Positive-type photosensitive resin composition, microlens, and method for manufacturing a microlens

Abstract

To provide a positive-type photosensitive resin composition that has good sensitivity and can improve dark-loss in unexposed areas of a pattern consisting of dots having a rectangular cross-section, a microlens made from a cured product of the aforementioned positive-type photosensitive resin composition, and a method for manufacturing a microlens using the aforementioned positive-type photosensitive resin composition. [Solution] A positive-type photosensitive resin composition is used for manufacturing convex microlens patterns and comprises a resin (A) whose solubility in alkali increases with the action of an acid, and a photoacid generator (B). The resin comprises a structural unit (a1) derived from hydroxystyrene as the resin (A), and a structural unit (a2) in which at least one hydrogen atom of a hydroxyl group in the structural unit derived from hydroxystyrene is replaced with a group containing an acid-dissociation-inhibiting group, and a photo-disintegrable base (C) that decomposes upon exposure and loses its acid diffusion controllability.

Description

[Technical Field]

[0001] The present invention relates to a positive-type photosensitive resin composition comprising a resin containing structural units of a specific structure and a photodegradable base, a microlens made from a cured product of the positive-type photosensitive resin composition, and a method for manufacturing a microlens using the aforementioned positive-type photosensitive resin composition. [Background technology]

[0002] Traditionally, cameras, video cameras, and the like have used solid-state image sensors. These solid-state image sensors include CCD (charge-coupled device) image sensors and CMOS (complementary metal-oxide semiconductor) image sensors. The image sensor is equipped with a tiny focusing lens (hereinafter referred to as a microlens) to improve light-gathering efficiency.

[0003] A method called thermal flow is widely used industrially to form such microlenses. In the thermal flow method, a photoresist film is first formed on top of a CCD element or the like. The photoresist film is a film made of a photosensitive resin composition or the like. Then, the photoresist film is exposed to light and developed to form a dot pattern made of resin on the element. The dot pattern consists of multiple dots located where microlenses are to be formed. Each dot constituting the dot pattern has a substantially cylindrical shape or a substantially frustoconical shape. By heating the dot pattern at a temperature above the glass transition temperature of the resin material constituting the dots, the resin material constituting the dots flows, and due to surface tension, the shape of each dot changes to a hemispherical lens shape. In this way, a microlens pattern is formed (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-133733 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, with the miniaturization of microlenses, the effect of dark-loss (film thinning in unexposed areas) due to light leakage during exposure for dot pattern formation has become significant. The shape of the dot pattern can be improved using a quencher. However, in this case, the sensitivity to exposure decreases, and a large amount of exposure is required to form the dot pattern.

[0006] The present invention has been made in view of the above-mentioned conventional circumstances, and aims to provide a positive-type photosensitive resin composition that has good sensitivity and can improve dark-loss in unexposed areas of a pattern consisting of dots having a rectangular cross-section, a microlens made from a cured product of the aforementioned positive-type photosensitive resin composition, and a method for manufacturing a microlens using the aforementioned positive-type photosensitive resin composition. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by using a positive-type photosensitive resin composition, which is used in the manufacture of convex microlens patterns and comprises a resin (A) whose solubility in alkali increases with the action of an acid, and a photoacid generator (B), wherein the resin (A) has a constituent unit (a1) derived from hydroxystyrene, and a constituent unit (a2) in which at least one hydrogen atom of a hydroxyl group in the constituent unit derived from hydroxystyrene is replaced with a group containing an acid-dissociation-inhibiting group, and a photo-disintegrable base (C) that decomposes upon exposure and loses its acid diffusion controllability, leading to the present invention. Specifically, the present invention provides the following.

[0008] A first aspect of the present invention is a positive-type photosensitive resin composition used in the manufacture of a convex microlens pattern, The positive-type photosensitive resin composition contains a resin (A) whose solubility in alkali increases with the action of an acid, a photoacid generator (B), and a photodecayable base (C) that decomposes upon exposure and loses its ability to control acid diffusion. The resin (A) is a positive-type photosensitive resin composition having a structural unit (a1) derived from hydroxystyrene and a structural unit (a2) in which at least one hydrogen atom of a hydroxyl group in the structural unit derived from hydroxystyrene is replaced with an acid-dissociation-inhibiting group-containing group.

[0009] A second aspect of the present invention is a microlens made from a cured product of a positive-type photosensitive resin composition according to the first aspect.

[0010] A third aspect of the present invention involves forming a positive-type photosensitive resin composition layer using the positive-type photosensitive resin composition according to the first aspect, Positionally exposing a positive-type photosensitive resin composition layer, Developing the exposed positive-type photosensitive resin composition layer, A method for manufacturing microlenses, comprising heating a positive-type photosensitive resin composition layer after development to deform it into a microlens shape.

[0011] A fourth aspect of the present invention involves laminating a positive-type photosensitive resin composition layer on a lens material layer using the positive-type photosensitive resin composition according to the first aspect, Positionally exposing a positive-type photosensitive resin composition layer, Developing the exposed positive-type photosensitive resin composition layer, The positive-type photosensitive resin composition layer is heated after development to form a mask layer having a microlens pattern, A method for manufacturing microlenses, comprising dry etching a lens material layer and a mask layer to transfer the shape of a microlens pattern onto the lens material layer. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a positive-type photosensitive resin composition that has good sensitivity and can improve dark-loss in unexposed areas of a pattern consisting of dots having a rectangular cross-section, a microlens made from a cured product of the positive-type photosensitive resin composition, and a method for manufacturing a microlens using the aforementioned positive-type photosensitive resin composition. [Modes for carrying out the invention]

[0013] The present invention will be described below based on embodiments. In this specification, (meth)acrylate is a general term for acrylate and methacrylate.

[0014] <Positive-type photosensitive resin composition> A positive-type photosensitive resin composition used for manufacturing microlens patterns on a convex surface is characterized by containing a resin (A) whose solubility in alkali increases with the action of an acid, a photoacid generator (B), and a photodecayable base (C) that decomposes upon exposure and loses its ability to control acid diffusion. Hereinafter, the resin (A) whose solubility in alkali increases with the action of an acid will also be referred to as "resin (A)". The components contained in the positive-type photosensitive resin composition will be described in detail below.

[0015] <Resin (A)> Resin (A), whose solubility in alkalis increases with the action of an acid, is a resin having a constituent unit (a1) derived from hydroxystyrene and a constituent unit (a2) in which at least one hydrogen atom of a hydroxyl group in the constituent unit derived from hydroxystyrene is replaced with an acid-dissociation-inhibiting group. Resin (A) may also contain other constituent units other than constituent units (a1) and (a2) as long as the desired purpose is not impaired.

[0016] The constituent unit (a1) is preferably the constituent unit represented by the following formula (a1-1). The constituent unit (a2) is preferably the constituent unit represented by the following formulas (a2-1), (a2-2), or (a2-3). Hereinafter, the structural unit represented by formula (a1-1) is also referred to as "structural unit (a1-1)". The structural unit represented by formula (a2-1) is also referred to as "structural unit (a2-1)". The structural unit represented by formula (a2-2) is also referred to as "structural unit (a2-2)".

[0017]

Chem.

[0018]

Chem.

[0019] In formula (a1-1), formula (a2-1), formula (a2-2), and formula (a2-3), R a1 and R a3 represent a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group. R a1 and R a3 is not particularly limited in the number of carbon atoms of the alkyl group as R a1 and R a3 preferably has 1 to 5 carbon atoms in the alkyl group as Ra1 , and R a3 The alkyl group may be linear or branched. a1 , and R a3 Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and neopentyl groups. Industrially, the methyl group is preferred. R a1 , and R a3 Specific examples of halogen atoms as halogens, or halogen atoms in alkyl halides, include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, fluorine atoms are preferred. As alkyl halides, groups in which some or all of the hydrogen atoms in the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms are preferred. Alkyl halides may be linear or branched. Preferred specific examples of alkyl halides include fluorinated alkyl groups such as trifluoromethyl groups, pentafluoroethyl groups, heptafluoropropyl groups, and nonafluorobutyl groups. R a1 , and R a3 Preferably, the component is a hydrogen atom or a methyl group, with a hydrogen atom being more preferred.

[0020] R a2 , and R a4 The number of carbon atoms in the alkyl group is preferably 1 or more and 5 or less. a2 , and R a4 A preferred example of an alkyl group as is R a1 , and R a3 Similar to preferred examples of alkyl groups.

[0021] q, s, and t are each independent integers between 0 and 4. Of these, q, s, and t are preferably 0 or 1, and are particularly preferably 0 from an industrial standpoint.

[0022] In equation (a1-1), if q is 1, R a2The substitution site is on the benzene ring in formula (a1-1), R a1 The carbon atom bonded to the carbon atom can be in any of the orthogonal, metagonal, or para positions. If q is an integer between 2 and 4, then R a2 It can be bonded at any position on the benzene ring in formula (a1).

[0023] In equations (a2-1) and (a2-3), when t is 1, R a4 The substitution sites are on the benzene ring in formula (a2-1) and formula (a2-3), R a3 The carbon atom bonded to the carbon atom can be in any of the orthogonal, metagonal, or para positions. If t is an integer between 2 and 4, then R a4 It can be bonded to any position on the benzene ring in formula (a2-1) and formula (a2-3).

