Negative photopolymerizable composition for forming microlens-shaped patterns and method for manufacturing optical elements

Abstract

To provide a negative-type photopolymerizable composition for forming microlens-shaped patterns that exhibits excellent sensitivity and stability over time after exposure, has a uniform shape, and has excellent chemical resistance, and a method for manufacturing an optical element using the negative-type photopolymerizable composition. [Solution] A method comprising KrF exposure, in which a photosensitive layer is irradiated with KrF rays; formation of a dot pattern consisting of multiple dots by heating and developing the exposed photosensitive layer; and formation of a microlens-shaped pattern consisting of multiple microlens-shaped dots by heating and deforming the dots, wherein the negative-type photopolymerizable composition for forming a microlens-shaped pattern used for forming the photosensitive layer comprises a photopolymerizable compound (A) and a photosensitive agent (B).

Description

[Technical Field]

[0001] The present invention relates to a negative-type photopolymerizable composition for forming microlens-shaped patterns, and to a method for manufacturing an optical element using the negative-type photopolymerizable 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 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 should be formed. Each dot in the dot pattern has a roughly cylindrical or roughly frustoconical shape. By heating the dot pattern at a temperature above the glass transition temperature of the resin material that makes up the dots, the resin material makes up the dots to flow, and due to surface tension, the shape of each dot changes to a hemispherical lens shape. In this way, a pattern of microlenses consisting of multiple microlenses is formed.

[0004] Furthermore, the etch-back method is known as one method for manufacturing microlenses for CCD or CMOS image sensors. In this method, first, a resin layer for microlenses is formed on a color filter. Next, using a photosensitive resin composition in the same manner as the thermal flow method described above, a pattern corresponding to the shape of the microlens is formed on the resin layer for microlenses. The pattern thus formed, corresponding to the shape of the microlens, is used as an etching mask to etch back the underlying resin layer for microlenses, and the pattern of the etching mask (a pattern corresponding to the shape of the microlens) is transferred to the resin layer for microlenses, thereby manufacturing the microlens pattern (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-203913 [Overview of the project] [Problems that the invention aims to solve]

[0006] Depending on the application of the optical element, microlenses of different sizes, refractive indices, or shapes may be formed within the optical element. In this case, the thermal flow method and etch-back method described above require many steps to form microlens shape patterns (microlens patterns or etching mask patterns). Consequently, dot patterns, microlens shape patterns, etc., are frequently exposed to chemicals such as organic solvents during the manufacturing process of optical elements. Furthermore, in order to form two or more microlenses of different sizes, refractive indices, or shapes within an optical element, it is necessary to form microlens shape patterns (microlens patterns or etching mask patterns) of the desired size, refractive index, or shape at predetermined locations. For this purpose, the photosensitive resin composition is required to have good photolithography properties, particularly high sensitivity. Furthermore, it is required that a microlens shape pattern (such as a microlens pattern or an etching mask pattern) with a uniform shape be formed. A microlens shape pattern with a uniform shape means that, in the case of a microlens shape pattern, if there is only one type of microlens, that one type of microlens has a uniform shape, or if there are two or more types of microlenses, at least one type of microlens has a uniform shape. Furthermore, in the formation of microlens shape patterns (microlens patterns and etching mask patterns), it is desirable that the resulting microlens patterns and etching mask patterns undergo minimal changes in dimensions, etc., even after the photosensitive layer has been left for a certain period of time after exposure; in other words, that the post-exposure delay (PED) is excellent. As described above, photosensitive resin compositions used for forming microlens-shaped patterns (patterns of microlenses or patterns of etching masks) are required to have excellent sensitivity, stability over time after exposure, and the ability to form microlens-shaped patterns that have a uniform shape and excellent chemical resistance.

[0007] This invention has been made in view of the above conventional circumstances, and aims to provide a negative-type photopolymerizable composition for forming microlens-shaped patterns that can form microlens-shaped patterns that have excellent sensitivity and stability over time after exposure, a uniform shape, and excellent chemical resistance, and a method for manufacturing an optical element using the negative-type photopolymerizable composition. [Means for solving the problem]

[0008] The inventors have discovered that the above problems can be solved by a negative-type photopolymerizable composition for forming microlens-shaped patterns, which is used for forming a photosensitive layer and comprises a photopolymerizable compound (A) and a photosensitive agent (B), in a method that includes KrF exposure, in which a photosensitive layer is irradiated with KrF rays; formation of a dot pattern consisting of multiple dots by heating and developing the exposed photosensitive layer; and formation of a microlens-shaped pattern consisting of multiple microlens-shaped dots by heating and deforming the dots, and have arrived at the present invention. Specifically, the present invention provides the following.

[0009] A first aspect of the present invention is a method comprising KrF exposure, in which a photosensitive layer is irradiated with KrF rays; formation of a dot pattern consisting of a plurality of dots by heating and developing the exposed photosensitive layer; and formation of a microlens-shaped pattern consisting of a plurality of microlens-shaped dots by heating and deforming the dots, wherein a negative-type photopolymerizable composition for forming a microlens-shaped pattern is used for forming the photosensitive layer, This is a negative-type photopolymerizable composition for forming microlens-shaped patterns, comprising a photopolymerizable compound (A) and a photosensitive agent (B).

[0010] A second aspect of the present invention is: A method for manufacturing an optical element comprising a plurality of microlenses, including n types of microlenses, on a substrate, USn is an integer greater than or equal to 2, The aforementioned manufacturing method Forming a resin film on the aforementioned substrate, Forming an etching mask on the resin film having a shape corresponding to the shape of the plurality of microlenses, The process includes etching the resin film together with the etching mask to form the plurality of microlenses on which the shape of the etching mask has been transferred, The etching mask is as follows (i) to (iii): (i) Applying the m-th photosensitive composition onto the resin film to form the m-th photosensitive layer, (ii) KrF exposure by irradiating the m-th photosensitive layer with a KrF line, heating and developing after the KrF exposure, thereby forming the m-th dot at a position corresponding to the position where the m-th microlens is formed on the substrate, (iii) Heating the m-th dot to deform it into a shape corresponding to the shape of the m-th microlens, This is formed by repeating the operation n times. The aforementioned m is an integer between 1 and n, The first to nth photosensitive compositions used in forming the etching mask may be the same or different. A method for manufacturing an optical element, wherein at least one of the first to nth photosensitive compositions is a negative-type photopolymerizable composition according to the first embodiment.

[0011] A third aspect of the present invention is: A method for manufacturing an optical element comprising a plurality of microlenses, including n types of microlenses, on a substrate, USn is an integer greater than or equal to 2, The aforementioned multiple microlenses are arranged as follows: (iv)~(vi): (iv) Applying the m-th photosensitive composition to the substrate to form the m-th photosensitive layer, (v) KrF exposure by irradiating the m-th photosensitive layer with a KrF line, heating and developing after the KrF exposure to form the m-th dot at a position corresponding to the position where the m-th microlens is formed on the substrate, (vi) By heating the m-th dot, the m-th dot is deformed into a shape corresponding to the shape of the m-th microlens, The process involves repeating an operation having n times to form the desired result. The aforementioned m is an integer between 1 and n, The first to nth photosensitive compositions used in the formation of the plurality of microlenses may be the same or different. A method for manufacturing an optical element, wherein at least one of the first to nth photosensitive compositions is a negative-type photopolymerizable composition according to the first embodiment. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a negative-type photopolymerizable composition for forming microlens-shaped patterns that have excellent sensitivity and stability over time after exposure, a uniform shape, and excellent chemical resistance, and a method for manufacturing an optical element using the negative-type photopolymerizable composition. [Modes for carrying out the invention]

[0013] <<Negative-type photopolymerizable composition>> The negative-type photopolymerizable composition is a negative-type photopolymerizable composition for forming a microlens-shaped pattern, used in a method that includes KrF exposure, in which a photosensitive layer is irradiated with KrF rays; formation of a dot pattern consisting of multiple dots by heating and developing the exposed photosensitive layer; and formation of a microlens-shaped pattern consisting of multiple microlens-shaped dots by heating and deforming the dots. A negative-type photopolymerizable composition comprises a photopolymerizable compound (A) and a photosensitive agent (B). The negative-type photopolymerizable composition may also contain components other than the photopolymerizable compound (A) and the photosensitive agent (B).

[0014] The photopolymerizable compound (A) may be a resin (A1) or a compound that is not a polymer. An example of resin (A1) is an alkali-soluble resin (A1-1). Examples of compounds that are not polymers include polyfunctional (meth)acrylates (A2), epoxy group-containing compounds (A3), and methylol-type compounds (A4). In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate." "(meth)acrylic" means both "acrylic" and "methacrylic." "(meth)acryloyloxy" means both "acryloyloxy" and "methacrylicoxy." Examples of photosensitive agents (B) include photoradical polymerization initiators (B1) and photoacid generators (B2).

[0015] The negative-type photopolymerizable composition is a photosensitive composition that forms a microlens pattern as a microlens shape pattern, or a photosensitive composition that forms an etching mask pattern as a microlens shape pattern, in a method (hereinafter also referred to as "method for forming a microlens shape pattern") that includes KrF exposure, in which a photosensitive layer is irradiated with KrF rays; formation of a dot pattern consisting of multiple dots by heating and developing the exposed photosensitive layer; and formation of a microlens shape pattern consisting of multiple dots by heating and deforming the dots. Furthermore, if the negative-type photopolymerizable composition is a photosensitive composition that forms a microlens pattern as a microlens-shaped pattern, then the multiple microlens-shaped dots (microlens-shaped pattern) in the method for forming the microlens-shaped pattern are multiple microlenses (microlens patterns). Furthermore, if the negative-type photopolymerizable composition is a photosensitive composition that forms an etching mask pattern as a microlens shape pattern, then the multiple microlens-shaped dots (microlens shape pattern) in the method for forming the microlens shape pattern are an etching mask (etching mask pattern) in a method for manufacturing microlenses that includes forming an etching mask on a resin film having a shape corresponding to the shape of multiple microlenses, and forming multiple microlenses on which the shape of the etching mask has been transferred by etching the resin film together with the etching mask. The resin film is a microlens material layer. The multiple microlenses may also include two or more types of microlenses.

[0016] The negative-type photopolymerizable composition described above, when used in a method that includes KrF exposure, in which a photosensitive layer is irradiated with KrF rays; formation of a dot pattern consisting of multiple dots by heating and developing the exposed photosensitive layer; and formation of a microlens-shaped pattern consisting of multiple microlens-shaped dots by heating and deforming the dots, can form a microlens-shaped pattern with a uniform shape and excellent chemical resistance, and also exhibits excellent sensitivity and post-exposure storage stability (PED). On the other hand, if the composition is not a negative-type photopolymerizable composition (for example, a positive-type composition or one that does not contain photopolymerizable compound (A)), or if the exposure method is not one that irradiates with KrF rays, then sensitivity, post-exposure stability over time, uniformity of the formed lens shape, and chemical resistance will be inferior.

[0017] The essential and optional components of the negative-type photopolymerizable composition are described below.

[0018] <<Photopolymerizable compound (A)>> As described above, the photopolymerizable compound (A) may be a resin (A1) or a compound that is not a polymer. Alternatively, a monomer that yields resin (A1) may be included in the negative-type photopolymerizable composition. If the negative-type photopolymerizable composition contains a monomer that yields resin (A1) as the photopolymerizable compound (A), the monomer generates resin (A1) by exposing or heating the negative-type photopolymerizable composition.

[0019] <Resin (A1)> The resin (A1) may be either an alkali-soluble resin (A1-1) or a non-alkali-soluble resin, but it is preferable that it be an alkali-soluble resin (A1-1). In this specification, an alkali-soluble resin refers to a resin that dissolves to a thickness of 0.01 μm or more when a resin film with a thickness of 1 μm is formed on a substrate using a resin solution with a resin concentration of 18% by mass (solvent: propylene glycol monomethyl ether acetate) and immersed in a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution for 1 minute.

