. Next, the exposed positive photosensitive resin composition layer was developed for 60 seconds at room temperature (23° C.) using a 2.38% by mass aqueous tetramethylammonium hydroxide solution. Thereafter, rinsing with pure water for 30 seconds and dehydrobake treatment at 110° C. for 60 seconds were performed to form a dot pattern consisting of a plurality of dots.

<Evaluation of flow margin>
The dot patterns formed according to the above method were post-baked for 300 seconds at temperatures of 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, and 170°C. . The cross-sectional shape in the pressure direction of the dotted substrate baked under each temperature condition was observed using a scanning electron microscope (SEM, S-9220 (manufactured by Hitachi, Ltd.)). From the results of the SEM observation, the lowest temperature T1 at which the cross-sectional shape of the dots changes to a substantially semicircular convex lens shape by the above-mentioned post-bake treatment was determined. Further, from the results of SEM observation, the lowest temperature T2 at which adjacent dots that had flowed due to heating came into contact with each other near the substrate surface was determined. Based on the value of the difference between T2 and T1 (=T2-T1), the flow margin was evaluated according to the following criteria. The results are shown in Table 2.
◎ (Good): T2-T1 is over 10°C ○ (Slightly good): T2-T1 is 5°C or more and 10°C or less × (Poor): T2-T1 is less than 5°C

<Evaluation of film thickness change after development>
A dot pattern was formed in the same manner as above. The thickness Th1 of the resin film after the PEB treatment and the thickness Th2 of the dots after the dehydrobake treatment were measured.
Based on the measured value of the film thickness, the rate of change in the film thickness of the cured film was calculated based on the following formula.
Film thickness change rate (%) = Th2/Th1 x 100
Based on the calculated value of the film thickness change rate, the film thickness change after development was evaluated according to the following criteria. The results are shown in Table 2.
◎ (Good): Film thickness change rate is over 90% and 100% or less ○ (Slightly good): Film thickness change rate is over 80% and 90% or less × (Poor): Film thickness change rate is 80% or less

<Evaluation of rectangularity>
The shape of the dots formed in the same manner as above after the dehydrobake treatment was observed using an SEM (Scanning Electron Microscope S-9220 (manufactured by Hitachi, Ltd.)), and an electron microscope image showing the cross-sectional shape of the dots was obtained. Ta. Based on the obtained electron microscope image, the rectangularity of the cross-sectional shape of the dots was evaluated according to the following criteria. The results are shown in Table 2.
◎ (Good): The shape of the dots in the thickness direction of the substrate is rectangular or approximately rectangular.
○ (slightly good): The shape of the cross section of the dot in the thickness direction of the substrate is trapezoidal.
× (Poor): The shape of the cross section of the dot in the thickness direction of the substrate is rounded and not square.

According to Tables 1 and 2, the resins (A1) and (A2) mentioned above as the resin (A), the compound (B) which is a crosslinkable compound, and the onium as the photoacid generator (C) The positive photosensitive resin composition of the example containing a salt-based photoacid generator and a tertiary aliphatic amine as a quencher (D) exhibited a wide flow margin and did not exhibit excessive film thinning after development. It can be seen that a resist pattern with excellent rectangularity can be obtained.
On the other hand, as the resin (A), the positive photosensitive resin compositions of Comparative Examples 1, 4, and 5 that do not contain a combination of resin (A1) and resin (A2), and the photoacid generator (C ), the positive photosensitive resin composition of Comparative Example 2 not containing the onium salt photoacid generator (C-1), and the onium salt photoacid generator (C-1) as the photoacid generator (C). ) and a secondary aliphatic amine or a tertiary aliphatic amine as the quencher (D), the positive photosensitive resin composition of Comparative Example 3 has a wide flow margin and a It lacked one or more of the following: resistance to film thinning and good rectangularity of the resist pattern.

Claims (7)

A resin (A) having an acid-dissociable dissolution-inhibiting group and whose solubility in alkali increases by the action of an acid, a compound (B) having a functional group that crosslinks the resin (A), and a photoacid generator ( A positive photosensitive resin composition containing C) and a quencher (D),
The resin (A) includes resin (A1) and resin (A2),
The resin (A1) has a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2-1),
The resin (A2) has a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2-2) or (a2-3),
The photoacid generator (C) includes an onium salt photoacid generator,
The quencher (D) is a positive photosensitive resin composition containing one or more selected from secondary aliphatic amines and tertiary aliphatic amines.

(In formula (a1), R ^a1 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, R ^a2 represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 5, and q indicates an integer between 0 and 4.)

(In formulas (a2-1) to (a2-3), R ^a3 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, and R ^a4 , R ^a5 and R ^a6 each independently represent hydrogen represents an atom or an alkyl group, R ^a7 represents an alkyl group or a cycloalkyl group, R ^a8 represents an organic group having a tertiary carbon atom, and in formula (a2-2) and formula (a2-3), , the bond between O and R ^a8 is a bond between the oxygen atom and the tertiary carbon atom, r represents an integer of 1 to 5, and s and t each independently represent 0 to 4. (Indicates the following integer.) The photoacid generator (C) has the following formula (c9):
R ^20c SO ₃ ^--- (c9)
(In formula (c9), R ^20c represents a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms.)
The positive photosensitive resin composition according to claim 1, comprising an onium salt photoacid generator having an anion moiety represented by: The ratio of the structural unit represented by the formula (a2-1) to all the structural units constituting the resin (A) is 10 mol% or more and 35 mol% or less,
The ratio of the structural unit represented by the formula (a2-2) and/or the structural unit represented by the formula (a2-3) to all the structural units constituting the resin (A) is 2 mol%. The positive photosensitive resin composition according to claim 1, wherein the content is 15 mol% or less. A content of the onium salt photoacid generator contained in the photoacid generator (C) in the positive photosensitive resin composition is 2 equivalents or more and 10 equivalents or less with respect to the quencher (D). 1. The positive photosensitive resin composition according to 1. A microlens comprising a cured product of the positive photosensitive composition according to any one of claims 1 to 4. Forming a positive photosensitive resin composition layer using the positive photosensitive resin composition according to any one of claims 1 to 4;
positionally selectively exposing the positive photosensitive resin composition layer;
Developing the exposed positive photosensitive resin composition layer;
A method for manufacturing a microlens, comprising heating the positive photosensitive resin composition layer after development to transform it into a microlens shape. Laminating a positive photosensitive resin composition layer using the positive photosensitive resin composition according to any one of claims 1 to 4 on the lens material layer;
positionally selectively exposing the positive photosensitive resin composition layer;
Developing the exposed positive photosensitive resin composition layer;
heating the positive photosensitive resin composition layer after development to form a mask layer having a microlens pattern;
A method for manufacturing a microlens, comprising dry etching the lens material layer and the mask layer to transfer the shape of the microlens pattern to the lens material layer.