[0024] In equation (a1-1), p is an integer between 1 and 5, preferably between 1 and 3, and more preferably 1. In equations (a2-1) and (a2-3), s is an integer between 0 and 4, preferably between 0 and 3, and more preferably 0 or 1. If p is 1 or s is 1, the substitution position of the hydroxyl group in formulas (a1-1), (a2-1), and (a2-3) is R on the benzene ring in formulas (a1-1), (a2-1), or (a2-3). a1 , or R a3 The position of the carbon atom bonded to the carbon atom can be any of the ortho-, meta-, or para-positions, but the para-position is preferred because monomers that give the constituent units represented by formulas (a1-1), (a2-1), or (a2-3) are readily available and inexpensive. In formula (a1-1), if p is an integer between 2 and 5, or in formulas (a2-1) and (a2-3), if s is an integer between 2 and 4, then the hydroxyl group can be bonded to any position on the benzene ring in formulas (a1-1), (a2-1), and (a2-3).

[0025] In equations (a2-1) and (a2-3), r is an integer between 1 and 5, preferably between 1 and 3, and more preferably 1. When r is 1, -C(R) in equations (a2-1) and (a2-3) a5 )(R a6 )OR a7 A group represented by -O-CO-OR a8 The substitution site of the group represented by is on the benzene ring in formula (a2-1) or formula (a2-3), R a3 The carbon atom bonded to the carbon atom can be in any of the orthogonal, metagonal, or para positions. In equations (a2-1) and (a2-3), if r is an integer between 2 and 5, then -C(R a5 )(R a6 )OR a7 A group represented by -O-CO-OR a8 The group represented by can be bonded to any position on the benzene ring in formulas (a2-1) and (a2-3).

[0026] -C(R) in equation (a2-1) a5 )(R a6 )OR a7 In the acid dissociation-inhibiting group represented by R a5 and R a6 Each of these independently represents either a hydrogen atom or an alkyl group. a7 R represents an alkyl group or a cycloalkyl group. a5 , R a6 , and R a7 At least two of these may be joined together to form a ring.

[0027] In equation (a2-2) or equation (a2-3), R a8 This represents an acid-dissociation-inhibiting group, an organic group having a tertiary carbon atom. O and R in formulas (a2-2) and (a2-3). a8 The bond between them is a bond between an oxygen atom and the tertiary carbon atom.

[0028] R a5 , or R a6The number of carbon atoms in the alkyl group is preferably 1 or more and 6 or less. a5 , or R a6 The alkyl group may be linear or branched. R a7 The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less. a7 The alkyl group may be linear or branched. R a7 The number of carbon atoms in the cycloalkyl group is preferably, for example, 3 to 10.

[0029] R a5 , R a6 , or R a7 Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, and neopentyl group. R a7 Specific examples of cycloalkyl groups include cyclopentyl groups and cyclohexyl groups.

[0030] -C(R) in equation (a2-1) a5 )(R a6 )OR a7 Specific examples of acid-dissociative dissolution inhibitory groups represented by include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propyloxyethyl group, 1-isopropyloxyethyl group, 1-n-butyloxyethyl group, 1-isobutyloxyethyl group, 1-tert-butyloxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methylethyl group, and 1-ethoxy-1-methylethyl group.

[0031] R in equation (a2-2) a8 This is an acid-dissociation-inhibiting group, which is an organic group having a tertiary carbon atom. Such an organic group is -C(R A1 )(R A2 )(R A3 A group represented by ) is preferred. 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 cyclic group having 5 to 20 carbon atoms. R A1 , R A2 , and R A3 Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. R A1 , R A2 , and R A3 the fluorinated alkyl group is a group obtained by substituting part or all of hydrogen atoms of the above alkyl group with fluorine atoms. R A1 , R A2 , and R A3 Specific examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specific examples include 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. In particular, groups obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have a substituent) are preferred.

[0032] -C(R A1 )(R A2 )(R A3 ) Specific examples of the group represented by the formula include the following groups. Among the following groups, a tert-butyl group is preferred.

Chemical Formula

[0033] In formula (a2-3), -COOR a8 Specific examples of acid-dissociation-inhibiting groups represented by include the tert-butoxycarbonyl group.

[0034] The resin (A) may contain one or more constituent units (a1-1). The resin (A) may contain one or more constituent units (a2-1). The resin (A) may contain one or more constituent units (a2-2). The resin (A) may contain one or more constituent units (a2-3). The sum of the ratios of constituent units (a1-1), (a2-1), (a2-2), and (a2-3) in resin (A) is preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, even more preferably 50 mol% to 100 mol%, particularly preferably 70 mol% to 100 mol%, and most preferably 100 mol%. When the above ratios are within the above range, it is easy to obtain a positive-type photosensitive resin composition that does not experience excessive film thickness reduction after development and can form a pattern consisting of dots with a rectangular cross-section.

[0035] The proportion of constituent unit (a2-1), constituent unit (a2-2), or (a2-3) in the total number of moles of constituent unit (a1-1), constituent unit (a2-1), constituent unit (a2-2), and constituent unit (a2-3) (i.e., the protection rate of hydroxystyrene) is preferably 10 mol% or more and 50 mol% or less, and 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-type photosensitive resin composition does not experience excessive film thickness reduction after development and is likely to be able to form a pattern consisting of dots with a rectangular cross-section.

[0036] The resin (A) may contain other constituent units other than constituent unit (a1), constituent unit (a2-1), constituent unit (a2-2), and constituent unit (a2-3).

[0037] Other monomers that provide other building blocks include (meth)acrylic acid esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and maleimides. These compounds can be used individually or in combination of two or more.

[0038] Examples of (meth)acrylic acid esters include linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and tert-octyl (meth)acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, and furfuryl (meth)acrylate; glycidyl (meth)acrylate; and (meth)acrylic acid esters having groups with an alicyclic skeleton. In (meth)acrylic acid esters having a group with an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl and cyclohexyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups.

[0039] Examples of (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, and N-hydroxyethyl-N-methyl(meth)acrylamide.

[0040] 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; and others.

[0041] Examples of vinyl ethers include aliphatic vinyl ethers such as 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-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; and the like.

[0042] Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

[0043] Examples of styrenes include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; halostyrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and so on.

[0044] Examples of maleimides include N-substituted maleimides with alkyl groups having 1 to 10 carbon atoms, such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, Nn-pentylmaleimide, and Nn-hexylmaleimide; N-substituted maleimides with alicyclic groups having 3 to 20 carbon atoms, such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, and N-cycloheptylmaleimide; N-arylmaleimides with aryl groups having 6 to 20 carbon atoms, such as N-phenylmaleimide, N-α-naphthylmaleimide, and N-β-naphthylmaleimide; and N-aralkylmaleimides with aralkyl groups having 7 to 20 carbon atoms, such as N-benzylmaleimide and N-phenethylmaleimide.

[0045] <Other resins> The resin contained in the positive-type photosensitive resin composition may also contain other resins in addition to resin (A). The other resins are not particularly limited as long as the desired effect is not impaired. Various resins that have been conventionally incorporated into positive-type photosensitive resin compositions that can be developed with an alkaline developer can be used as the other resins without any particular limitations.

[0046] For ease of obtaining the desired effect, the ratio of the mass of resin (A) to the mass of resin contained in the positive-type photosensitive resin composition is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and most preferably 100% by mass. By including resin (A) in such proportions within the positive-type photosensitive resin composition, it is easy to obtain a positive-type photosensitive resin composition that does not experience excessive film thickness reduction after development and can form a pattern consisting of dots with a rectangular cross-section.

[0047] The weight-average molecular weight (Mw) of resin (A) is preferably 5,000 to 30,000, more preferably 6,000 to 25,000, and even more preferably 8,000 to 20,000. The same applies to the mass-average molecular weight of resin (A). When the weight-average molecular weight is within the above range, it is easy to obtain a positive-type photosensitive resin composition that does not experience excessive film thickness reduction after development and can form a pattern consisting of dots with a rectangular cross-section. In this specification, the weight-average molecular weight is the weight-average molecular weight on a polystyrene basis calculated by gel permeation chromatography (GPC).

[0048] The content of resin (A) in the positive-type photosensitive resin composition may be adjusted according to the resist film thickness to be formed.

[0049] <Photoacid Generator (B)> The photoacid generator (B) is not particularly limited as long as it is a compound that generates acid upon irradiation with active light or radiation. The photoacid generator (B) can be used alone or in combination of two or more. Examples of photoacid generators (B) include onium salt-based photoacid generators and nonionic photoacid generators.

[0050] As the photoacid generator (B), the photoacid generators of the first to fifth embodiments described below are preferred. Hereinafter, preferred examples of the photoacid generator (B) will be described as the first to fifth embodiments. Of the photoacid generators according to the first to fifth embodiments, the photoacid generator according to the first embodiment and the photoacid generator according to the fourth embodiment are onium salt-based photoacid generators. In addition, the photoacid generators according to the second, third, and fifth embodiments are nonionic photoacid generators.

[0051] A first embodiment of the photoacid generator (B) is a compound represented by the following formula (b1-1).

[0052] [ka]

[0053] In the above formula (b1-1), X 1b represents a sulfur or iodine atom with valence g, where g is 1 or 2. h represents the number of repeating units in the structure within parentheses. R 1b X 1b The organic group bonded to the atom is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms. 1bmay be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogen. R 1b has a number of g+h(g-1)+1, and R 1b may each be the same as or different from each other. In addition, two or more R 1b may be bonded to each other directly or via -O-, -S-, -SO-, -SO2-, -NH-, -NR 2b -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group, to form a ring structure containing X 1b . R 2b is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0054] X 2b is a structure represented by the following formula (b1-2).

[0055]

Chemical Formula

[0056] In the above formula (b1-2), X 4b 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, and X 4b may be substituted with at least one selected 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 groups, and halogen. X 5b is -O-, -S-, -SO-, -SO2-, -NH-, -NR 2b-, -CO-, -COO-, -CONH-, alkylene groups with 1 to 3 carbon atoms, or phenylene groups. h represents the number of repeating units in the structure in parentheses. h+1 X 4b and h X 5b These may be the same or different. 2b This is the same as the definition mentioned above.