[0020] The alkali-soluble resin (A1-1) preferably has epoxy group-containing units. The epoxy group-containing unit is a constituent unit having an epoxy group-containing group. Examples of epoxy group-containing units include structural units represented by the following formula (a1). [ka] (In formula (a1), R 1 R is a hydrogen atom or a methyl group, 2 R is a single bond or an alkylene group having 1 to 5 carbon atoms. 3 (This is an epoxy group-containing group.)

[0021] In formula (a1), R 2 The alkylene group may be linear or branched, but linear is preferred. 2Specific examples of the alkylene group as such include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and the like. Among these groups, a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group are preferable, a methylene group, an ethane-1,2-diyl group, and a propane-1,3-diyl group are more preferable, and a methylene group is particularly preferable.

[0022] In formula (a1), R 3 is a group containing an epoxy group. In formula (a1), the group represented by -R 2 -R 3 is preferably a glycidyl group.

[0023] Also, in formula (a1), the epoxy group-containing group as R 3 may be an alicyclic epoxy group. The alicyclic epoxy group is an alicyclic group in which two carbon atoms as adjacent ring-constituting atoms are bonded via an oxygen atom. That is, the alicyclic epoxy group has an epoxy group containing a three-membered ring composed of two carbon atoms and one oxygen atom on the alicyclic ring. In formula (a1), when the epoxy group-containing group as R 3 is an alicyclic epoxy group, the structural unit represented by formula (a1) is preferably a structural unit derived from 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 decane-8-yl (meth)acrylate, or 3,4-epoxytricyclo[5.2.1.0 2,6 decane-9-yl (meth)acrylate.

[0024] The alkali-soluble resin (A1-1) may have a structural unit represented by the following formula (a2).

Chemical formula

[0025] In formula (a2), R 4 The divalent hydrocarbon group can be a divalent linear or branched aliphatic hydrocarbon group, or a divalent aromatic hydrocarbon group. Examples of divalent linear or branched aliphatic hydrocarbon groups include alkylene groups such as methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. Examples of divalent aromatic hydrocarbon groups include phenylene groups and naphthalene groups.

[0026] The alkali-soluble resin (A1-1) preferably has a structural unit represented by the following formula (a3). [ka] (In formula (a3), R 1 R is a hydrogen atom or a methyl group, 5 R is a single bond or a divalent linking group. 6 (This refers to an organic group containing two or more benzene rings.)

[0027] In formula (a3), R 5 The divalent linking group is not particularly limited as long as it does not hinder the objectives of the present invention. Preferred examples of divalent linking groups include alkylene groups having 1 to 6 carbon atoms, divalent groups selected from the group consisting of -O-, -S-, -CO-, -SO2-, -CO-NH-, -CO-NH-CO-, -NH-CO-NH-, -CO-O-, -CO-O-CO-, -O-CO-O-, -NH-, and -SS-, and groups that combine two or more divalent groups selected from the aforementioned group.

[0028] In formula (a3), R 6Examples of organic groups containing two or more benzene rings include the following polycyclic compounds, or compounds to which substituents have been introduced, from which one hydrogen atom has been removed. In the following formulas, X is -O-, -S-, -CO-, -SO2-, -CO-NH-, -CO-NH-CO-, -NH-CO-NH-, -CO-O-, -CO-O-CO-, -O-CO-O-, -NH-, -SS-, -CH2-, -CH(CH3)-, or -C(CH3)2-. [ka]

[0029] Substituents that can be introduced into the above polycyclic compounds include halogen atoms, alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aliphatic acyl groups having 2 to 6 carbon atoms, nitro groups, and cyano groups. When substituents are introduced to the above polycyclic compound, the number of substituents is not particularly limited, but it is preferably 4 or less, and preferably 1 or 2.

[0030] The alkali-soluble resin (A1-1) may have constituent units derived from monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid.

[0031] When the alkali-soluble resin (A1-1) has a structural unit represented by formula (a1), the content of the structural unit represented by formula (a1) in the alkali-soluble resin (A1-1) is preferably 1 mol% or more and 70 mol% or less, and more preferably 3 mol% or more and 50 mol% or less.

[0032] When the alkali-soluble resin (A1-1) has a structural unit represented by formula (a2), the content of the structural unit represented by formula (a2) in the alkali-soluble resin (A1-1) is preferably 0.5 mol% or more and 75 mol% or less, more preferably 1 mol% or more and 50 mol% or less, and even more preferably 5 mol% or more and 40 mol% or less.

[0033] When the alkali-soluble resin (A1-1) has a structural unit represented by formula (a3), the content of the structural unit represented by formula (a3) ​​in the alkali-soluble resin (A1-1) is preferably 5 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 90 mol% or less, and even more preferably 50 mol% or more and 90 mol% or less.

[0034] When the alkali-soluble resin (A1-1) contains constituent units derived from monocarboxylic acids, the content of constituent units derived from monocarboxylic acids in the alkali-soluble resin (A1-1) is preferably 1 mol% or more and 50 mol% or less, and more preferably 5 mol% or more and 40 mol% or less.

[0035] The weight-average molecular weight (Mw) of resin (A1) is preferably 5,000 to 30,000, and more preferably 5,000 to 10,000. In this specification, the weight-average molecular weight is the weight-average molecular weight on a polystyrene basis determined by gel permeation chromatography (GPC).

[0036] When the negative-type photopolymerizable composition contains resin (A1), the content of resin (A1) is preferably 30% to 90% by mass, more preferably 35% to 85% by mass, and particularly preferably 40% to 70% by mass, based on the total solid content of the negative-type photopolymerizable composition. In this specification, solid content refers to components other than the organic solvent (S) and water.

[0037] <Compounds that are not polymers> Examples of non-polymer compounds that can be used as photopolymerizable compounds (A) include, as mentioned above, polyfunctional (meth)acrylates (A2), epoxy group-containing compounds (A3), and methylol-type compounds (A4).

[0038] [Polyfunctional (meth)acrylate (A2)] The polyfunctional (meth)acrylate (A2) has two or more (meth)acryloyloxy groups. Examples of polyfunctional (meth)acrylate compounds (A2) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Examples include acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester di(meth)acrylate, glycerin tri(meth)acrylate, glycerin polyglycidyl ether poly(meth)acrylate, and ethoxylated dipentaerythritol polyacrylate. Dipentaerythritol hexa(meth)acrylate is preferred as the polyfunctional (meth)acrylate compound (A2).

[0039] When the negative-type photopolymerizable composition contains a polyfunctional (meth)acrylate (A2), the content of the polyfunctional (meth)acrylate (A2) is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and particularly preferably 10% by mass or more and 40% by mass or less, based on the total solid content of the negative-type photopolymerizable composition.

[0040] [Epoxy group-containing compound (A3)] Epoxy group-containing compounds (A3) are compounds that have two or more epoxy groups in their molecule. The epoxy group-containing compound (A3) can react with phenolic hydroxyl groups of alkali-soluble resins (D), etc., as described later, to crosslink the alkali-soluble resins (D), etc.

[0041] Examples of epoxy group-containing compounds (A3) include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidylamine type epoxy resins such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmetaxylylenediamine, and tetraglycidylbisaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; phloroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydr Examples include trifunctional epoxy resins such as roxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; and tetrafunctional epoxy resins such as pentaerythritol tetraglycidyl ether, tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidylbenzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxy biphenyl.

[0042] When the negative-type photopolymerizable composition contains an epoxy group-containing compound (A3), the content of the epoxy group-containing compound (A3) is preferably 1% to 60% by mass, more preferably 5% to 50% by mass, and particularly preferably 10% to 40% by mass, based on the total solid content of the negative-type photopolymerizable composition.

[0043] [Methylol-type compounds (A4)] A methylol-type compound (A4) is a compound having two or more groups selected from methylol groups, alkoxymethyl groups, and acyloxymethyl groups in its molecule. The methylol-type compound (A4) can react with phenolic hydroxyl groups of alkali-soluble resins (D), etc., as described later, to crosslink the alkali-soluble resins (D), etc.

[0044] The alkoxy group in the alkoxymethyl group and the acyl group in the acyloxymethyl group may be substituted with halogen atoms. The methylol-type compound (A4) is preferably a compound having two or more groups selected from a methylol group and an alkoxymethyl group.

[0045] In the methylol-type compound (A4), the number of groups selected from methylol groups and alkoxymethyl groups in one molecule is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 4.

[0046] The number of carbon atoms in the alkoxymethyl group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. In other words, the methoxymethyl group is the most preferred alkoxymethyl group. The alkoxy group in the alkoxymethyl group may be linear or branched, but it is preferable that it be linear.

[0047] The acyloxy group in the acyloxymethyl group is not particularly limited as long as it is a group represented by R-CO-O-. R is an organic group. R is bonded to the carbonyl group by a CC bond. The organic group for R is preferably an alkyl group or an aryl group, with alkyl groups being more preferred. The number of carbon source atoms of the organic group for R is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6.

[0048] Suitable examples of methylol-type compounds (A4) include methylolmelamine compounds, methylolguanamine compounds, methylolurea compounds, resol resins, and aromatic compounds having a methylol group or alkoxymethyl group on the aromatic ring. Among these, methylolmelamine compounds, methylolguanamine compounds, methylolurea compounds, and aromatic compounds having a methylol group or alkoxymethyl group on the aromatic ring are preferred.

[0049] Aromatic compounds having a methylol group or an alkoxymethyl group on the aromatic ring include the compounds described in paragraphs

[0136] to

[0139] of Japanese Patent Publication No. 2013-064829, and the compounds described in paragraphs

[0029] to

[0036] of Japanese Patent Publication No. 10-0120940.

[0050] As the methylol-type compound (A4), compounds having a methylol group bonded to a nitrogen atom, or an alkoxymethyl group bonded to a nitrogen atom, are particularly preferred. As methylol-type compounds (A4) having a methylol group bonded to a nitrogen atom or an alkoxymethyl group bonded to a nitrogen atom, methylolmelamine compounds, methylolguanamine compounds, and methylolurea compounds are preferred, methylolmelamine compounds and methylolurea compounds are more preferred, and methylolmelamine compounds are even more preferred.

[0051] As the methylolmelamine compound, the compound represented by the following formula (a4) is preferred. [ka]

[0052] In formula (a4), R a11 ~R a16 Each of these is independently a hydrogen atom, or -CH2-OR a It is a group represented by R. a is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. However, R a11 ~Ra16 At least two of them are -CH2-OR a It is a base represented by .

[0053] R a The alkyl group may be linear or branched, but linear is preferred. a The number of carbon atoms in the alkyl group is 1 to 6, preferably 1 to 4, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1.

[0054] In formula (a4), R a11 ~R a16 -CH2-OR a The number of groups represented is preferably 4 to 6, more preferably 5 or 6, and even more preferably 6.

[0055] As the methylolguanamine compound, the compound represented by the following formula (a5) is preferred. [ka]

[0056] In equation (a5), R a21 R is a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. a22 ~R a25 Each of these is independently a hydrogen atom, or -CH2-OR a It is a group represented by R. a22 ~R a25 At least two of them are -CH2-OR a It is a base represented by .

[0057] R a21 The alkyl group may be linear or branched, but linear is preferred. a21 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. R a21The number of carbon atoms in the cycloalkyl group is preferably 3 to 10, more preferably 3 to 8, even more preferably 4 to 7, and particularly preferably 5 or 6. R a21 The number of carbon atoms in the aryl group is preferably 6 to 14, and more preferably 6 to 10. A phenyl group is preferred as the aryl group. R a21 Preferably, the atoms are hydrogen atoms, methyl groups, and phenyl groups; more preferably, hydrogen atoms and phenyl groups; and even more preferably, phenyl groups.