[0057] X 3b- The counterions of onium include fluorinated alkylfluorophosphate anions represented by the following formula (b1-3) or borate anions represented by the following formula (b1-4), as well as fluoroalkyl sulfonate ions or aryl sulfonate ions in which some or all of the hydrogen atoms are fluorinated.

[0058] [ka]

[0059] In the above formula (b1-3), R 3b R represents an alkyl group in which more than 80% of the hydrogen atoms are replaced by fluorine atoms. j indicates the number of such alkyl groups and is an integer between 1 and 5. 3b These may be the same or different.

[0060] [ka]

[0061] In the above formula (b1-4), R 4b ~R 7b Each of these independently represents a fluorine atom or a phenyl group, and some or all of the hydrogen atoms of the phenyl group may be substituted with at least one selected from the group consisting of fluorine atoms and trifluoromethyl groups.

[0062] The onium ions in the compound represented by formula (b1-1) 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, and bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide. Fido, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi Examples include -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-tolylsulfonium, 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.

[0063] Among the onium ions in the compound represented by the above formula (b1-1), a preferred onium ion is the sulfonium ion represented by the following formula (b1-5).

[0064] [ka]

[0065] In the above formula (b1-5), R 8b Each of these independently represents a group selected from the group consisting of a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, halogen atom, aryl, and arylcarbonyl, which may have substituents. 2b This is X in the above equation (b1-1). 2b It expresses the same meaning.

[0066] Specific examples of sulfonium ions represented by the above formulas (b1-5) 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.

[0067] In the fluorinated alkyl fluorophosphate anion represented by the above formula (b1-3), R 3cThe symbol (b1-1) represents an alkyl group substituted with a fluorine atom, with a preferred number of carbon atoms being 1 to 8, and a more preferred number of carbon atoms being 1 to 4. 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 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The percentage of hydrogen atoms in the alkyl group that are substituted with fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. If the fluorine atom substitution rate is less than 80%, the acid strength of the onium fluorinated alkyl fluorophosphate represented by the above formula (b1-1) decreases.

[0068] Particularly preferred R 3b This refers to a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a 100% fluorine substitution rate. Specific examples include CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C. 3c The number j is an integer between 1 and 5, preferably between 2 and 4, and particularly preferably 2 or 3.

[0069] A specific example of a preferred fluorinated alkylfluorophosphate anion is [(CF3CF2)2PF4]. - [(CF3CF2)3PF3] - [((CF3)2CF)2PF4] - [((CF3)2CF)3PF3] - [(CF3CF2CF2)2PF4] - [(CF3CF2CF2)3PF3] - [((CF3)2CFCF2)2PF4] - [((CF3)2CFCF2)3PF3] - [(CF3CF2CF2CF2)2PF4] - , or [(CF3CF2CF2)3PF3] -These include [(CF3CF2)3PF3] - [(CF3CF2CF2)3PF3] - [((CF3)2CF)3PF3] - [((CF3)2CF)2PF4] - [((CF3)2CFCF2)3PF3] - , or [((CF3)2CFCF2)2PF4] - That is particularly preferable.

[0070] A preferred specific example of the borate anion represented by the above formula (b1-4) is tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ), tetrakis[(trifluoromethyl)phenyl]borate([B(C6H4CF3)4] - ), difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ), trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - ), tetrakis(difluorophenyl)borate ([B(C6H3F2)4] - ) are some examples. Among these, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ) is particularly preferable.

[0071] The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched, or cyclic, having 1 to 20 carbon atoms. It is preferable that the alkyl group has 1 to 10 carbon atoms, considering the bulk of the generated acid and its diffusion distance. Branched and cyclic alkyl groups are particularly preferred due to their short diffusion distance. Furthermore, methyl, ethyl, propyl, butyl, and octyl groups are preferred because they can be synthesized inexpensively.

[0072] The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and may or may not be substituted with an alkyl group or a halogen atom, such as a phenyl group or a naphthyl group. In particular, an aryl group having 6 to 10 carbon atoms is preferred because it can be synthesized inexpensively. Specific examples of preferred aryl groups include phenyl group, toluenesulfonyl group, ethylphenyl group, naphthyl group, and methylnaphthyl group.

[0073] In the above-mentioned fluoroalkyl sulfonate ions or aryl sulfonate ions, when some or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% to 100%, more preferably 50% to 100%, and particularly preferred when all of the hydrogen atoms are replaced with fluorine atoms, as this increases the acid strength. Specific examples of such ions include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.

[0074] Among these, a preferred anion part is the one represented by the following formula (b1-6).

[0075] [ka]

[0076] In the above formula (b1-6), R 20b This is a group represented by the following formulas (b1-7), (b1-8), and (b1-9).

[0077] [ka]

[0078] In the above equation (b1-7), x represents an integer between 1 and 4. Also, in the above equation (b1-8), R 21brepresents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms, and y represents an integer between 1 and 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

[0079] The second embodiment of the photoacid generator (B) is 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 [2-(3,4-methylenedioxyphenyl)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- Liazine, 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-(3,Examples include halogen-containing triazine compounds such as [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, and tris(2,3-dibromopropyl)-1,3,5-triazine, as well as halogen-containing triazine compounds represented by the following formula (b2-1), such as tris(2,3-dibromopropyl)isocyanurate.

[0080] [ka]

[0081] In the above formula (b2-1), R 9b , R 10b , R 11b Each of these independently represents an alkyl halogenated compound.

[0082] Furthermore, a third embodiment of the photoacid generator (B) 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 compounds represented by the following formula (b3-1) that contain an oxime sulfonate group.

[0083] [ka]

[0084] In the above formula (b3-1), R 12b R represents a monovalent, divalent, or trivalent organic group. 13brepresents 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.

[0085] In the above formula (b3-1), the aromatic group refers to a group of a compound that exhibits physical and chemical properties characteristic of aromatic compounds, such as aryl groups like phenyl and naphthyl groups, and heteroaryl groups like furyl and thienyl groups. These may have one or more appropriate substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, or nitro groups. 13b The alkyl group having 1 to 6 carbon atoms is particularly preferred, and examples include the methyl group, ethyl group, propyl group, and butyl group. In particular, R 12b R is an aromatic group, 13b Compounds in which the alkyl group has 1 to 4 carbon atoms are preferred.

[0086] As the acid generator represented by the above formula (b3-1), when n=1, R 12b R is one of a phenyl group, a methylphenyl group, or a methoxyphenyl group, 13b Examples of compounds with a methyl group include α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, and [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophene-3-ylidene](o-tolyl)acetonitrile. When n=2, examples of acid generators represented by the above formula (b3-1) include acid generators represented by the following formula.

[0087] [ka]

[0088] Furthermore, a fourth embodiment of the photoacid generator (B) is an onium salt having a naphthalene ring in the cation portion. "Having a naphthalene ring" means having a structure derived from naphthalene, and that the structure of at least two rings and their aromaticity are maintained. This naphthalene ring may have substituents such as linear or branched alkyl groups having 1 to 6 carbon atoms, hydroxyl groups, or linear or branched alkoxy groups having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be monovalent (one free valency) or divalent (two or more free valencies), but it is preferable that it be monovalent (however, in this case, the free valency is counted excluding the portion bonded to the substituent). The number of naphthalene rings is preferably 1 to 3.

[0089] As the cation portion of an onium salt having a naphthalene ring in the cation portion, a cation represented by the following formula (b4-1) is preferred.

[0090] [ka]

[0091] In the above formula (b4-1), R 14b , R 15b , R 16b At least one of these represents a group represented by the following formula (b4-2), and the remainder represents a linear or branched alkyl group having 1 to 6 carbon atoms, a optionally substituted phenyl group, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, R 14b , R 15b , R 16b One of these is a group represented by the following formula (b4-2), and the remaining two are each independently linear or branched alkylene groups having 1 to 6 carbon atoms, and their ends may be bonded together to form a ring.

[0092] [ka]

[0093] In the above formula (b4-2), R 17b , R 18b Each of these independently represents a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R 19b represents a linear or branched alkylene group having 1 to 6 carbon atoms, which may have single bonds or substituents. l and m each independently represent integers between 0 and 2, and l+m is 3 or less. However, R 17b If multiple instances exist, they may be the same or different from one another. Also, R 18b If multiple instances exist, they may be the same or different from one another.

[0094] The above R 14b , R 15b , R 16b Of the above, the number of groups represented by formula (b4-2) is preferably one from the viewpoint of the stability of the compound, and the remainder are linear or branched alkylene groups having 1 to 6 carbon atoms, and their ends 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 the sulfur atom) constituting the ring is preferably 5 to 6.

[0095] Furthermore, examples of substituents that the alkylene group may have include an oxygen atom (in this case, forming a carbonyl group together with the carbon atoms constituting the alkylene group), a hydroxyl group, and the like.

[0096] Furthermore, examples of substituents that the phenyl group may have include linear or branched alkoxy groups having 1 to 6 carbon atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, and the like.

[0097] Suitable cations for these cation portions include cations represented by the following formulas (b4-3) or (b4-4), with the structure represented by formula (b4-4) being particularly preferred.

[0098] [ka]

[0099] The cation portion can be either an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable from the standpoint of acid generation efficiency, etc.

[0100] Therefore, as the anion suitable for the anionic portion of an onium salt having a naphthalene ring in the cation portion, an anion capable of forming a sulfonium salt is desirable.

[0101] The anionic portion of such an acid generator is a fluoroalkyl sulfonate ion or aryl sulfonate ion in which some or all of the hydrogen atoms are fluorinated. Such anionic portion is the same as that of the fluoroalkyl sulfonate ion or aryl sulfonate ion in which some or all of the hydrogen atoms are fluorinated, as described in the first embodiment.

[0102] Furthermore, as the anion portion, an anion portion containing nitrogen represented by the following formula (b4-5) or formula (b4-6) can also be used.

[0103] [ka]

[0104] In the above formulas (b4-5) and (b4-6), X b This represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkylene group is 2 to 6, preferably 3 to 5, and most preferably 3. b , Z b Each of these independently represents 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 to 10, preferably 1 to 7, and more preferably 1 to 3.

[0105] X b The number of carbon atoms in the alkylene group, or Y b , Z b A smaller number of carbon atoms in the alkyl group is preferable because it results in better solubility in organic solvents.

[0106] Also, X b The alkylene group or Y b , Z b In the alkyl group, the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid, which is preferable. The proportion of fluorine atoms in the alkylene group or alkyl group, i.e., the fluorination rate, is preferably 70% to 100%, more preferably 90% to 100%, and most preferably a perfluoroalkyl group or perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

[0107] Preferred onium salts having a naphthalene ring in the cation region include compounds represented by the following formulas (b4-7) or (b4-8).

[0108] [ka]

[0109] Furthermore, a fifth aspect of the photoacid generator (B) is bissulfonyl diazomethanes such as bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane; 2-nitrobenzyl p-toluenesulfonic acid, 2,6-dinitrobenzyl p-toluenesulfonic acid, nitrobenzyl tosylate, dinitrobenzyl tosylate, and nitrobenzyl sulfonate. Nitrobenzyl derivatives such as nitrobenzylcarbonate and dinitrobenzylcarbonate; sulfonic acid esters such as pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, and N-methylsulfonyloxyphthalimide; N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoro Examples include trifluoromethanesulfonic acid esters such as N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(trifluoromethylsulfonyloxy)-4-butyl-1,8-naphthalimide, and N-(trifluoromethylsulfonyloxy)-4-butylthio-1,8-naphthalimide; onium salts such as diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, and (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; benzoin tosylates such as benzoin tosylate and α-methylbenzoin tosylate; and other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, and benzylcarbonates.

[0110] The content of the photoacid generator (B) in the positive-type photosensitive resin composition is not particularly limited as long as it does not hinder the objective of the present invention. Preferably, the content of the photoacid generator (B) is 0.1 parts by mass or more and 15 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of resin (A).

[0111] <Photodecayable base (C)> By including a photodegradable base (C) in the positive-type photosensitive resin composition, the contrast between exposed and unexposed areas can be improved when forming a patterned resin film using the positive-type photosensitive resin composition. The photo-decayable base (C) is not particularly limited as long as it is a compound that decomposes upon exposure and loses its ability to control acid diffusion. Preferred photo-decayable bases (C) are the compound represented by the following formula (c1-1) (hereinafter referred to as "component (c1-1)"), the compound represented by the following formula (c1-2) (hereinafter referred to as "component (c1-2)"), and the compound represented by the following formula (c1-3) (hereinafter referred to as "component (c1-3)"). Components (c1-1), (c1-2), and (c1-3) lose their basicity in the exposed areas of a coating film made of a positive-type photosensitive resin composition and therefore do not act as quenchers. On the other hand, in the unexposed areas of a coating film made of a photosensitive composition, components (c1-1), (c1-2), and (c1-3) act as quenchers.

[0112] [ka]

[0113] In equation (c1-1), R c1 This is a cyclic group, an alkyl group, or an alkenyl group, which may have substituents, bonded to the carbonyl group in formula (c1-1) via a single bond or via linking groups represented by formulas (y-al-1) to (y-al-5) described below.

[0114] The linking groups represented by formulas (y-al-1) to (y-al-7) are represented by the following chemical formulas.

[0115] -V ’101 -CO-OV ’102 - (y-al-1) -V ’101 -CO-OV ’102 -O-CO- (y-al-2) -V ’101 -O-CO- (y-al-3) -V ’101 -O- (y-al-4) -V ’101 -OV ’102 -O-CO- (y-al-5) -V ’101 -SO2-OV ’102 - (y-al-6) -V ’101 -SO2-OV ’102 -O-CO- (y-al-7)

[0116] In equations (y-al-1) to (y-al-7), V ’101 This is a single bond or an alkylene group having 1 to 5 carbon atoms. ’102 This is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.

[0117] V ’102 As the divalent saturated hydrocarbon group, an alkylene group having 1 to 30 carbon atoms is preferred. ’102 The number of carbon atoms in the alkylene group is more preferably 1 to 10, and even more preferably 1 to 5.

[0118] V ’101 The alkylene group as and V ’102 The alkylene group may be linear or branched, but linear is preferred. V ’101 The alkylene group as and V ’102Preferred specific examples of alkylene groups include methylene groups [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; ethylene groups [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)C Examples include alkylethylene groups such as H2-; trimethylene groups (n-propylene groups) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; tetramethylene groups [-CH2CH2CH2CH2-]; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and pentamethylene groups [-CH2CH2CH2CH2CH2-].

[0119] V ’101 , and V ’102 Some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. Preferred aliphatic cyclic groups are cyclohexylene, adamantane-1,5-diyl, and adamantane-2,6-diyl.

[0120] In equation (c1-2), R c2 R is an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. However, R in formula (c1-2) c2 In this case, a fluorine atom does not bond to a carbon atom adjacent to a sulfur atom.

[0121] In equation (c1-3), R c3 , and R c4 These are, independently, a cyclic group which may have substituents, an alkyl group which may have substituents, or an alkenyl group which may have substituents. c1 It is a single bond or a divalent linking group.

[0122] In equations (c1-1) to (c1-3), m is an integer greater than or equal to 1, and M m+ These are each independently m-valent organic cations.

[0123] ((c1-1) component) · Anion Club In equation (c1-1), R c1 This is a cyclic group, an alkyl group, or an alkenyl group, which may have substituents, bonded to the carbonyl group in formula (c1-1) via a single bond or via linking groups represented by the aforementioned formulas (y-al-1) to (y-al-5).

[0124] The cyclic group constituting the optionally substituted cyclic group in formula (c1-1) is not particularly limited. The cyclic group may be a cyclic hydrocarbon group or a heterocyclic group. The heterocyclic group may contain heteroatoms such as nitrogen, oxygen, and sulfur atoms as ring constituent atoms. The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group.

[0125] As the cyclic group, a cyclic hydrocarbon group is preferred. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. A cyclic aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The cyclic aliphatic hydrocarbon group may have one or more unsaturated bonds. The cyclic aliphatic hydrocarbon group is preferably a saturated cyclic aliphatic hydrocarbon group.

[0126] In formula (c1-1), the number of carbon atoms in the aromatic hydrocarbon ring constituting the optionally substituted aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. In formula (c1-1), the aromatic hydrocarbon rings constituting the optionally substituted aromatic hydrocarbon group are preferably a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring.

[0127] In formula (c1-1), the aromatic hydrocarbon rings constituting the optionally substituted aralkyl group are preferably a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring. In formula (c1-1), the alkylene group constituting the optionally substituted aralkyl group is preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group and an ethane-1,2-diyl group (ethylene group), and even more preferably a methylene group.

[0128] In formula (c1-1), the number of carbon atoms in the aliphatic hydrocarbon ring constituting the optionally substituted cyclic aliphatic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 12. The optionally substituted cyclic aliphatic hydrocarbon group may be a group obtained by removing one hydrogen atom from an optionally substituted monocycloalkane, or a group obtained by removing one hydrogen atom from an optionally substituted polycycloalkane.

[0129] The number of carbon atoms in the substituted monocycloalkane is preferably 3 to 6. Note that the number of carbon atoms in the substituents is not included in the total number of carbon atoms in the monocycloalkane. Preferred substituted monocycloalkanes are substituted cyclopentane and substituted cyclohexane.

[0130] The number of carbon atoms in the substituted polycycloalkane is preferably 7 to 30. Preferred substituted polycycloalkanes are polycycloalkanes having a substituted crosslinked ring system polycyclic skeleton and fused aliphatic hydrocarbon rings having a steroid skeleton, which may be substituted. Examples of polycycloalkanes include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0131] In formula (c1-1), the heterocyclic group can be the lactone-containing cyclic group represented by the following formulas (c2-r-1) to (c2-r-7). [ka]

[0132] In equations (c2-r1) to (c2-r7), Rc ’21 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -CO-OR'', -O-CO-R'', a hydroxyalkyl group, or a cyano group. R'' is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cyclic aliphatic hydrocarbon group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2-containing cyclic group. A'' is an alkylene group having 1 to 5 carbon atoms, which may be interrupted by an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom. n' is an integer between 0 and 2. m' is 0 or 1.

[0133] In equations (c²-r-1) to (c²-r-7), Rc ’21 The number of carbon atoms in the alkyl group is preferably 1 to 6. ’21 The alkyl group may be linear or branched.

[0134] Rc ’21 Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and n-hexyl groups. Among these, methyl and ethyl groups are preferred, with methyl groups being more preferred.

[0135] Rc ’21 The number of carbon atoms in the alkoxy group is preferably 1 to 6. ’21 The alkoxy group may be linear or branched.

[0136] Rc ’21 Specific examples of alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, neopentyloxy, and n-hexyloxy groups. Among these, methoxy and ethoxy groups are preferred, with methoxy groups being more preferred.

[0137] Rc ’21 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine being preferred.

[0138] Rc ’21 As for alkyl halogens, the aforementioned Rc ’21 Examples include groups in which some or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms. Fluorinated alkyl groups are preferred as halogenated alkyl groups, and perfluoroalkyl groups are more preferred.

[0139] Rc ’21 In -CO-OR" and -O-CO-R", R'' is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cyclic aliphatic hydrocarbon group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or an -SO2-containing cyclic group.