[0058] In formula (a5), R a22 ~R a25 -CH2-OR a The number of groups represented is preferably 2 or more and 4 or less, more preferably 3 or 4, and even more preferably 4.

[0059] As the methylolurea compound, the compound represented by the following formula (a6) is preferred. [ka]

[0060] In equation (a6), R a31 , and R a33 Each of these is independently a hydrogen atom, an alkyl group, or a cycloalkyl group. a32 , and R a34 is -CH2-OR a It is a group represented by R. a31 , and R a33 These may be joined to each other to form a ring. a31 , and R a33 The ring formed by the bonding of these rings may have other rings fused to it. It is represented by formula (a6), R a31 , and R a33 Compounds containing rings formed by the bonding of these elements may also undergo condensation.

[0061] R a31 , also R a33The alkyl group may be linear or branched, but linear is preferred. a31 , also R a33 The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. R a31 , also R a33 The number of carbon atoms in the cycloalkyl group is preferably 3 to 10, more preferably 3 to 8, even more preferably 4 to 7, and particularly preferably 5 or 6.

[0062] In equation (a6), R a31 , and R a33 It is preferable that both are hydrogen atoms or that they are bonded to each other to form a ring. a31 , and R a33 When a ring is formed, the compound represented by formula (a6) is preferably the compound represented by the following formula (a7) or formula (a8). The compound represented by the following formula (a8) is also called a methylol glycoluryl compound. [ka]

[0063] In formula (a7), R a41 , and R a42 is -CH2-OR a It is a group represented by R. a43 , and R a44 L is a hydrogen atom or a monovalent organic group. L is a single bond or a divalent linking group.

[0064] In equation (a7), R a41 , and R a42 Preferably, all of these are methoxymethyl groups.

[0065] In equation (a7), R a43 , and R a44The group is preferably a monovalent organic group. The monovalent organic group is not particularly limited. Preferably, the monovalent organic group is an alkyl group or an alkoxy group, and more preferably an alkoxy group. The number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1.

[0066] In formula (a7), L is preferably a single bond. A divalent linking group for L is preferably an alkylene group. The alkylene group may be interrupted by an oxygen atom, a carbonyl group, or a carboxylic acid ester bond.

[0067] In formula (a8), R a51 ~R a54 is a hydrogen atom, or -CH2-OR a It is a group represented by R. a51 ~R a54 At least two of them are -CH2-OR a It is a group represented by R. a51 ~R a54 -CH2-OR a The number of groups represented is preferably 3 or 4, and more preferably 4.

[0068] The following compounds are suitable examples of the methylol-type compounds (A4) described above. [ka]

[0069] [ka]

[0070] [ka]

[0071] Commercially available methylol-type compounds (A4) can also be used. Specific examples of commercially available products include Nikalac MX-270, Nikalac MW-100LM, Nikalac MX-280, and Nikalac MX-290 (all manufactured by Sanwa Chemical Co., Ltd.).

[0072] The methylol-type compound (A4) may be used alone or in combination of two or more types.

[0073] When the negative-type photopolymerizable composition contains a methylol-type compound (A4), the content of the methylol-type compound (A4) is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and particularly preferably 10% by mass or more and 40% by mass or less, based on the total solid content of the negative-type photopolymerizable composition.

[0074] <<Photosensitive agent (B)>> Examples of photosensitive agents (B) include photoradical polymerization initiators (B1) and photoacid generators (B2).

[0075] <Photoradical polymerization initiator (B1)> The photoradical polymerization initiator (B1) is not particularly limited as long as it is a compound that generates active radicals etc. upon the action of light and can initiate polymerization of the photopolymerizable compound (A), and any known photoradical polymerization initiator can be used. The photoradical polymerization initiator (B1) is preferably a polymerization initiator that includes at least one selected from the group consisting of oxime ester compounds (B1-1) such as O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds, and a polymerization initiator that includes an oxime ester compound (B1-1) of an O-acyloxime compound is more preferred. These polymerization initiators tend to be highly sensitive.

[0076] O-acyloxime compounds are compounds having the structure represented by formula (b1). Below, * represents a combination. [ka]

[0077] Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy Examples include -1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine. Commercially available products such as Irgacure® OXE01, OXE02 (both manufactured by BASF Ltd.) and N-1919 (manufactured by ADEKA Corporation) may also be used.

[0078] Alkylphenone compounds are compounds having the structure represented by formula (b2-1) or formula (b2-2). In these structures, the benzene ring may have substituents. [ka]

[0079] Examples of compounds having the structure represented by formula (b2-1) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure® 369, 907, and 379 (all manufactured by BASF Ltd.) may also be used. Alternatively, polymerization initiators having a group capable of inducing chain transfer, as described in Japanese Patent Publication No. 2002-544205, may also be used. Examples of compounds having the structure represented by formula (b2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. In terms of sensitivity, alkylphenone compounds having the structure represented by formula (b2-1) are preferred.

[0080] Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[ Examples include 2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0081] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Ltd.) may also be used.

[0082] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Publication No. 6-75372, Japanese Patent Publication No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenate). Examples include (nyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), and biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Publication No. 7-10913, etc.).

[0083] Furthermore, examples of photoradical polymerization initiators (B1) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; and 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

[0084] When the negative-type photopolymerizable composition contains a photoradical polymerization initiator (B1), the content of the photoradical polymerization initiator (B1) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, and even more preferably 1 part by mass or more and 8 parts by mass or less, per 100 parts by mass of the photopolymerizable compound (A).

[0085] <Photoacid Generator (B2)> The photoacid generator (B2) is a compound that generates acid upon irradiation with KrF rays (wavelength 248 nm). When a negative-type photopolymerizable composition contains an epoxy group-containing compound (A3) or a methylol-type compound (A4), the reaction of the epoxy group-containing compound (A3) or the methylol-type compound (A4) proceeds due to the action of the acid generated by the photoacid generator (B2) upon exposure to KrF rays. Furthermore, if the negative-type photopolymerizable composition contains a resin having acid-dissociable groups, exposure to KrF light causes the acid-dissociable groups of the resin to detach due to the action of the acid generated by the photoacid generator (B2), changing the solubility of the resin in the developer, thereby allowing the negative-type photopolymerizable composition to be suitably applied to patterning by photolithography.

[0086] Examples of photoacid generators (B2) include onium salt type photoacid generators such as iodonium salts and sulfonium salts, and diazomethane type photoacid generators. Among these, onium salt type photoacid generators or diazomethane type photoacid generators are preferred, and onium salt type photoacid generators are more preferred, as they make it easier to obtain highly sensitive negative-type photopolymerizable compositions. The onium salt type acid generator is also referred to as onium salt (B2-1).

[0087] [Onium salt (B2-1)] Onium salt (B2-1) (onium salt type acid generator) is composed of an anionic part and a cationic part. The anionic portion that constitutes the onium salt (B2-1) is as follows. The cationic portion that constitutes the onium salt type photoacid generator (B2) is as follows.

[0088] (Anime Club) Suitable anions for the anionic portion of the onium salt (B2-1) are those capable of forming a sulfonium salt.

[0089] Examples of anionic components include fluoroalkyl sulfonic acid and aryl sulfonic acid ions, in which some or all of the hydrogen atoms are fluorinated.

[0090] 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 groups are particularly preferred due to their shorter diffusion distance. Furthermore, methyl, ethyl, propyl, butyl, and octyl groups are preferred because they can be synthesized inexpensively.

[0091] Examples of aryl groups in arylsulfonic acid ions include aryl groups having 6 to 20 carbon atoms, which may be substituted. Examples of aryl groups having 6 to 20 carbon atoms, which may be substituted, include alkyl groups, phenyl groups, and naphthyl groups, which may or may not be substituted with halogen atoms. In particular, aryl groups having 6 to 10 carbon atoms, which may be substituted, are preferred because they can be synthesized inexpensively. Preferred specific examples of aryl groups in arylsulfonic acid ions include phenyl groups, methylphenyl groups, ethylphenyl groups, triisopropylphenyl groups, naphthyl groups, and methylnaphthyl groups.

[0092] In the above-mentioned fluoroalkyl sulfonic acid ions, the fluorination rate when some or all of the hydrogen atoms are fluorinated 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, and perfluorooctanesulfonate.

[0093] Among these, a preferred anion part is the one represented by the following formula (b11).

[0094] [ka]

[0095] In the above equation (b11), R b13 This is a group represented by the following formulas (b12), (b13), or (b14).

[0096] [ka]

[0097] In equation (b12) above, x represents an integer between 1 and 4. Also, in equation (b13) above, R b14represents 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 of 1 to 3.

[0098] (Cation part) The cation part constituting the onium salt (B2-1) is not particularly limited, and an organic cation known as the cation part constituting a conventionally known onium salt type acid generator can be appropriately used. As such a cation part, a sulfonium cation is preferable. Specific examples include, for example, sulfonium cations represented by the following formula (bc-1) or (bc-2). [Chemical formula] (In formula (bc-1) and (bc-2), R bc1 ~R bc5 each independently represents an aryl group, an alkyl group, a cycloalkyl group, or an alkenyl group which may have a substituent. R bc1 ~R bc5 may be bonded to each other to form a ring together with the sulfur atom in the formula. R bc6 ~R bc7 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R bc8 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a SO2-containing cyclic group which may have a substituent. L bc1 represents -C(=O)- or -C(=O)-O-.)

[0099] In formula (bc-1) and (bc-2), R bc1 ~R bc5 Examples of the aryl group as R<000069​​​​​​​bc1 ~R bc5 The number of carbon atoms in the cycloalkyl group is preferably 3 to 30. R bc1 ~R bc5 The number of carbon atoms in the alkenyl group is preferably 2 to 10. R bc1 ~R bc5 , and R bc8 Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, aryl groups, and groups represented by the following formulas (bc-r-1) to (bc-r-7).

[0100] [ka] (In formulas (bc-r-1) to (bc-r-7), R' b11 These are, independently, a hydrogen atom, an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group.

[0101] R' b11 As the cyclic group, a cyclic hydrocarbon group is preferred. The cyclic hydrocarbon group may be an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a group containing an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. The alicyclic hydrocarbon group may be saturated or unsaturated. The alicyclic hydrocarbon group is preferably a saturated alicyclic hydrocarbon group.

[0102] R' b11 The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents.

[0103] R' b11Specific examples of aromatic hydrocarbon rings included in an aromatic hydrocarbon group include benzene rings, fluorene rings, naphthalene rings, anthracene rings, phenanthrene rings, and biphenyl rings.

[0104] R' b11 The cyclic group may include an aromatic heterocycle in which some of the carbon atoms constituting the aromatic hydrocarbon ring described above are replaced by heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, nitrogen atoms, and the like.

[0105] R' b11 Specific examples of aromatic hydrocarbon groups include the phenyl group, naphthalene-1-yl group, naphthalene-2-yl group, 4-phenylphenyl group, 3-phenylphenyl group, and 2-phenylphenyl group.

[0106] R' b11 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 12. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is a cycloalkyl group. The number of carbon atoms in the cycloalkyl group is preferably 3 to 6. Suitable examples of cycloalkyl groups include cyclopentyl groups and cyclohexyl groups. As for the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferred. The number of carbon atoms in the polycycloalkane is preferably 7 to 30. Suitable examples of polycycloalkanes include polycycloalkanes having a crosslinked ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton.

[0107] Among them, R' b11 As the alicyclic hydrocarbon group, adamantyl and norbornyl groups are preferred, with adamantyl group being more preferred.

[0108] R' b11 The cyclic hydrocarbon group may be a heterocyclic ring containing a heteroatom. Specifically, this includes lactone-containing cyclic groups, -SO2--containing cyclic groups, and other heterocyclic groups.

[0109] R' in equations (bc-r-1)~(bc-r-7) b11 Examples of substituents in a cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. As the alkyl group substituent, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl, ethyl, propyl, n-butyl, and tert-butyl groups are more preferred. As the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are even more preferred. As the halogen atom used as a substituent, a fluorine atom is preferred. Examples of alkyl halides used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with halogen atoms. A carbonyl group as a substituent is a group that substitutes for a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0110] R' b11 The alkyl group can be either linear or branched. The number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The number of carbon atoms in the branched alkyl group is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 10. Specific examples of branched alkyl groups include isopropyl group, sec-butyl group, isobutyl group, sec-pentyl group, 2-methylbutyl group, isopentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0111] R' b11 The alkenyl group can be either linear or branched. The number of carbon atoms in the linear alkenyl group is preferably 2 to 10, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Specific examples of linear alkenyl groups include vinyl groups, 1-propenyl groups, 2-propenyl groups (allyl groups), and butenyl groups. Specific examples of branched alkenyl groups include 1-methylvinyl group, 1-methylpropenyl group, and 2-methylpropenyl group. As for the alkenyl group, a linear alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

[0112] R' b11 Examples of substituents that the alkyl and alkenyl groups may have include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above R' b11 Examples include cyclic groups.

[0113] Among them, R' b11 Preferably, the group is a cyclic group which may have substituents, and more preferably, a cyclic hydrocarbon group which may have substituents. More specifically, for example, phenyl groups, naphthyl groups, groups obtained by removing one or more hydrogen atoms from polycycloalkanes, lactone-containing cyclic groups, -SO2--containing cyclic groups, etc. are preferred.

[0114] R in equation (bc-1) or (bc-2) bc1 ~R bc3When two of the elements bond to each other to form a ring with the sulfur atom in the formula, they may be bonded via heteroatoms such as sulfur atoms, oxygen atoms, nitrogen atoms, or functional groups such as carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(RN)- (where RN is an alkyl group having 1 to 5 carbon atoms). The formed ring is preferably a 3 to 10-membered ring, and particularly preferably a 5 to 7-membered ring, including the sulfur atom. Specific examples of the ring include thiophene rings, thiazole rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthene rings, thioxanthone rings, thianthlene rings, phenoxatiyne rings, tetrahydrothiophenium rings, and tetrahydrothiopyranium rings.

[0115] R bc6 ~R bc7 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. bc6 ~R bc7 Preferably, this is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. bc6 , and R bc7 If both are alkyl groups, bc6 , and R bc7 These may be bonded together to form a ring.

[0116] R bc8 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted SO2-containing cyclic group. R bc8 If the aryl group is an aryl group, it is preferably an unsubstituted aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group, a naphthalene-1-yl group, and a naphthalene-2-yl group. R bc8 If the alkyl group is an alkyl group, it may be a linear or cyclic alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 30. R bc8If the group is an alkenyl group, the number of carbon atoms in the alkenyl group is preferably 2 or more and 10 or less. R bc8 SO2-containing cyclic groups that may have substituents are preferably "-SO2-containing polycyclic groups".

[0117] The following are suitable cations represented by formula (bc-1).

[0118] [ka]

[0119] [ka]

[0120] [ka] (In equations (bc-1-35) to (bc-1-37), g1, g2, and g3 represent the number of repetitions of the base in parentheses, where g1 is an integer between 1 and 5, g2 is an integer between 0 and 20, and g3 is an integer between 0 and 20.)

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka] (In the formula, R” b11 is a hydrogen atom or a substituent, and the substituent is R bc1 ~Rbc5 , and R bc8 (Similar to substituents that may be present.)

[0125] [ka]

[0126] Suitable specific examples of cations represented by formula (bc-2) include the cations represented by the following formulas (bc-2-1) to (bc-2-6).

[0127] [ka]

[0128] The cation portion of the onium salt (B2-1) is preferably a cation represented by formulas (bc-1-1) to (bc-1-6) or (bc-1-52) to (bc-1-60).

[0129] [Diazomethane-type photoacid generator] Examples of diazomethane-type photoacid generators include bissulfonyl diazomethane compounds such as bis(alkylsulfonyl)diazomethane, bis(cycloalkylsulfonyl)diazomethane, and bis(arylsulfonyl)diazomethane.

[0130] Specific examples of bissulfonyl diazomethane compounds include bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane.

[0131] Poly(bissulfonyl)diazomethane can also be used as a diazomethane-type photoacid generator. Examples of poly(bissulfonyl)diazomethane include 1,3-bis(phenylsulfonyldiazomethylsulfonyl)propane, 1,4-bis(phenylsulfonyldiazomethylsulfonyl)butane, 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane, 1,10-bis(phenylsulfonyldiazomethylsulfonyl)decane, 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane, 1,3-bis(cyclohexylsulfonyldiazomethylsulfonyl)propane, 1,6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane, and 1,10-bis(cyclohexylsulfonyldiazomethylsulfonyl)decane.

[0132] The photoacid generator (B2) may be used alone or in combination of two or more types.

[0133] When the negative-type photopolymerizable composition contains a photoacid generator (B2), the content of the photoacid generator (B2) is preferably 0.001% to 20% by mass, more preferably 0.01% to 15% by mass, and particularly preferably 0.1% to 10% by mass, based on the total solid content of the negative-type photopolymerizable composition. Furthermore, it is preferable that the negative-type photopolymerizable composition does not contain a thermal acid generator. A thermal acid generator is a compound that generates acid when heated.

[0134] <Metal oxide fine particles (C)> The negative-type photopolymerizable composition may contain metal oxide fine particles (C). The negative-type photopolymerizable composition contains metal oxide fine particles (C), which facilitates the formation of microlens-shaped patterns with high refractive indices. The type of metal oxide constituting the metal oxide nanoparticles (C) is not particularly limited as long as the desired effect is not impaired. Preferred examples of metal oxide nanoparticles (C) include at least one selected from the group consisting of zirconium oxide nanoparticles, titanium oxide nanoparticles, barium titanate nanoparticles, cerium oxide nanoparticles, and niobium pentoxide nanoparticles. From the viewpoint of sensitivity, it is particularly preferable that the metal oxide nanoparticles (C) are titanium oxide nanoparticles. Metal oxide nanoparticles (C) may be used individually or in combination of two or more types.

[0135] Examples of metal oxide nanoparticles (C) include metal salts such as calcium carbonate and barium sulfate, metal hydroxides such as aluminum hydroxide, silicon dioxide (silica), titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), glass, magnesium oxide, zinc oxide, and other metal oxides. The metal oxide nanoparticles (C) may be surface-treated. One type of metal oxide nanoparticle (C) may be used, or two or more types of metal oxide nanoparticles (C) may be used. The shape of the metal oxide nanoparticles (C) is not limited, but spherical metal oxide nanoparticles (C) are preferred from the viewpoint of being able to easily control the light extraction efficiency and light collection efficiency.

[0136] The average particle size of the metal oxide fine particles (C) is preferably 20 nm to 1600 nm. For example, in the case of zirconium oxide, it is preferably 20 nm to 50 nm. For example, in the case of titanium oxide, it is preferably 20 nm to 200 nm, and more preferably 120 nm to 200 nm. For example, in the case of silicon dioxide (silica), it is preferably 80 nm to 1600 nm. If the average particle size of the metal oxide fine particles (C) is large, it may settle in the negative-type photopolymerizable composition, so it is preferable that it be within the above range. By setting the average particle size of the metal oxide fine particles (C) within the above range, the developability when forming a film using the negative-type photopolymerizable composition can be further improved, and the resolution can also be further improved. If the average particle size of the metal oxide fine particles (C) is less than 5 μm, it can be measured by dynamic light scattering, and if it is 5 μm or more, it can be measured by laser diffraction. In this specification, the average particle size of the metal oxide fine particles (C) represents the primary particle size.

[0137] When a negative-type photopolymerizable composition contains metal oxide fine particles (C), the content of metal oxide fine particles (C) in the negative-type photopolymerizable composition is preferably 10% to 90% by mass, more preferably 30% to 90% by mass, even more preferably 35% to 85% by mass, even more preferably 35% to 80% by mass, and even more preferably 45% to 75% by mass, based on the total solid content of the negative-type photopolymerizable composition. By setting the content of metal oxide fine particles (C) within the above range, it becomes easier to obtain the effects of improving refractive index, developing properties, and resolution by adding metal oxide fine particles (C).

[0138] <<Alkali-soluble resin (D)>> The negative-type photopolymerizable composition may contain an alkali-soluble resin (D). The alkali-soluble resin (D) is a resin that does not fall under the category of photopolymerizable compound (A).

[0139] As the alkali-soluble resin (D), polyhydroxystyrene resin (D1) is preferred. Polyhydroxystyrene resin (D1) is a resin having constituent units derived from hydroxystyrene.

[0140] The polyhydroxystyrene resin (D1) preferably has a constituent unit represented by the following formula (d1).

[0141] [ka] (In formula (d1), R d1 R is a hydrogen atom, an alkyl group, a halogen atom, or an alkyl halide. d2 (where p is a hydrogen atom or an alkyl group; p is an integer between 1 and 5; q is an integer between 0 and 4.)

[0142] In formula (d1), R d1 This is a hydrogen atom, an alkyl group, a halogen atom, or an alkyl halide. R d1 The number of carbon atoms in the alkyl group is not particularly limited, as long as the desired effect is not impaired. d1 The number of carbon atoms in the alkyl group is preferably 1 or more and 5 or less. d1 The alkyl group may be linear or branched. d1 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.

[0143] R d1Specific examples of the halogen atom as such or the halogen atom in the halogenated alkyl include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among these, a fluorine atom is preferable. As the halogenated alkyl group, a group in which some or all of the hydrogen atoms in the above-mentioned alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms is preferable. The halogenated alkyl group may be linear or branched. Preferable specific examples of the halogenated alkyl group include fluorinated alkyl groups such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group.

[0144] R d1 As such, a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable.

[0145] q is an integer of 0 or more and 4 or less. Among these, q is preferably 0 or 1, and particularly preferably 0 from an industrial perspective.

[0146] In formula (d1), when q is 1, R d2 The substitution position of may be any of the o-position, m-position, and p-position with respect to the carbon atom bonded to the carbon atom to which R d1 is bonded on the benzene ring in formula (d1). When q is an integer of 2 or more and 4 or less, R d2 can be bonded to any position on the benzene ring in formula (d1).

[0147] In formula (d1), p is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1. When p is 1, the substitution position of the hydroxyl group in formula (d1) may be any of the o-position, m-position, and p-position with respect to the carbon atom bonded to the carbon atom to which R d1 is bonded on the benzene ring in formula (d1), and the p-position is preferable because the monomer giving the structural unit represented by formula (d1) is easily available and inexpensive. In formula (d1), if p is an integer between 2 and 5, the hydroxyl group can be bonded to any position on the benzene ring in formula (d1).

[0148] The polyhydroxystyrene resin (D1) may have one or more constituent units represented by formula (d1).

[0149] The polyhydroxystyrene resin (D1) may have constituent units represented by the following formula (d2). [ka] (In formula (d2), R d3 R is a hydrogen atom, an alkyl group, a halogen atom, or an alkyl halide. d4 , R d5 , and R d6 Each of these is independently either a hydrogen atom or an alkyl group. d7 (where is an alkyl group or cycloalkyl group; r is an integer between 1 and 5; s and t are each independently integers between 0 and 4.)

[0150] In formula (d2), d3 This is a hydrogen atom, an alkyl group, a halogen atom, or an alkyl halide. R d3 The number of carbon atoms in the alkyl group is not particularly limited, as long as the desired effect is not impaired. d3 The number of carbon atoms in the alkyl group is preferably 1 or more and 5 or less. d3 The alkyl group may be linear or branched. d3 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.

[0151] R d3Specific 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.

[0152] R d3 Preferably, the atoms are hydrogen atoms and methyl groups, with hydrogen atoms being more preferred.

[0153] R d4 The number of carbon atoms in the alkyl group is preferably 1 or more and 5 or less. d4 A preferred example of an alkyl group as is R d3 Similar to preferred examples of alkyl groups.