[0140] The alkyl group, which may have substituents as R'', may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 or 2. Note that the number of carbon atoms in the alkyl group does not include the number of carbon atoms in substituents. Methyl and ethyl groups are particularly preferred as alkyl groups as R''.

[0141] The number of carbon atoms in the cyclic aliphatic hydrocarbon group, which may have substituents as R'', is preferably 3 to 30, more preferably 3 to 15, even more preferably 4 to 12, and particularly preferably 5 to 10. The number of carbon atoms in the cyclic aliphatic hydrocarbon group does not include the number of carbon atoms in substituents.

[0142] Examples of cyclic aliphatic hydrocarbon groups that may have substituents include groups obtained by removing one hydrogen atom from monocycloalkanes that may be substituted with a fluorine atom or a fluorinated alkyl group; and groups obtained by removing one hydrogen atom from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, examples of cyclic aliphatic hydrocarbon groups include monocycloalkanes such as cyclopentane and cyclohexane from which one hydrogen atom has been removed; and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane from which one or more hydrogen atoms have been removed.

[0143] The lactone-containing cyclic group as R'' is the group represented by the above formulas (c2-r-1) to (c2-r-7), and Rc ’21 However, in the case of -CO-OR" or -O-CO-R", R" is a group that is not a lactone-containing cyclic group.

[0144] The following are suitable examples of lactone-containing cyclic groups represented by any of the formulas (c2-r-1) to (c2-r-7). [ka]

[0145] [ka]

[0146] As the carbonate-containing cyclic group for R'', the group represented by the following formulas (cx3-r-1) to (cx3-r-3) is preferred. [Chem.]

[0147] In formula (cx3-r-1) to formula (cx3-r-3), Rc ’x31 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -CO-O-R", -O-CO-R", a hydroxyalkyl group, or a cyano group. R" represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloaliphatic hydrocarbon group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2- containing cyclic group. A" represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom. p' represents an integer of 0 to 3. q' is 0 or 1.

[0148] The alkylene group as A" in formula (cx3-r-1) to formula (cx3-r-3) may be linear or branched. Examples of the alkylene group as A" include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, and a propane-1,2-diyl group. Among these alkylene groups, a methylene group is preferred.

[0149] The alkylene group as A" may be interrupted by an oxygen atom or a sulfur atom. Examples of alkylene groups interrupted by an oxygen atom or a sulfur atom include -CH2-O-CH2-, -CH2-O-CH2CH2-, -CH2-CH2-O-CH2-CH2-, -CH2-S-CH2-, -CH2-S-CH2CH2-, and -CH2-CH2-S-CH2-CH2-.

[0150] Rc ’x31 The alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -CO-O-R", -O-CO-R", and hydroxyalkyl group as Rc are the same as the Rc in formula (c2-r-1) to formula (c2-r-7) ’21This is similar to alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, -CO-OR'', -O-CO-R'', and hydroxyalkyl groups. However, the carbonate-containing cyclic group as R'' is the group represented by the above formulas (cx3-r-1) to (cx3-r-3), and Rc ’x31 However, in the case of -CO-OR" or -O-CO-R", R" is a group that is not a carbonate-containing cyclic group.

[0151] The following are some preferred examples of carbonate-containing cyclic groups represented by any of the formulas (cx3-r-1) to (cx3-r-3). [ka]

[0152] As the -SO2-containing cyclic group for R'', the group represented by the following formulas (c5-r-1) to (c5-r-3) is preferred. [ka]

[0153] In equations (c5-r-1) to (c5-r-3), Rc ’51 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -CO-OR'', -O-CO-R'', a hydroxyalkyl group, or a cyano group. R'' is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cyclic aliphatic hydrocarbon group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2--containing cyclic group. A'' is an alkylene group having 1 to 5 carbon atoms, which may be interrupted by an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom. n' is an integer between 0 and 2.

[0154] In formulas (c5-r-1) to (c5-r-3), an alkylene group which may be interrupted by an oxygen atom or a sulfur atom as A'' is the same as the alkylene group which may be interrupted by an oxygen atom or a sulfur atom as A'' in formulas (cx3-r-1) to (cx3-r-3).

[0155] Rc ’51 Alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, -CO-OR'', -O-CO-R'', and hydroxyalkyl groups as Rc in formulas (c2-r-1) to (c2-r-7). ’21 This is similar to alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, -CO-OR'', -O-CO-R'', and hydroxyalkyl groups. However, the -SO2-containing cyclic group as R'' is the group represented by the above formulas (c5-r-1) to (c5-r-3), and Rc ’51 However, in the case of -CO-OR" or -O-CO-R", R" is a group that is not a -SO2-containing cyclic group.

[0156] The following are suitable examples of -SO2-containing cyclic groups represented by any of the formulas (c5-r-1) to (c5-r-3). In the following formulas, Ac represents the acetyl group.

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] Rc ’21The number of carbon atoms in the hydroxyalkyl group is preferably 1 or more and 6 or less. The hydroxyalkyl group may be linear or branched. The number of hydroxy groups contained in the hydroxyalkyl group is not particularly limited, and is preferably 1 or 2, more preferably 1. Preferable examples of the hydroxyalkyl group include a hydroxymethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group.

[0161] In formula (c2-r-2), formula (c2-r-3), and formula (c2-r-5), A'' is an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom. A'' in formula (c2-r-2), formula (c2-r-3), and formula (c2-r-5) is the same as A'' described above for formula (cx3-r-1) to formula (cx3-r-3).

[0162] R c1 Specific examples of the lactone-containing groups represented by formula (c2-r-1) to formula (c2-r-7), which are preferable as the heterocyclic group, are the same as the specific examples of the lactone-containing cyclic group as R'' described for formula (c2-r-1) to formula (c2-r-7).

[0163] R c1 The heterocyclic group is also preferably the aforementioned carbonate-containing cyclic group or the aforementioned -SO₂--containing cyclic group.

[0164] R c1 As the heterocyclic group, heterocyclic groups represented by the following formulas (r-hr-1) to (r-hr-16) are also preferable.

Chemical Formula

[0165] R c1 Examples of the substituent that the cyclic group may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxo group (=O), and a nitro group.

[0166] R c1 Alkyl groups that may have substituents may be linear or branched. The number of carbon atoms in a linear alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The number of original atoms in a branched alkyl group is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 10.

[0167] R c1 Specific examples of alkyl groups that may have substituents as such include 1-methylethyl group (isopropyl group), 1-methylpropyl group (sec-butyl group), 2-methylpropyl group (isobutyl group), 1-methylbutyl group (sec-pentyl group), 2-methylbutyl group, 3-methylbutyl group (isopentyl group), 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group (isohexyl group).

[0168] R c1 The number of carbon atoms in the aralkyl group, which may have substituents as such, is preferably 7 to 20, and more preferably 7 to 12. Specific examples of aralkyl groups include benzyl group, phenethyl group, 3-phenylpropyl group, 4-phenylbutyl group, naphthalene-1-ylmethyl group, naphthalene-2-ylmethyl group, naphthalene-1-ylethyl group, and naphthalene-2-ylmethyl group.

[0169] R c1 The alkenyl group, which may have substituents, may be linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 10, more preferably 2 to 5, and even more preferably 2 to 4.

[0170] Examples of linear alkenyl groups include vinyl group, 2-propenyl group (allyl group), 1-propenyl group, 3-butenyl group, 2-butenyl group, and 1-butenyl group. Examples of branched alkenyl groups include 1-methylvinyl group, 1-methyl-2-propenyl group, and 2-methyl-2-propenyl group. As for the alkenyl group, a linear alkenyl group is preferred, a vinyl group, a 2-propenyl group, and a 1-propenyl group are more preferred, and a vinyl group is even more preferred.

[0171] R c1 Examples of substituents on cyclic groups, alkyl groups, aralkyl groups, and alkenyl groups include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, oxo groups (=O), cyano groups, and nitro groups.

[0172] R c1 Preferably, the bonded group is an optionally substituted aromatic hydrocarbon group, an optionally substituted aliphatic cyclic group, or an optionally substituted alkyl group, which is bonded to the carbonyl group in formula (c1-1) via a single bond or via a linking group represented by the aforementioned formulas (y-al-1) to (y-al-5). Substituents that these groups may have include hydroxyl groups, oxo groups (=O), alkyl groups, aryl groups, fluorine atoms, iodine atoms, bromine atoms, fluorinated alkyl groups, and lactone-containing cyclic groups represented by the above formulas (c2-r-1) to (c2-r-7). Examples of aromatic hydrocarbon groups include the phenyl group and the naphthyl group. As aliphatic cyclic groups, groups obtained by removing one hydrogen atom from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are more preferred. The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less. Specific examples of alkyl groups include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; and branched alkyl groups such as 1-methylethyl group (isopropyl group), 1-methylpropyl group (sec-butyl group), 2-methylpropyl group (isobutyl group), 1-methylbutyl group (sec-pentyl group), 2-methylbutyl group, 3-methylbutyl group (isopentyl group), 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group (isohexyl group).