[0154] s and t are each independent integers between 0 and 4, inclusive. Of these, s and t are preferably 0 or 1, and are particularly preferably 0 from an industrial standpoint.

[0155] In equation (d2), if t is 1, R d4 The substitution site is on the benzene ring in formula (d2), R d3 The carbon atom bonded to the carbon atom can be in any of the orthogonal, metagonal, or paragonal positions. If t is an integer between 2 and 4, then R d4 It can be bonded at any position on the benzene ring in formula (d2).

[0156] In equation (d2), s is an integer between 0 and 4, preferably between 0 and 3, and more preferably 0 or 1. When s is 1, the substitution position of the hydroxyl group in formula (d2) is R on the benzene ring in formula (d2). d3 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 the monomer that gives the constituent unit represented by formula (d2) is readily available and inexpensive. In formula (d2), if s is an integer between 2 and 4, the hydroxyl group can be bonded to any position on the benzene ring in formula (d2).

[0157] In equation (d2), r is an integer between 1 and 5, preferably between 1 and 3, and more preferably 1. When r is 1, -OC(R) in equation (d2) d5 )(R d6 )OR d7 The substitution position of the group represented by is on the benzene ring in formula (d2), R d3 The carbon atom bonded to the carbon atom can be in any of the orthogonal, metagonal, or paragonal positions. In equation (d2), if r is an integer between 2 and 5 (inclusive), then -OC(R d5 )(R d6 )OR d7 The group represented by can be bonded to any position on the benzene ring in formula (d2).

[0158] -C(R) in equation (d2) d5 )(R d6 )OR d7 In the acetal protecting group represented by R d5 , and R d6 Each of these is independently either a hydrogen atom or an alkyl group. d7 R is an alkyl group or a cycloalkyl group. d5 , R d6 , and R d7 At least two of these may be joined together to form a ring.

[0159] R d5 , or R d6 The number of carbon atoms in the alkyl group is preferably 1 or more and 6 or less. d5, or R d6 The alkyl group as R may be straight-chain or branched-chain. R d7 The number of carbon atoms of the alkyl group as R is preferably 1 or more and 10 or less. R d7 The alkyl group as R may be straight-chain or branched-chain. R d7 The number of carbon atoms of the cycloalkyl group as R is preferably, for example, 3 or more and 10 or less.

[0160] R d5 , R d6 , or R d7 Specific examples of the alkyl group as R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group, etc. R d7 Specific examples of the cycloalkyl group as R include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, and a cyclooctyl group, etc.

[0161] In formula (d2), -C(R d5 )(R d6 )OR d7 Specific examples of the acetal-type protecting group represented by include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, a 1-isopropoxyethyl group, a 1-n-butoxyethyl group, a 1-isobutoxyethyl group, a 1-tert-butoxyethyl group, a 1-cyclohexyloxyethyl group, a 1-methoxypropyl group, a 1-ethoxypropyl group, a 1-methoxy-1-methyl-ethyl group, and a 1-ethoxy-1-methylethyl group, etc.

[0162] The polyhydroxystyrene resin (D1) may contain other constitutional units (d3) other than the constitutional unit represented by the above formula (d1) and the constitutional unit represented by formula (d2). Other monomers that provide other constituent units (d3) 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.

[0163] 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, 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 group and cyclohexyl group. Examples of polycyclic alicyclic groups include norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, and tetracyclododecyl group.

[0164] 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.

[0165] 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.

[0166] 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; and 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.

[0167] 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.

[0168] 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, ethoxystyrene, propoxystyrene, isopropoxystyrene, and dimethoxystyrene; and halostyrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene.

[0169] 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.

[0170] When the polyhydroxystyrene resin (D1) has a structural unit represented by formula (d1), the content of the structural unit represented by formula (d1) in the polyhydroxystyrene resin (D1) is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 80 mol% or less, and even more preferably 15 mol% or more and 80 mol% or less.

[0171] When the polyhydroxystyrene resin (D1) has a structural unit represented by formula (d2), the content of the structural unit represented by formula (d2) in the polyhydroxystyrene resin (D1) is preferably 10 mol% or more and 95 mol% or less, more preferably 15 mol% or more and 90 mol% or less, and even more preferably 20 mol% or more and 85 mol% or less.

[0172] When the polyhydroxystyrene resin (D1) has structural units derived from (meth)acrylic acid ester, the content of structural units derived from (meth)acrylic acid ester in the polyhydroxystyrene resin (D1) is preferably 1 mol% or more, more preferably 1 mol% to 50 mol%, and even more preferably 10 mol% to 40 mol%.

[0173] When the polyhydroxystyrene resin (D1) has structural units derived from styrenes, the content of structural units derived from styrenes in the polyhydroxystyrene resin (D1) is preferably 1 mol% or more, more preferably 1 mol% to 50 mol%, and even more preferably 10 mol% to 40 mol%.

[0174] The weight-average molecular weight (Mw) of the alkali-soluble resin (D) is preferably between 2500 and 30000. Furthermore, it is preferable that the alkali-soluble resin (D) does not have blocked isocyanate groups. A blocked isocyanate group refers to an isocyanate group that has been blocked by a thermally dissociable protecting group.

[0175] When the negative-type photopolymerizable composition contains an alkali-soluble resin (D), the content of the alkali-soluble resin (D) is preferably 40% to 95% by mass, more preferably 50% to 85% by mass, and particularly preferably 60% to 80% by mass, based on the total solid content of the negative-type photopolymerizable composition.

[0176] <Organic solvent (S)> The negative-type photopolymerizable composition may contain an organic solvent (S). The inclusion of an organic solvent (S) in the negative-type photopolymerizable composition facilitates adjustment of the coating properties of the composition and the film thickness of the photosensitive layer formed using the negative-type photopolymerizable composition. The organic solvent (S) can be used alone or in combination of two or more types.

[0177] 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 polyhydric alcohols such as their monomethyl ethers (e.g., propylene glycol monomethyl ether acetate), monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether. Examples include: derivatives thereof; cyclic ethers such as dioxane; esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; and so on.

[0178] The content of the organic solvent (S) in the negative-type photopolymerizable composition is not particularly limited. Preferably, the content of the organic solvent (S) in the negative-type photopolymerizable composition is such that the solid content concentration of the negative-type photopolymerizable composition is 1% by mass or more and 30% by mass, and more preferably 5% by mass or more and 20% by mass.

[0179] <Other ingredients> The negative-type photopolymerizable 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 photosensitive compositions. Specific examples of other components include quenchers, polyvinyl resins, surfactants, and acids or acid anhydrides.

[0180] Negative-type photopolymerizable compositions may contain a quencher (acid diffusion inhibitor). Typically, low-molecular-weight compounds (non-polymers) are used as quenchers. Examples of quenchers include amines such as aliphatic amines and aromatic amines. Aliphatic amines are preferred as quenchers, and secondary and tertiary aliphatic amines are particularly preferred. Here, an aliphatic amine is an amine having one or more aliphatic groups. The number of carbon atoms in the aliphatic group of the aliphatic amine is preferably 1 to 20.

[0181] Examples of aliphatic amines include alkylamines in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl group having 20 or fewer carbon atoms, alkanolamines in which at least one hydrogen atom of ammonia (NH3) is substituted with a hydroxyalkyl group, and cyclic amines.

[0182] Specific examples of alkylamines and alkanolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, stearyldiethanolamine, and lauryldiethanolamine. Among these, trialkylamines and alkanolamines are preferred.

[0183] Examples of cyclic amines include nitrogen-containing heterocyclic compounds. These nitrogen-containing heterocyclic compounds may be monocyclic aliphatic amines or polycyclic aliphatic amines.

[0184] Examples of aliphatic monocyclic amines include piperidine and piperazine. The number of carbon atoms in the aliphatic polycyclic amine is preferably 6 to 10. Examples of aliphatic polycyclic amines include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0185] Other aliphatic amines include, specifically, tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, and tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine.

[0186] Examples of aromatic amines include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, trimenzylamine, 2,6-diisopropylaniline, 2,2'-dipyridyl, 4,4'-dipyridyl, and the like.

[0187] Sulfonium salts can also be used as quenchers. Examples of the cation portion constituting the sulfonium salt include the sulfonium cation represented by formula (bc-1) or (bc-2) of the photoacid generator (B2) mentioned above. The anion portion constituting the sulfonium salt is represented by the following formula (f1).

[0188] [ka] (In formula (f1), R 101 R is a cyclic group which may have substituents. 102 This is a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. 101 This is an alkylene group. 101 (This is a divalent linking group containing an oxygen atom.)

[0189] In formula (f1), R 101Examples of cyclic groups include heterocycles. These heterocycles include five-membered rings containing at least one nitrogen atom, preferably five to seven-membered rings. These heterocycles may also include fused rings. Examples of heterocycles include piperidine rings, morpholine rings, and thiomorpholine rings. Among these, morpholine rings are preferred.

[0190] R 102 Examples of fluorinated alkyl groups having 1 to 5 carbon atoms include perfluoroalkyl groups having 1 to 5 carbon atoms.

[0191] Y 101 As the alkylene group, a linear alkylene group is preferred. Preferred specific examples of linear alkylene groups include the methylene group, ethane-1,2-diyl group (ethylene group), propane-1,3-diyl group (trimethylene group), butane-1,4-diyl group (tetramethylene group), and pentane-1,5-diyl group (pentamethylene group), hexane-1,6-diyl group (hexamethylene group), heptane-1,7-diyl group (heptamethylene group), octane-1,8-diyl group (octamethylene group), nonane-1,9-diyl group (nonameethylene group), decane-1,10-diyl group (decamethylene group), and the like.

[0192] V 101 Examples of divalent linking groups containing an oxygen atom include -COO-, -OCO-, and -O-.

[0193] Other examples of quenchers include diaryliodonium carboxylates such as diphenyliodonium carboxylate. [ka]

[0194] Quenchers may be used alone or in combination of two or more types.

[0195] When the negative-type photopolymerizable composition contains a quencher, the quencher content is preferably 0.01% to 5% by mass, more preferably 0.01% to 4% by mass, and particularly preferably 0.01% to 3% by mass, relative to the total solid content of the negative-type photopolymerizable composition.

[0196] The negative-type photopolymerizable composition 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.

[0197] The negative-type photopolymerizable composition may contain an adhesion promoter to improve adhesion to the underlying layer (resin film or substrate) on which the photosensitive layer is formed using the negative-type photopolymerizable composition.

[0198] Negative-type photopolymerizable 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 fluorinated 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, and Polyfox PF-6520 (all manufactured by OMNOVA Solutions Co., Ltd.).

[0199] The negative-type photopolymerizable composition may contain an acid or acid anhydride to fine-tune its solubility in the developer.

[0200] 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.

[0201] The negative-type photopolymerizable composition preferably comprises a resin (A1) and a polyfunctional (meth)acrylate (A2) as the photopolymerizable compound (A), wherein the resin (A1) is an alkali-soluble resin (A1-1), the alkali-soluble resin (A1-1) contains epoxy group-containing units, the photosensitive agent (B) is a photoradical polymerization initiator (B1), and it is even more preferable that it contains metal oxide fine particles (C).

[0202] Furthermore, it is preferable that the negative-type photopolymerizable composition contains an epoxy group-containing compound (A3) and / or a methylol-type compound (A4) as the photopolymerizable compound (A), a photoacid generator (B2) as the photosensitizer (B), and an alkali-soluble resin (D) that does not correspond to the photopolymerizable compound (A), wherein the alkali-soluble resin (D) is a resin (D1) having constituent units derived from hydroxystyrene. When forming an etching mask pattern as a microlens-shaped pattern, the negative-type photopolymerizable composition may contain a photoradical polymerization initiator (B1) instead of the photoacid generator (B2), but from the viewpoint of sensitivity, it is preferable that the negative-type photopolymerizable composition contains a photoacid generator (B2).

[0203] The negative-type photopolymerizable composition preferably has a viscosity of 0.5 cP to 10 cP, as measured by a Canon-Fenske viscometer at 1 atmosphere and 20°C. This is because it is possible to form microlenses of a predetermined height.

[0204] The negative-type photopolymerizable composition preferably satisfies the following [Requirement 1]. [Requirement 1] The residual film percentage X1 (%), determined by the following steps 1-1) to 1-11), is between 95% and 110%. 1-1) In a silicon substrate having a 0.16 μm thick anti-reflective underlayer film and a 1 μm thick cured film of thermosetting acrylic resin on its surface, the negative-type photopolymerizable composition is applied onto the cured film of thermosetting acrylic resin, and then heated at 100°C for 60 seconds to obtain a coating film with a thickness of 600 nm. 1-2) The coated film is exposed to a KrF excimer laser through a mask for forming a dot pattern with a dot diameter of 0.40 μm and a dot spacing of 0.30 μm, at the optimal exposure dose that forms a dot pattern according to the mask dimensions, under the conditions of NA / s = 0.68 / 0.75. 1-3) Heat the exposed coated film at 100°C for 90 seconds. 1-4) After heating, develop by contacting with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at room temperature (23°C) for 60 seconds. 1-5) After development, the silicon substrate (M1) on which microlenses are formed is heated at 200°C for 5 minutes. 1-6) After applying KrF resist (TDUR-P3435, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to a silicon substrate on which microlenses have been formed using a spin coater, the mixture is heated at 100°C for 60 seconds to obtain a coated film with a thickness of 550 nm. 1-7) The coated film obtained in 1-6) above was exposed to a KrF excimer laser at an exposure dose of 50 mJ / cm². 2 Full-screen exposure is performed under the conditions NA / s = 0.68 / 0.75. 1-8) The coated film after exposure as described in 1-7) above is heated at 100°C for 90 seconds. 1-9) After heating as described in 1-8) above, develop by contacting with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds at room temperature (23°C). 1-10) After development as described in 1-9 above, the silicon substrate (M2) on which microlenses are formed is heated at 150°C for 5 minutes to obtain the silicon substrate (M2). 1-11) The residual film percentage X1 is calculated from the average height T1 of the microlens of M1 and the average height T2 of the microlens of M2 based on the following formula. Remaining film rate X1(%)=T2 / T1×100

[0205] When a negative-type photopolymerizable composition satisfies [Requirement 1], it can form microlens-shaped patterns (microlens patterns or etching mask patterns) with extremely excellent chemical resistance.

[0206] Furthermore, the negative-type photopolymerizable composition is preferably satisfied with the following [Requirement 2]. [Requirement 2] The residual film percentage X2 (%), determined by the following steps 2-1) to 2-4), is between 95% and 110%. 2-1) After applying the negative-type photopolymerizable composition onto a silicon substrate, it is heated at 90°C for 90 seconds to dry and form a resin layer with a thickness of 1 μm. 2-2) The formed resin layer is heated at 200°C for 5 minutes to cure it and obtain a cured layer. 2-3) Immerse the resulting hardened layer in acetone at room temperature (23°C) for 5 minutes. 2-4) The residual film percentage X2 is calculated based on the following formula, using the thickness U1 of the hardened layer before acetone immersion and the thickness U2 of the hardened layer after acetone immersion. Remaining film rate X2(%)=U2 / U1×100

[0207] When a negative-type photopolymerizable composition satisfies [Requirement 2], it can form a photosensitive layer (coating film) with extremely excellent chemical resistance.

[0208] <Method for producing a negative-type photopolymerizable composition> Negative-type photopolymerizable compositions can be prepared by mixing and stirring the above components in a conventional manner. If necessary, dispersion and mixing may be carried out using dispersers such as dissolvers, homogenizers, or three-roll mills. After mixing, the mixture may be further filtered using a mesh, membrane filter, or the like.

[0209] ≪Manufacturing Method for Optical Elements≫ The aforementioned negative-type photopolymerizable composition is used in a method for manufacturing an optical element comprising a plurality of microlenses, including n types of microlenses, on a substrate.

[0210] n types of microlenses differ from one another. The differences between n types of microlenses are not particularly limited. For example, n types of microlenses differ from one another in one or more of the following: optical properties such as refractive index and light transmittance; chemical properties such as solvent resistance and chemical resistance; mechanical properties such as hardness and elastic modulus; chemical composition of the material constituting the microlens; size; and shape. Typically, n types of microlenses differ from one another in size.

[0211] The following describes a method for manufacturing an optical element comprising multiple microlenses, including n types of microlenses, on a substrate.

[0212] In the above manufacturing method, n is an integer of 2 or more. n is preferably an integer between 2 and 4, more preferably 2 or 3, and particularly preferably 2. In other words, an optical element comprising two types of microlenses is preferably manufactured.

[0213] The above manufacturing method involves forming a resin film on a substrate, Forming an etching mask on a resin film with a shape corresponding to the shape of multiple microlenses, The process includes etching a resin film together with the etching mask to form multiple microlenses on which the shape of the etching mask has been transferred.

[0214] The resin film is formed on the substrate as a lens material layer. 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.

[0215] Next, an etching mask is formed on the resin film, with a shape corresponding to the shape of the multiple microlenses. The etching masks are as follows (i)~(iii): (i) Applying the m-th photosensitive composition onto the resin film to form the m-th photosensitive layer, (ii) The m-th photosensitive layer is formed by KrF exposure with KrF light, heating and development after the KrF exposure, thereby forming the m-th dot at a position corresponding to the position where the m-th microlens is formed on the substrate, (iii) By heating the m-th dot, the m-th dot is deformed into a shape corresponding to the shape of the m-th microlens, It is formed by repeating the operation n times. The above m is an integer between 1 and n, The first to nth photosensitive compositions used in forming the etching mask may be the same or different. At least one of the first to nth photosensitive compositions is the aforementioned negative-type photopolymerizable composition.

[0216] The following describes a method for forming a microlens-shaped etching mask on a resin film to create the first microlens. First, the first photosensitive composition is applied to the resin film to form the first photosensitive layer. As the first photosensitive composition, a photosensitive composition used to form a microlens-shaped etching mask in the aforementioned etch-back method can be used. The aforementioned negative-type photopolymerizable composition is preferred as the first photosensitive composition.

[0217] The method for applying the first photosensitive composition is not particularly limited. For example, the first photosensitive layer can be formed by applying the first photosensitive composition to a desired film thickness using a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or slit coater, or a non-contact type coating device such as a spinner (rotary coating device) or curtain flow coater.

[0218] The first photosensitive layer formed by coating the photosensitive composition may be subjected to appropriate heat treatment (pre-bake (post-application bake (PAB)) treatment) to remove the solvent in the first photosensitive layer. The conditions for the above heat treatment vary depending on the type and proportion of each component of the photosensitive composition, the thickness of the photosensitive layer, etc. 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 first photosensitive layer is preferably in the range of 100 nm to 4.0 μm, and more preferably in the range of 400 nm to 2.0 μm.

[0219] Next, the first photosensitive layer is subjected to KrF exposure by irradiating it with KrF rays, followed by heating and development after the KrF exposure to form the first dot at a position corresponding to the position where the first microlens is formed on the substrate.

[0220] KrF exposure is performed positionally so that the first dot is formed at a predetermined location. Positionally selective exposure can be performed, for example, via a desired mask pattern. Exposure is performed using a KrF excimer laser.

[0221] Next, the first photosensitive layer, exposed to the KrF line, is heated and then developed. This dissolves and removes any unwanted parts.

[0222] In the alkaline development process, development is carried out using an alkaline developer. In the solvent development process, development is carried out using a developer containing an organic solvent (organic developer).

[0223] As the alkaline 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 obtained by adding appropriate amounts of water-soluble organic solvents such as methanol and ethanol, or surfactants, to the above-mentioned aqueous solutions of alkalis can also be used as the developer. As the alkaline developer, an aqueous solution of tetramethylammonium hydroxide with a concentration of 0.1% to 10% by mass is preferred.

[0224] The organic solvent used as an organic developer can be appropriately selected from known organic solvents. Suitable examples of organic solvents include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0225] Ketone solvents are organic solvents having a structure represented by CC(=O)-C. Ester solvents are organic solvents having a carboxylic acid ester group. Alcohol solvents are organic solvents having an alcoholic hydroxyl group. Nitrile solvents are organic solvents having a nitrile group. Amide solvents are organic solvents containing a carboxylic acid amide group. The nitrogen atom in the carboxylic acid amide group may be substituted with an organic group, preferably a hydrocarbon group. Ether solvents are organic solvents containing an ether bond.

[0226] Some organic solvents contain multiple functional groups in their structure that characterize each of the above-mentioned solvents. In such cases, they are considered to fall under any of the solvent types that contain the functional groups that the organic solvent possesses. For example, diethylene glycol monomethyl ether is considered to fall under either the alcohol-based solvent or the ether-based solvent in the above classification. Hydrocarbon solvents consist of hydrocarbons that may be halogenated and do not have substituents other than halogen atoms. Fluorine atoms are preferred as the halogen atom. Among the above, polar solvents are preferred as organic solvents contained in organic developers, and ketone solvents, ester solvents, and nitrile solvents are preferred.

[0227] The development time varies depending on the composition of the first photosensitive composition, such as the negative-type photopolymerizable composition mentioned above, and the thickness of the first photosensitive layer, but is usually between 20 seconds and 5 minutes. Any of the development methods may be used, such as the liquid-filling method, dipping method, paddle method, or spray development method.

[0228] The developed first photosensitive layer is washed with running water or the like, if necessary, and then dried. In this way, a dot pattern consisting of the first dots is formed.

[0229] Next, the first dot is heated to deform it into a shape corresponding to the shape of the first microlens. In this way, an etching mask with a shape corresponding to the shape of the first microlens can be formed on the resin film. The heating conditions vary depending on the type and proportion of each component in the photosensitive composition, such as the negative-type photopolymerizable composition mentioned above, the thickness of the photosensitive layer, etc. For example, the heating temperature is preferably 100°C to 300°C, and more preferably 150°C to 250°C. The heating time is preferably, for example, 1 minute to 30 minutes, and more preferably 3 minutes to 10 minutes.

[0230] As described above, an etching mask with a shape corresponding to the shape of the first microlens is formed on the resin film.

[0231] Next, an etching mask shaped to match the shape of the second microlens is formed on a resin film having an etching mask shaped to match the shape of the first microlens on its surface, using a second photosensitive composition. The method for forming the mask shaped to match the shape of the second microlens is the same as the method for forming the mask shaped to match the shape of the first microlens. The second photosensitive layer is preferably the negative-type photopolymerizable composition described above.

[0232] By repeating this operation n times, n types of etching masks, corresponding to the shapes of n types of microlenses, are formed on the resin film. A resin film equipped with n types of etching masks is etched together with the etching masks so that the resin film is etched, thereby forming multiple microlenses on a substrate, each with the shape of the n types of etching masks transferred onto it.

[0233] The above describes a method for manufacturing an optical element comprising multiple microlenses, including n types of microlenses, on a substrate, in which an etching mask is manufactured using the aforementioned negative-type photopolymerizable composition. Next, in the method for manufacturing an optical element comprising a plurality of microlenses, including n types of microlenses, on a substrate, the case in which the microlenses are manufactured using the aforementioned negative-type photopolymerizable composition will be described below. Furthermore, in a method for manufacturing an optical element comprising a plurality of microlenses, including n types of microlenses, on a substrate, an etching mask may be manufactured using the aforementioned negative-type photopolymerizable composition, and the microlenses may also be manufactured using the aforementioned negative-type photopolymerizable composition.