[0173] When the alkyl group is a fluorinated alkyl group having a fluorine atom as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain atoms other than fluorine. Examples of atoms other than fluorine include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0174] Suitable anions for the anionic portion constituting component (c1-1) include the following anions: [ka]

[0175] • Cation section In formula (c1-1), M m+ This is an m-valent organic cation. M m+ Suitable examples of organic cations as such include the following cations: [ka]

[0176] [ka]

[0177] [ka]

[0178] In the following formula, g2 and g3 are the number of repeating methylene groups. g2 and g3 are integers between 0 and 20, inclusive. [ka]

[0179] [ka]

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] Among the cations mentioned above, the cation corresponding to the cation portion in formula (c0-1) is preferred. In other words, it is preferable that the positive-type photosensitive resin composition contains a sulfonium salt containing a sulfonium cation having a fluorine atom as the photodecayable base (C). Therefore, the following cations are preferred as the cation portion. [ka]

[0184] From the viewpoint of improving sensitivity, component (c1-1) preferably contains a compound represented by the following formula (c0-1) (hereinafter also referred to as "component (C0)"). [ka]

[0185] In equation (c0-1), X 0 R is a bromine atom or an iodine atom. m This is a hydroxyl group, an alkyl group, a fluorine atom, or a chlorine atom. nc1 is an integer between 1 and 5 (inclusive). nc2 is an integer between 0 and 4 (inclusive). (nc1 + nc2) is between 1 and 5 (inclusive). Yc 0 is a divalent linking group or a single bond. Mm+ is an m-valent organic cation. m is an integer greater than or equal to 1.

[0186] • Anionic part of component (C0) In equation (c0-1), X 0 This is a bromine atom or an iodine atom, and is preferably an iodine atom.

[0187] In formula (c0-1), R m R is a hydroxyl group, an alkyl group, a fluorine atom, or a chlorine atom. m As the alkyl group, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl groups and ethyl groups are more preferred.

[0188] In equation (c0-1), nc1 is an integer between 1 and 5 (inclusive). nc2 is an integer between 0 and 4 (inclusive). (nc1+nc2) is between 1 and 5 (inclusive). nc1 is preferably an integer between 1 and 3. From the viewpoint of radiation absorption, nc1 is more preferably 2 or 3, and even more preferably 3. nc2 is preferably an integer between 0 and 3, more preferably 0 or 1, and even more preferably 0.

[0189] In equation (c0-1), Yc 0Yc is a divalent linking group or a single bond. 0 As a divalent linking group, a divalent linking group containing an oxygen atom is preferred. Yc 0 A divalent linking group containing an oxygen atom may also contain heteroatoms other than oxygen, such as nitrogen, sulfur, phosphorus, or silicon atoms, in addition to carbon, hydrogen, and oxygen atoms. Examples of divalent linking groups containing an oxygen atom include divalent oxygen atom-containing groups such as -O-, -CO-O-, -CO-NH-, -CO-, -O-CO-O-, and -SO2-; and combinations of one or more divalent oxygen atom-containing groups and one or more alkylene groups. Yc 0 It is preferably a divalent linking group containing an oxygen atom, or a single bond, and more preferably a single bond.

[0190] The following anions are suitable examples of the anionic portion in the (C0) component. [ka]

[0191] • Cationic part of component (C0) In equation (c0-1), M m+ M is an organic cation with an m-valence. m+ A preferred example of this is M in equation (c1-1). m+ This is similar to a suitable example.

[0192] The following compounds are examples of suitable components for (C0). The (C0) component is not limited to the following compounds. [ka]

[0193] (c1-1) Component (c1-1) may be used alone or in combination of two or more components.

[0194] ((c1-2) component) · Anion Club In equation (c1-2), R c2 This is a cyclic group which may have substituents, an alkyl group which may have substituents, or an alkenyl group which may have substituents. R c2 The optionally substituted cyclic groups, optionally substituted alkyl groups, and optionally substituted alkenyl groups are as described above in R c1 This is similar to a cyclic group which may have substituents, an alkyl group which may have substituents, and an alkenyl group which may have substituents. However, R c2 In this mixture, no fluorine atom is bonded to the carbon atom adjacent to the sulfur atom. As a result, the (c1-2) anion is a moderately weak acidic anion, and the quenching ability of the (c1-2) component is improved. R c2 Preferred members include alkyl groups which may have substituents, and aliphatic cyclic groups which may have substituents. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 3 to 10. Preferred aliphatic cyclic groups include groups obtained by removing one hydrogen atom from adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and groups obtained by removing one elementary atom from camphor, etc. Such aliphatic cyclic groups may have substituents. R c2 The hydrocarbon group may have substituents. As substituents, in formula (c1-1), R c2 Examples of substituents that the hydrocarbon group may have include similar groups.

[0195] (c1-2) The following anions are specific examples of anions suitable as the anionic portion constituting the component. [ka]

[0196] • Cation section In equation (c1-2), M m+ M is an organic cation with an m-valence. m+This is M in equation (c1-1). m+ It is similar to that.

[0197] (c1-2) Components may be used individually or in combination of two or more.

[0198] ((c1-3) component) · Anion Club In equation (c1-3), R c3 This is a cyclic group which may have substituents, an alkyl group which may have substituents, or an alkenyl group which may have substituents. R c3 The optionally substituted cyclic groups, optionally substituted alkyl groups, and optionally substituted alkenyl groups are as described above in R c1 This is similar to a cyclic group which may have substituents, an alkyl group which may have substituents, and an alkenyl group which may have substituents. R c3 Preferred members include cyclic groups containing a fluorine atom, alkyl groups which may have substituents, and alkenyl groups which may have substituents, with fluorinated alkyl groups being more preferred. As for fluorinated alkyl groups, Rd 1 A fluorinated alkyl group similar to that used as a fluorinated alkyl group is preferred.

[0199] In equation (c1-3), R c4 This is a cyclic group which may have substituents, an alkyl group which may have substituents, or an alkenyl group which may have substituents. R c4 The optionally substituted cyclic groups, optionally substituted alkyl groups, and optionally substituted alkenyl groups are as described above in R c1 This is similar to a cyclic group which may have substituents, an alkyl group which may have substituents, and an alkenyl group which may have substituents. R c4 The number of carbon atoms in the alkyl group is preferably 1 or more and 5 or less. c4The alkyl group may be linear or branched. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and neopentyl groups. R c4 Some of the hydrogen atoms in the alkyl group may be substituted with hydroxyl groups, cyano groups, etc.

[0200] R c4 Preferred alkenyl groups include vinyl groups, 2-propenyl groups (allyl groups), 1-propenyl groups, 1-methyl-2-propenyl groups, and 2-methyl-2-propenyl groups.

[0201] R c4 Preferred cyclic groups include monocycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, or alicyclic groups obtained by removing one hydrogen atom from polycycloalkanes; aromatic groups such as phenyl and naphthyl groups.

[0202] In equation (c1-3), Y c1 It is a single bond or a divalent linking group. Y c1 Examples of divalent linking groups include, but are not limited to, divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. The divalent hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a combination of an aromatic hydrocarbon group and an aliphatic hydrocarbon group. Y c1 Preferred materials include carbonyl groups, ester bonds, amide bonds, alkylene groups, or combinations thereof. The alkylene group may be linear or branched. Methylene groups and ethylene groups are preferred as alkylene groups.

[0203] (c1-3) The following anions are specific examples of anions suitable as the anionic portion constituting the components. [ka]

[0204] [ka]

[0205] • Cation section In equation (c1-3), M m+ M is an m-valent organic cation. m+ This is M in equation (c1-1). m+ It is similar to that.

[0206] As the photodecayable base (C), only one of components (c1-1), (c1-2), and (c1-3) may be used, or two or more may be used in combination. Of components (c1-1), (c1-2), and (c1-3), component (c1-1) is preferred.

[0207] When a positive-type photosensitive resin composition contains a photodegradable base (C), the content of the photodegradable base (C) in the positive-type photosensitive resin composition is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, more preferably 0.05 parts by mass or more and 3.0 parts by mass or less, and even more preferably 0.10 parts by mass or more and 1.0 part by mass or less, per 100 parts by mass of resin (A).

[0208] <Organic solvent (S)> The positive-type photosensitive resin composition may contain an organic solvent (S). The inclusion of an organic solvent (S) in the positive-type photosensitive resin composition facilitates adjustment of the coatability of the composition and the film thickness of the positive-type photosensitive resin layer formed using the composition. The organic solvent (S) can be used alone or in combination of two or more types.

[0209] Specific examples of organic solvents (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, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, as well as their monomethyl ethers (e.g., propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA)), monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl Examples include polyhydric alcohols such as ethers and their derivatives; cyclic ethers such as dioxanes; esters such as ethyl formate, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc.; aromatic hydrocarbons such as toluene and xylene; and so on.

[0210] In the positive-type 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 more preferably 100 parts by mass or more and 2000 parts by mass or less, per 100 parts by mass of component (A). When the content is within the above range, the coatability of the positive-type photosensitive resin composition is easily improved, and the film thickness of the positive-type photosensitive resin composition layer formed using the positive-type photosensitive resin composition is easily adjusted.

[0211] <Other ingredients> The positive-type photosensitive resin composition may contain various additives along with the above-mentioned components, to the extent that the desired effect is not impaired. The additives can be appropriately selected from various additives that have conventionally been incorporated into positive-type photosensitive resin compositions. Specific examples of other components include polyvinyl resin, surfactants, and acids or acid anhydrides.

[0212] Positive-type photosensitive resin compositions may contain polyvinyl resin to improve the plasticity of the formed film. Specific examples of polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof.

[0213] Positive-type photosensitive resin compositions may contain adhesion enhancers to improve adhesion to the support.

[0214] Positive-type photosensitive resin compositions may contain surfactants to improve coatability, defoaming properties, leveling properties, etc. Specific examples of surfactants include BM-1000, BM-1100 (both manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all manufactured by DIC), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon Examples of commercially available silicone-based or fluorine-based surfactants include, but are not limited to, S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.), Polyfox PF-136A, Polyfox PF-156A, Polyfox PF-151N, Polyfox PF-636, Polyfox PF-656, Polyfox PF-6520 (all manufactured by OMNOVA Solutions Co., Ltd.), BYK-310, BYK-330 (manufactured by Bic Chemie Japan Co., Ltd.).