[0234] When manufacturing microlenses using the aforementioned negative-type photopolymerizable composition, in the above manufacturing method, n is an integer of 2 or more. n is preferably an integer between 2 and 4, more preferably 2 or 3, and particularly preferably 2. In other words, an optical element comprising two types of microlenses is preferably manufactured.

[0235] In the above manufacturing method, when manufacturing microlenses using the aforementioned negative-type photopolymerizable composition, Multiple microlenses are as follows: (iv)~(vi): (iv) Applying the m-th photosensitive composition to the substrate to form the m-th photosensitive layer, (v) KrF exposure by irradiating the m-th photosensitive layer with a KrF line, heating and developing after the KrF exposure to form the m-th dot at a position corresponding to the position where the m-th microlens is formed on the substrate, (vi) By heating the m-th dot, the m-th dot is deformed into a shape corresponding to the shape of the m-th microlens, It is formed by repeating the operation having n times. The above m is an integer between 1 and n, The first to nth photosensitive compositions used in the formation of multiple microlenses may be the same or different. At least one of the first to nth photosensitive compositions is the aforementioned negative-type photopolymerizable composition.

[0236] The following describes a method for forming the first microlens on a substrate. First, the first photosensitive composition is applied to the substrate to form the first photosensitive layer. As the first photosensitive composition, a photosensitive composition used for forming microlenses in the thermal flow method described above can be used. The negative-type photopolymerizable composition described above is preferred as the first photosensitive composition.

[0237] The method for applying the first photosensitive composition is not particularly limited. For example, the first photosensitive layer can be formed by applying the first photosensitive composition to a desired film thickness using a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or slit coater, or a non-contact type coating device such as a spinner (rotary coating device) or curtain flow coater.

[0238] The first photosensitive layer formed by coating the photosensitive composition may be subjected to appropriate heat treatment (pre-bake (post-application bake (PAB)) treatment) to remove the solvent in the first photosensitive layer. The conditions for the above heat treatment vary depending on the type and proportion of each component of the photosensitive composition, the thickness of the photosensitive layer, etc. 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 first photosensitive layer is preferably in the range of 100 nm to 4.0 μm, and more preferably in the range of 400 nm to 2.0 μm.

[0239] Next, the first photosensitive layer is subjected to KrF exposure by irradiating it with KrF rays, followed by heating and development after the KrF exposure to form the first dot at a position corresponding to the position where the first microlens is formed on the substrate.

[0240] KrF exposure is performed positionally so that the first dot is formed at a predetermined location. Positionally selective exposure can be performed, for example, via a desired mask pattern. Exposure is performed using a KrF excimer laser.

[0241] Next, the first photosensitive layer, exposed to the KrF line, is heated and then developed. This dissolves and removes any unwanted parts.

[0242] In the alkaline development process, development is carried out using an alkaline developer. In the solvent development process, development is carried out using a developer containing an organic solvent (organic developer). The alkaline developers and organic developers are the same as those described above.

[0243] The development time varies depending on the composition of the first photosensitive composition, such as the negative-type photopolymerizable composition mentioned above, and the thickness of the first photosensitive layer, but is usually between 20 seconds and 5 minutes. Any of the development methods may be used, such as the liquid-filling method, dipping method, paddle method, or spray development method.

[0244] The developed first photosensitive layer is washed with running water or the like, if necessary, and then dried. In this way, a dot pattern consisting of the first dots is formed.

[0245] Next, the first dot is heated to deform it into the shape of the first microlens. In this way, the first microlens can be formed on the substrate. The heating conditions vary depending on the type and proportion of each component in the photosensitive composition, such as the negative-type photopolymerizable composition mentioned above, the thickness of the photosensitive layer, etc. For example, the heating temperature is preferably 100°C to 300°C, and more preferably 150°C to 250°C. The heating time is preferably, for example, 1 minute to 30 minutes, and more preferably 3 minutes to 10 minutes.

[0246] In this manner, the first microlens is formed on the substrate.

[0247] Next, a second microlens is formed on a substrate having the first microlens on its surface using a second photosensitive composition. The method for forming the second microlens is the same as the method for forming the first microlens. The second photosensitive layer is preferably the negative-type photopolymerizable composition described above.

[0248] By repeating this operation n times, n types of microlenses are formed on the substrate.

[0249] As described above, the present inventors provide the following [1] to

[17] . [1] A method comprising KrF exposure, in which a photosensitive layer is irradiated with KrF rays; formation of a dot pattern consisting of a plurality of dots by heating and developing the exposed photosensitive layer; and formation of a microlens-shaped pattern consisting of a plurality of microlens-shaped dots by heating and deforming the dots, wherein a negative-type photopolymerizable composition for forming a microlens-shaped pattern is used for forming the photosensitive layer, A negative-type photopolymerizable composition for forming microlens-shaped patterns, comprising a photopolymerizable compound (A) and a photosensitive agent (B). [2] The plurality of microlens-shaped dots Forming an etching mask on a resin film with a shape corresponding to the shape of multiple microlenses, Together with the etching mask, a plurality of microlenses are formed by etching the resin film, thereby transferring the shape of the etching mask. A negative-type photopolymerizable composition according to [1], which is the etching mask in a method for manufacturing microlenses. [3] The negative-type photopolymerizable composition according to [2], wherein the plurality of microlenses comprises two or more types of microlenses. [4] The negative-type photopolymerizable composition according to any one of [1] to [3], wherein the negative-type photopolymerizable composition comprises metal oxide fine particles (C). [5] A negative-type photopolymerizable composition according to any one of [1] to [4], wherein the photopolymerizable compound (A) comprises a resin (A1). [6] The photopolymerizable compound (A) comprises a resin (A1) and a polyfunctional (meth)acrylate (A2), The resin (A1) is an alkali-soluble resin (A1-1), The alkali-soluble resin (A1-1) contains epoxy group-containing units, The negative-type photopolymerizable composition according to [5], wherein the photosensitive agent (B) is a photoradical polymerization initiator (B1). [7] The negative-type photopolymerizable composition according to [6], wherein the photoradical polymerization initiator (B1) is an oxime ester compound (B1-1). [8] A negative-type photopolymerizable composition according to any one of [1] to [7], comprising an alkali-soluble resin (D) that does not fall under the photopolymerizable compound (A). [9] The photopolymerizable compound (A) is an epoxy group-containing compound (A3) and / or a methylol-type compound (A4), The aforementioned photosensitive agent (B) is a photoacid generator (B2), The negative-type photopolymerizable composition according to [9], wherein the alkali-soluble resin (D) is a resin (D1) having structural units derived from hydroxystyrene.

[10] The negative-type photopolymerizable composition according to [9], wherein the photoacid generator (B2) is an onium salt (B2-1).

[11] A negative-type photopolymerizable composition according to any one of [1] to

[10] , wherein the viscosity measured by a Cannon-Fenske viscometer at 1 atmosphere and 20°C is 0.5 cP or more and 10 cP or less.

[12] A negative-type photopolymerizable composition according to any one of [1] to

[11] that satisfies the following [Requirement 1]. [Requirement 1] The residual film percentage X1 (%), determined by the following steps 1-1) to 1-11), is between 95% and 110%. 1-1) In a silicon substrate having a 0.16 μm thick anti-reflective underlayer film and a 1 μm thick cured film of thermosetting acrylic resin on its surface, the negative-type photopolymerizable composition is applied onto the cured film of thermosetting acrylic resin, and then heated at 100°C for 60 seconds to obtain a coating film with a thickness of 600 nm. 1-2) The coated film is exposed to a KrF excimer laser through a mask for forming a dot pattern with a dot diameter of 0.40 μm and a dot spacing of 0.30 μm, at the optimal exposure dose that forms a dot pattern according to the mask dimensions, under the conditions of NA / s = 0.68 / 0.75. 1-3) Heat the exposed coated film at 100°C for 90 seconds. 1-4) After heating, develop by contacting with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at room temperature (23°C) for 60 seconds. 1-5) After development, the silicon substrate (M1) on which microlenses are formed is heated at 200°C for 5 minutes. 1-6) After applying KrF resist (TDUR-P3435, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to a silicon substrate on which microlenses have been formed using a spin coater, the mixture is heated at 100°C for 60 seconds to obtain a coated film with a thickness of 550 nm. 1-7) The coated film obtained in 1-6) above was exposed to a KrF excimer laser at an exposure dose of 50 mJ / cm². 2 Full-screen exposure is performed under the conditions NA / s = 0.68 / 0.75. 1-8) The coated film after exposure as described in 1-7) above is heated at 100°C for 90 seconds. 1-9) After heating as described in 1-8) above, develop by contacting with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds at room temperature (23°C). 1-10) After development as described in 1-9 above, the silicon substrate (M2) on which microlenses are formed is heated at 150°C for 5 minutes to obtain the silicon substrate (M2). 1-11) The residual film percentage X1 is calculated from the average height T1 of the microlens of M1 and the average height T2 of the microlens of M2 based on the following formula. Remaining film rate X1(%)=T2 / T1×100

[13] A negative-type photopolymerizable composition according to any one of [1] to

[12] that satisfies the following [Requirement 2]. [Requirement 2] The residual film percentage X2 (%), determined by the following steps 2-1) to 2-4), is between 95% and 110%. 2-1) After applying the negative-type photopolymerizable composition onto a silicon substrate, it is heated at 90°C for 90 seconds to dry and form a resin layer with a thickness of 1 μm. 2-2) The formed resin layer is heated at 200°C for 5 minutes to cure it and obtain a cured layer. 2-3) Immerse the resulting hardened layer in acetone at room temperature (23°C) for 5 minutes. 2-4) The residual film percentage X2 is calculated based on the following formula, using the thickness U1 of the hardened layer before acetone immersion and the thickness U2 of the hardened layer after acetone immersion. Remaining film rate X2(%)=U2 / U1×100

[14] A method for manufacturing an optical element comprising a plurality of microlenses including n types of microlenses on a substrate, USn is an integer greater than or equal to 2, The aforementioned manufacturing method Forming a resin film on the aforementioned substrate, Forming an etching mask on the resin film having a shape corresponding to the shape of the plurality of microlenses, The process includes etching the resin film together with the etching mask to form the plurality of microlenses on which the shape of the etching mask has been transferred, The etching mask is as follows (i) to (iii): (i) Applying the m-th photosensitive composition onto the resin film to form the m-th photosensitive layer, (ii) KrF exposure by irradiating the m-th photosensitive layer with a KrF line, heating and developing after the KrF exposure, thereby forming the m-th dot at a position corresponding to the position where the m-th microlens is formed on the substrate, (iii) Heating the m-th dot to deform it into a shape corresponding to the shape of the m-th microlens, This is formed by repeating the operation n times. The aforementioned m is an integer between 1 and n, The first to nth photosensitive compositions used in forming the etching mask may be the same or different. A method for manufacturing an optical element, wherein at least one of the first to nth photosensitive compositions is a negative-type photopolymerizable composition according to any one of [1] to

[13] .

[15] The method for manufacturing an optical element according to

[14] , wherein n is 2.

[16] A method for manufacturing an optical element comprising a plurality of microlenses including n types of microlenses on a substrate, USn is an integer greater than or equal to 2, The aforementioned multiple microlenses are arranged as follows: (iv)~(vi): (iv) Applying the m-th photosensitive composition to the substrate to form the m-th photosensitive layer, (v) KrF exposure by irradiating the m-th photosensitive layer with a KrF line, heating and developing after the KrF exposure to form the m-th dot at a position corresponding to the position where the m-th microlens is formed on the substrate, (vi) By heating the m-th dot, the m-th dot is deformed into a shape corresponding to the shape of the m-th microlens, The process involves repeating an operation having n times to form the desired result. The aforementioned m is an integer between 1 and n, The first to nth photosensitive compositions used in the formation of the plurality of microlenses may be the same or different. A method for manufacturing an optical element, wherein at least one of the first to nth photosensitive compositions is a negative-type photopolymerizable composition according to any one of [1] to

[13] .