[0215] Positive-type photosensitive resin compositions may contain an acid or acid anhydride to fine-tune their solubility in the developer.

[0216] 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; hydroxymonocarboxylic acids such as lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, and syringic acid; 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, butanetetracarboxylic acid, trimellitic acid Examples include polycarboxylic acids such as triacidic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, and 1,2,5,8-naphthalenetetracarboxylic acid; and acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymicic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis-trimellitate anhydride, and glycerin tris-trimellitate anhydride.

[0217] <Method for producing a positive-type photosensitive resin composition> The above-described positive-type photosensitive resin composition can be prepared by mixing and stirring the above-described components in a conventional manner. If necessary, dispersion and mixing may be carried out using a disperser such as a dissolver, homogenizer, or three-roll mill. After mixing, the mixture may be further filtered using a mesh, membrane filter, or the like.

[0218] ≪Method for manufacturing microlenses≫ The following describes a method for manufacturing microlenses using the aforementioned positive-type photosensitive resin composition. As for the manufacturing method of microlenses, Forming a positive-type photosensitive resin composition layer using the aforementioned positive-type photosensitive resin composition, Positionally exposing a positive-type photosensitive resin composition layer, Developing the exposed positive-type photosensitive resin composition layer, One method for manufacturing microlenses is to heat a positive-type photosensitive resin composition layer after development to deform it into a microlens shape. This method will also be referred to as Method 1 below.

[0219] Other methods for manufacturing microlenses include: A positive-type photosensitive resin composition layer is formed on the lens material layer using the aforementioned positive-type photosensitive resin composition, Positionally exposing a positive-type photosensitive resin composition layer, Developing the exposed positive-type photosensitive resin composition layer, The positive-type photosensitive resin composition layer is heated after development to form a mask layer having a microlens pattern, One method for manufacturing microlenses is to dry etch a lens material layer and a mask layer to transfer the shape of a microlens pattern onto the lens material layer. This method will also be referred to as the second method below.

[0220] <Method 1> In the first method, a positive-type photosensitive resin composition layer is first formed using the aforementioned positive-type photosensitive resin composition. The method for forming the positive-type photosensitive resin composition layer is not particularly limited. Methods for forming the positive-type photosensitive resin composition layer include coating and lamination of a dry film. Coating is preferred as the lamination method.

[0221] The positive-type photosensitive resin composition layer is usually formed on a substrate. Examples of substrates include image elements containing photodiodes (organic photodiodes, inorganic photodiodes, etc.), silicon wafers on which color filter layers are provided, and silicon wafers on which an anti-reflective film is further formed in some cases.

[0222] The method for applying the positive-type photosensitive resin composition is not particularly limited. For example, a positive-type photosensitive resin composition layer can be formed by applying the positive-type photosensitive resin composition to a desired film thickness using contact transfer type coating devices such as roll coaters, reverse coaters, bar coaters, and slit coaters, or non-contact type coating devices such as spinners (rotary coating devices) and curtain flow coaters.

[0223] When forming a positive-type photosensitive resin composition layer, the coating film made of the positive-type photosensitive resin composition may be subjected to appropriate heat treatment (pre-bake (post-application bake (PAB)) treatment) to remove the solvent in the coating film. The conditions for the above heat treatment vary depending on the type, blending ratio, and coating thickness of each component in the positive-type photosensitive resin composition layer. The heating temperature is preferably 60°C to 150°C, and more preferably 70°C to 140°C. The heating time is preferably 0.5 minutes to 60 minutes, and more preferably 1 minute to 50 minutes. The thickness of the positive-type photosensitive resin composition layer is preferably in the range of 100 nm to 4.0 μm, and more preferably in the range of 200 nm to 1.0 μm.

[0224] The positive-type photosensitive resin composition layer formed as described above is then subjected to position-selective exposure such that dots are formed at the locations where microlenses are to be formed. Position-selective exposure can be performed, for example, via a desired mask pattern. The wavelength of the light used for exposure is not particularly limited. Exposure can be performed using radiation such as a KrF excimer laser, ArF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, or soft X-ray.

[0225] After exposure, the positive-type photosensitive resin composition layer is subjected to PEB (post-exposure bake) treatment (post-exposure heat treatment) as needed. The conditions for PEB treatment vary depending on the type and proportion of each component in the positive-type photosensitive resin composition, the coating thickness, etc. For example, the heating temperature is preferably 60°C to 150°C, and more preferably 70°C to 140°C. The heating time is preferably, for example, 0.5 minutes to 60 minutes, and more preferably 1 minute to 50 minutes.

[0226] Next, the exposed positive-type photosensitive resin composition layer is developed. This dissolves and removes unwanted portions.

[0227] As a developer, aqueous solutions of alkalis such as 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, and 1,5-diazabicyclo[4.3.0]-5-nonane can be used. Alternatively, aqueous solutions of the above alkalis to which appropriate amounts of water-soluble organic solvents such as methanol and ethanol or surfactants can be added can also be used as a developer. As a developer, an aqueous solution of tetramethylammonium hydroxide with a concentration of 0.1% to 10% by mass is preferred.

[0228] The development time varies depending on the composition of the positive-type photosensitive resin composition and the thickness of the positive-type photosensitive resin composition layer, but is usually between 1 minute and 30 minutes. Any of the development methods can be used, such as the liquid-filling method, dipping method, paddle method, or spray development method.

[0229] The developed positive-type 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. By heating the dots that make up the dot pattern in the positive-type photosensitive resin composition layer after development, a convex-lens-shaped microlens is formed. The heating conditions vary depending on the type and proportion of each component in the positive-type photosensitive resin composition, the coating film thickness, etc. For example, the heating temperature is preferably 130°C to 170°C, and more preferably 140°C to 160°C. The heating time is preferably, for example, 1 minute to 30 minutes, and more preferably 3 minutes to 10 minutes. The microlenses formed in this manner consist of a cured product of the aforementioned positive-type photosensitive resin composition.

[0230] <Second Method> In the second method, first, a positive-type photosensitive resin composition layer is laminated onto the lens material layer using a positive-type photosensitive resin composition. The lamination method is not particularly limited. Lamination methods include coating and attaching a dry film. Coating is preferred as the lamination method. The lens material layer is usually formed on a substrate. Examples of substrates include image elements containing photodiodes (organic photodiodes, inorganic photodiodes, etc.), silicon wafers on which color filter layers are provided, and silicon wafers on which an anti-reflective coating is further formed in some cases.

[0231] The method for applying the positive-type photosensitive resin composition onto the lens material layer is the same as the application method described in the first method.

[0232] When forming a positive-type photosensitive resin composition layer, the coating film made of the positive-type photosensitive resin composition may be subjected to appropriate heat treatment (pre-bake (post-application bake (PAB)) treatment) to remove the solvent in the coating film. The conditions for the above heat treatment are the same as those for the heat treatment described in the first method. The thickness of the positive-type photosensitive resin composition layer is preferably in the range of 100 nm to 4.0 μm, and more preferably in the range of 200 nm to 1.0 μm.

[0233] The positive-type photosensitive resin composition layer formed as described above is then exposed to position-selective exposure such that dots are formed at positions corresponding to the positions where microlenses are formed on the lens material layer. Position-selective exposure is performed in the same manner as exposure in the first method.

[0234] After exposure, if necessary, the positive-type photosensitive resin composition layer is subjected to PEB (post-exposure bake) treatment (post-exposure heat treatment). The conditions for the PEB treatment are the same as those for the PEB treatment in the first method.

[0235] Next, the positive-type photosensitive resin composition layer is exposed to light and developed in the same manner as in the first method. After development, the dots constituting the dot pattern in the positive-type photosensitive resin composition layer are heated to deform them into a microlens shape, thereby forming a mask layer having a convex lens-shaped microlens pattern.

[0236] By etching the lens material layer together with the mask, a microlens is formed in which the shape of the mask is transferred. The etching method is preferably dry etching. Dry etching is not particularly limited and includes, for example, dry etching by plasma (oxygen, argon, CF4, etc.) or corona discharge.

[0237] As described above, the present inventors provide the following [1] to [6]. [1] A positive-type photosensitive resin composition used in the manufacture of a convex microlens pattern, The positive-type photosensitive resin composition contains a resin (A) whose solubility in alkali increases with the action of an acid, a photoacid generator (B), and a photodecayable base (C) that decomposes upon exposure and loses its ability to control acid diffusion. A positive-type photosensitive resin composition in which the resin (A) is a resin having a constituent unit (a1) derived from hydroxystyrene and a constituent unit (a2) in which at least one hydrogen atom of a hydroxyl group in the constituent unit derived from hydroxystyrene is replaced with a group containing an acid-dissociation-inhibiting group. [2] The constituent unit (a1) is a constituent unit represented by the following formula (a1-1), The positive-type photosensitive resin composition according to [1], wherein the constituent unit (a2) is a constituent unit represented by the following formula (a2-1), (a2-2), or (a2-3). [ka] (In formula (a1), R a1 R represents a hydrogen atom, alkyl group, halogen atom, or halogenated alkyl group, a2 (where represents a hydrogen atom or an alkyl group, p represents an integer between 1 and 5, and q represents an integer between 0 and 4.) [ka] (In formulas (a2-1) to (a2-3), R a3 R represents a hydrogen atom, alkyl group, halogen atom, or halogenated alkyl group, a4 , R a5 and R a6 Each independently represents a hydrogen atom or an alkyl group, R a7 R represents an alkyl group or cycloalkyl group, a8 represents an organic group having a tertiary carbon atom, and in formulas (a2-2) and (a2-3), O and R a8 The bond between the oxygen atom and the tertiary carbon atom is a bond between the oxygen atom and the tertiary carbon atom, where r is an integer between 1 and 5, and s and t are each independently integers between 0 and 4. [3] The photo-disintegrating base (C) is a compound represented by the following formula (c1-1), (c1-2), or (c1-3), in the positive-type photosensitive resin composition described in [1]. [ka] (In formulas (c1-1) to (c1-3), R c1 ~R c4 R is an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. However, R in formula (d1-2) c2 In this case, no fluorine atom is bonded to the carbon atom adjacent to the S atom. c1is a single bond or a divalent linking group. m is an integer greater than or equal to M m+ These are each independently m-valent onium cations. A microlens comprising a cured product of a positive-type photosensitive resin composition described in any one of [4], [1], to [3]. Forming a positive-type photosensitive resin composition layer using any one of the positive-type photosensitive resin compositions described in [5], [1] to [3], Positionally exposing a positive-type photosensitive resin composition layer, Developing the exposed positive-type photosensitive resin composition layer, A method for manufacturing microlenses, comprising heating a positive-type photosensitive resin composition layer after development to deform it into a microlens shape. [6] Laminating a positive-type photosensitive resin composition layer on a lens material layer using any one of the positive-type photosensitive resin compositions described in [1] to [3], Positionally exposing a positive-type photosensitive resin composition layer, Developing the exposed positive-type photosensitive resin composition layer, The positive-type photosensitive resin composition layer is heated after development to form a mask layer having a microlens pattern, A method for manufacturing microlenses, comprising dry etching a lens material layer and a mask layer to transfer the shape of a microlens pattern onto the lens material layer. [Examples]

[0238] The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to these examples.

[0239] [Preparation of positive-type photosensitive resin composition] Positive-type photosensitive resin compositions were prepared by uniformly dissolving the type and amount of resin (A), photoacid generator (B), photodisintegrating base (C) or amine quencher (CA), and surfactant (D) 0.03 parts by mass in 1500 parts by mass of organic solvent (S). The numbers in parentheses in Table 1 represent the amount of each component blended (in parts by mass).

[0240] [Table 1]

[0241] Each component, surfactant (D), and organic solvent (S) listed in Table 1 is described below.

[0242] <Resin (A)> The following resins A-1 to A-4 were used as resins corresponding to the aforementioned resin (A). In the following formulas representing resins A-1 to A-4, the subscripts (x and y) attached to each repeating unit represent the ratio (mol%) of each repeating unit to the total number of repeating units contained in the resin.

[0243] A-1: A resin represented by the following formula (weight-average molecular weight 20000, x=64, y=36) [ka]

[0244] A-2: A resin represented by the following formula (weight-average molecular weight 8000, x=73, y=27) [ka]

[0245] A-3: Resin represented by the following formula (weight-average molecular weight 20000, x=68, y=32) [ka]

[0246] A-4: Resin represented by the following formula (weight-average molecular weight 10000, x=74, y=26) [ka]

[0247] <Photoacid Generator (B)> The following B-1 and B-2 were used as photoacid generators (B).

[0248] B-1: Bis(cyclohexylsulfonyl)diazomethane B-2: Compound represented by the following formula [ka]

[0249] <Photodecayable base (C)> The following C-1 and C-2 were used as photodecayable bases (C).

[0250] C-1: Compound represented by the following formula [ka]

[0251] C-2: Compound represented by the following formula [ka]

[0252] The following C-3 to C-6 were used as amine quenchers (CA). C-3: Trihexylamine C-4:2,6-di-tert-butylpyridine C-5: Triethanolamine C-6:2,6-diphenylpyridine

[0253] D-1 was used as the surfactant (D) described below. D-1: BYK-310 (manufactured by Big Chemie Japan Co., Ltd.)

[0254] The following S-1 was used as the organic solvent (S). S-1: Mixed solvent of propylene glycol monomethyl ether acetate / ethyl lactate / propylene glycol monomethyl ether = 50 / 25 / 25

[0255] The positive-type photosensitive resin compositions obtained in each example and comparative example were evaluated according to the following method, based on the items listed in Table 2.

[0256] <Formation of dot patterns> Using a spinner, the positive-type photosensitive resin compositions of each example and each comparative example were applied to form a coating film. The above coating film was then pre-baked on a hot plate at 100°C for 90 seconds to dry it, thereby forming a positive-type photosensitive resin composition layer with a thickness of 600 nm. Next, using a KrF exposure system NSR-S203 (Nikon, NA=0.68, S=0.75), the positive-type photosensitive resin composition layer was irradiated with a KrF excimer laser (wavelength: 248 nm) through a mask for forming a dot pattern with a dot diameter of 400 nm and an inter-dot distance of 300 nm. The exposure was performed with an exposure dose that could form an inter-dot distance of 300 nm. Subsequently, the positive-type photosensitive resin composition layer was subjected to PEB treatment at 110°C for 90 seconds. Next, the exposed positive-type photosensitive resin composition layer was developed at room temperature (23°C) for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. After that, a 30-second rinse with pure water and a dehydrobake treatment at 110°C for 60 seconds were performed to form a dot pattern consisting of multiple dots.

[0257] <Evaluation of Optimal Exposure (EoP)> In the exposure process for forming the dot pattern described above, the exposure amount that resulted in a dot-to-dot distance of 300 nm was measured. The dot-to-dot distance was measured using an FEB length measuring device S-9220 (manufactured by Hitachi High-Technologies Corporation). Based on the measured exposure levels, the optimal exposure level was evaluated according to the following criteria. The results are shown in Table 2. S (Good): Exposure amount between 15mJ and 40mJ A (Fair): Exposure amount less than 15 mJ, or between 40 mJ and 60 mJ. B (Defective): Exposure amount exceeds 60mJ

[0258] <<Evaluation of film loss (Dark-Loss)>> Based on the evaluation of the optimal exposure dose (EoP) described above, the film thickness Th1 of the resin film after PEB treatment and the dot thickness Th2 after dehydrobake treatment were measured using a scanning electron microscope SU-8000 (Hitachi High-Technologies Corporation) to form a dot pattern. Based on the measured film thickness, the rate of change in the cured film thickness was calculated using the following formula. Film thickness change rate (%) = Th2 / Th1 × 100 Based on the calculated film thickness change rate, the post-development film thickness change was evaluated according to the following criteria. The results are shown in Table 2. S (Good): Film thickness change rate is between 90% and 100%. A (Fairly Good): Film thickness change rate is between 80% and 90%. B (Defective): Film thickness change rate is 80% or less

[0259] [Table 2]

[0260] Tables 1 and 2 show that the positive-type photosensitive resin composition of the example, comprising resin (A), photoacid generator (B), and photodecayable base (C), exhibits good sensitivity and provides a resist pattern with minimal dark loss after development. On the other hand, the positive-type photosensitive resin compositions of Comparative Examples 1 to 4, which did not use a photodecayable base (C) but used an amine quencher, were found to have low sensitivity and produced a resist pattern with dark loss after development.

Claims

1. A positive-type photosensitive resin composition used in the manufacture of convex microlens patterns, The positive-type photosensitive resin composition contains a resin (A) whose solubility in alkali increases with the action of an acid, a photoacid generator (B), and a photodecayable base (C) that decomposes upon exposure and loses its ability to control acid diffusion. A positive-type photosensitive resin composition in which the resin (A) comprises a structural unit (a1) derived from hydroxystyrene and a structural unit (a2) in which at least one hydrogen atom of a hydroxyl group in the structural unit derived from hydroxystyrene is replaced with an acid-dissociation-inhibiting group-containing group.

2. The aforementioned constituent unit (a1) is a constituent unit represented by the following formula (a1-1), The positive-type photosensitive resin composition according to claim 1, wherein the constituent unit (a2) is a constituent unit represented by the following formula (a2-1), (a2-2), or (a2-3). 【Chemistry 1】 (In formula (a1), R ａ１ R represents a hydrogen atom, an alkyl group, a halogen atom, or an alkyl halogenate. ａ２ (where represents a hydrogen atom or an alkyl group, p represents an integer between 1 and 5, and q represents an integer between 0 and 4.) 【Chemistry 2】 (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 a hydrogen 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, the bond between O and R ａ８ in formulas (a2-2) and (a2-3) is a bond between an oxygen atom and said tertiary carbon atom, r represents an integer of 1 to 5, and s and t each independently represent an integer of 0 to 4.)

3. The positive-type photosensitive resin composition according to claim 1, wherein the photo-decayable base (C) is a compound represented by the following formulas (c1-1), (c1-2), or (c1-3). 【Transformation 3】 (In formulas (c1-1) to (c1-3), R ｃ１ ~R ｃ４ R is an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. However, R in formula (d1-2) ｃ２ In this example, no fluorine atom is bonded to the carbon atom adjacent to the sulfur atom. ｃ１ is a single bond or a divalent linking group. m is an integer of 1 or more, M ｍ＋ These are each independently m-valent onium cations.

4. A microlens comprising a cured product of a positive-type photosensitive resin composition according to any one of claims 1 to 3.

5. A positive-type photosensitive resin composition layer is formed using the positive-type photosensitive resin composition described in any one of claims 1 to 3, The positive-type photosensitive resin composition layer is exposed to positional exposure, Developing the exposed positive-type photosensitive resin composition layer, A method for manufacturing a microlens, comprising heating the positive-type photosensitive resin composition layer after development to deform it into a microlens shape.

6. A positive-type photosensitive resin composition layer is laminated on a lens material layer using the positive-type photosensitive resin composition described in any one of claims 1 to 3, The positive-type photosensitive resin composition layer is exposed to positional exposure, Developing the exposed positive-type photosensitive resin composition layer, The positive-type photosensitive resin composition layer after development is heated 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 onto the lens material layer.

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