[17] The method for manufacturing an optical element according to

[16] , wherein n is 2. [Examples]

[0250] 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.

[0251] [Examples 1-27, Comparative Examples 1-3] In the examples and comparative examples, resins A1-1-1 to A1-1-3, consisting of the following units, were used as the photopolymerizable compound (A) resin (A1). The number in the lower right corner of the parentheses in each constituent unit in the following structural formulas represents the content (mol%) of the constituent unit in the resin. The weight-average molecular weight (Mw) in polystyrene terms, as measured by gel permeation chromatography, is 15,000 for resin A1-1-1 and 10,000 for resins A1-1-2 and A1-1-3. The degree of dispersion (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is 2.5 for resin A1-1-1, 2.2 for resin A1-1-2, and 2.1 for resin A1-1-3.

[0252] [ka]

[0253] In the examples and comparative examples, the following A2-1 to A2-3 were used as the polyfunctional (meth)acrylate (A2) as the photopolymerizable compound (A). A2-1: Dipentaerythritol hexaacrylate A2-3: Ethylene glycol dimethacrylate

[0254] [ka]

[0255] In the examples and comparative examples, A3-1 was used as the epoxy group-containing compound (A3) as the photopolymerizable compound (A). [ka]

[0256] In the examples and comparative examples, A4-1 was used as the methylol-type compound (A4) as the photopolymerizable compound (A). [ka]

[0257] In the examples and comparative examples, B1-1 and B1-2 were used as the photoradical polymerization initiator (B1) as the photosensitive agent (B). [ka]

[0258] In the examples and comparative examples, the following B2-1 to B2-3 were used as the photoacid generator (B2) as the photosensitive agent (B). B2-1: Triphenylsulfonium 2,4,6-triisopropylbenzenesulfonate B2-2: Bis(tert-butylsulfonyl)diazomethane B2-3: Diphenyltolylsulfonium p-toluenesulfonate

[0259] In the examples and comparative examples, C-1 and C-2 were used as metal oxide fine particles (C) as described below. C-1: Titanium dioxide (average particle size 30 nm) C-2: Zirconium oxide (average particle size 30 nm)

[0260] In the examples and comparative examples, the alkali-soluble resins (D) that do not fall under the category of photopolymerizable compound (A) were resins D-1 to D-3 consisting of the following units. The number in the lower right corner of the parentheses in each constituent unit in the following structural formulas represents the content (mol%) of the constituent unit in the resin. The weight-average molecular weight (Mw) of resins D-1 and D-2, measured by gel permeation chromatography, is 2500 for polystyrene and 17000 for resin D-3. The degree of dispersion (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is 1.5 for resins D-1 and D-2, and 1.9 for resin D-1.

[0261] [ka]

[0262] In the examples and comparative examples, the following F-1 to F-4 were used as quenchers. F-2: 2,6-diisopropylaniline F-3: Triethylamine [ka]

[0263] The types and parts by mass of the photopolymerizable compound (A), photosensitive agent (B), alkali-soluble resin (D), quencher, and surfactant (polyether-modified silicone oil SH8400, manufactured by Toray Dow Corning Co., Ltd.) listed in Tables 1 and 2 were dissolved in a mixed solvent (propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 90 / 10 (mass ratio)) to obtain the photosensitive compositions of each example and each comparative example. Examples 1 to 27 are negative-type photopolymerizable compositions.

[0264] The sensitivity and post-exposure storage stability of the photosensitive composition, as well as the shape and chemical resistance of the microlens-shaped patterns formed using the photosensitive composition, were evaluated according to the following method. The evaluation results are shown in Table 3. In the method described below, Y1 and Y2 were used as the developing solutions. Y1: 2.38% by mass aqueous solution of tetramethylammonium hydroxide. Y2: Butyl acetate

[0265] [Chemical resistance 1 (residual film rate (after formation of microlens shape pattern (multiple microlenses)))] A silicon substrate had a 0.16 μm thick anti-reflective underlayer film and a 1 μm thick cured film of thermosetting acrylic resin on its surface. The photosensitive compositions of the examples and comparative examples were applied to the cured acrylic resin film using a spin coater. The photosensitive compositions applied to the silicon substrate were baked at 100°C for 60 seconds to obtain coated films (photosensitive layers) with the thicknesses shown in Table 3. The formed coated film (photosensitive layer) was exposed to a dot pattern formation mask with a dot diameter of 0.40 μm and a dot spacing of 0.30 μm. In Examples and Comparative Examples 1-2, a KrF excimer laser (NSR-S203, Nikon Corporation) was used at NA / s = 0.68 / 0.75, while in Comparative Example 3, an i-line exposure system FPA-5510iV (Canon Inc.) (NA 0.18) was used. The exposure amount was set to the optimal exposure amount that formed a dot pattern according to the mask dimensions. The optimal exposure amount was 10 mJ / cm² for the KrF excimer laser (Examples, Comparative Examples 1-2) or i-line (Comparative Example 3). 2 From 50 mJ / cm² 2 Up to 2 mJ / cm² 2 The exposure level was changed in increments, and this is the exposure level at which a dot pattern matching the mask dimensions was formed. The coated film (photosensitive layer) after exposure was heated at 100°C for 90 seconds (PEB). After heating, development was performed by contacting the film with the types of developer shown in Table 3 at room temperature (23°C) for 60 seconds. After development, the substrate (M1) was baked at 200°C for 5 minutes to obtain a silicon substrate with a microlens-shaped pattern (multiple microlenses) formed on it.

[0266] Next, a KrF resist (TDUR-P3435, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to a silicon substrate (M1) on which a microlens-shaped pattern (multiple microlenses) was formed, using a spin coater. The KrF resist applied to the silicon substrate was baked at 100°C for 60 seconds to obtain a coated film with a thickness of 550 nm. The coated film was exposed to a KrF excimer laser (NSR-S203, manufactured by Nikon) at an exposure dose of 50 mJ / cm². 2 Full-surface exposure was performed with NA / s = 0.68 / 0.75. The exposed coated film was baked at 100°C for 90 seconds. After baking, the samples were developed by contacting them with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at room temperature (23°C) for 60 seconds. After development, the substrate was baked at 150°C for 5 minutes. The silicon substrate with the microlens-shaped pattern (multiple microlenses) formed after baking is called the silicon substrate (M2).

[0267] <Residual film rate (after formation of microlens shape pattern (multiple microlenses))> The residual film percentage X1 was calculated based on the following formula using the average height T1 of the microlenses on silicon substrate (M1) and the average height T2 of the microlenses on silicon substrate (M2), and evaluated according to the following criteria. A to C indicates good performance. Remaining film rate X1(%)=(%)=T2 / T1×100 A: The residual film percentage X1 is between 99% and 103%. B: The residual film percentage X1 is 98% or more but less than 99%, or greater than 103% but less than or equal to 105%. C: The residual film percentage X1 is 95% or more but less than 98%, or greater than 105% but less than or equal to 110%. D: Residual film percentage X1 is less than 95% or greater than 110% The height of a microlens is determined by observing the microlens from a direction perpendicular to the thickness of the silicon substrate, and is the length of the longest point of the microlens in the thickness direction of the substrate. The average height of the microlenses is the average of the heights of each individual microlens. Furthermore, the average height T1 of the microlenses on the silicon substrate (M1) is the average height of the microlenses before exposure to the chemicals (KrF resist and developer), and the average height T2 of the microlenses on the silicon substrate (M2) is the average height of the microlenses after exposure to the same chemicals. Therefore, the chemical resistance of the microlenses can be evaluated using the residual film percentage X1.

[0268] [sensitivity] Using the optimal exposure amount determined in the above [Chemical Resistance 1 (Residual Film Rate (After Formation of Microlens Shape Pattern (Multiple Microlenses))]], sensitivity was evaluated according to the following criteria. A to D indicates good performance. A: The optimal exposure dose Eop is 30 mJ / cm². 2 below B: The optimal exposure dose Eop is 30 mJ / cm². 2 Super 40mJ / cm 2 below C: Optimal exposure Eop is 40 mJ / cm² 2 Super 45mJ / cm 2 below D: The optimal exposure Eop is 45 mJ / cm². 2 Super 50mJ / cm 2 below E: Optimal exposure Eop is 50 mJ / cm² 2 super

[0269] [Shape uniformity] For silicon substrates (M1) on which microlens-shaped patterns (multiple microlenses) were formed, prepared in the same manner as described above [Chemical Resistance 1 (Residual Film Rate (After Formation of Microlens Shape Pattern (Multiple Microlenses)))], the height of each microlens was measured using a scanning electron microscope (SEM), and the average value and standard deviation of the microlens heights were calculated. The value obtained by dividing the standard deviation by the thickness of the coating film (photosensitive layer) shown in Table 3 (standard deviation / thickness of the coating film (photosensitive layer) shown in Table 3): W was evaluated according to the following criteria. A to C indicates good performance. A:W is 0.01 or less B:W is greater than 0.01 and less than or equal to 0.02 C:W is greater than 0.02 and less than or equal to 0.03. D:W is greater than 0.03 The height of a microlens is determined by observing the microlens from a direction perpendicular to the thickness of the silicon substrate, and is the length of the longest point of the microlens in the thickness direction of the substrate. The average height of the microlenses is the average of the heights of each individual microlens.

[0270] [Chemical resistance 2 (residual film rate (coated film)] The photosensitive compositions of the examples and comparative examples were applied to a silicon substrate by spin coating, and dried using a hot plate under pre-bake conditions of 90°C for 90 seconds to obtain coated films (photosensitive layers) with the thicknesses shown in Table 3. The films were then cured by heating with a hot plate at 200°C for 5 minutes. The heated coated film (M3) was immersed in acetone at room temperature (23°C) for 5 minutes. The residual film thickness X2 was calculated based on the following formula using the film thickness (U1) before acetone immersion and the film thickness (U2) after acetone immersion, and evaluated according to the following criteria. A to C indicates good performance. Remaining film rate X2(%)=U2 / U1×100 A: The residual film percentage X2 is between 99% and 103%. B: The residual film percentage X2 is 98% or more but less than 99%, or greater than 103% but less than or equal to 105%. C: The residual film percentage X2 is 95% or more but less than 98%, or more than 105% but 110% or less. D: Residual film percentage X2 is less than 95% or greater than 110%

[0271] [Refractive index] The refractive index at a wavelength of 550 nm was measured using a spectroscopic ellipsometer for the heated coated film (M3), which was prepared in the same manner as described above for [Chemical Resistance 2 (Residual Film Rate (Coated Film)]. A to C indicates a good result. A: 1.75 or higher B: 1.65 or higher and less than 1.75 C: 1.55 or higher and less than 1.65 D: Less than 1.55

[0272] [PED] A silicon substrate (M1) with a microlens-shaped pattern (multiple microlenses) formed on it was formed using the same method as described in [Chemical Resistance 1 (Residual Film Rate (After Formation of Microlens-Shaped Pattern (Multiple Microlenses)))] above. At this time, the time between exposure and post-exposure heating (PEB) was set to 0 hours (PEB immediately after exposure) or 9 hours. The ratio (CD (Critical Dimension) variation rate) of the average diameter of the top of the pattern obtained when the time between exposure and PEB was 9 hours was calculated to the average diameter of the top of the pattern (dot pattern) obtained when PEB was performed immediately after exposure, after development and before baking at 200°C for 5 minutes. A to C indicates good results. A: 5% or less B: More than 5% and less than 7.5% C: More than 7.5% and less than 10% D: More than 10%

[0273] [Table 1]

[0274] [Table 2]

[0275] [Table 3]

[0276] Examples 1 to 27 show that when a negative-type photopolymerizable composition for forming microlens-shaped patterns, comprising a photopolymerizable compound (A) and a photosensitive agent (B), is used in a method that includes KrF exposure, where a photosensitive layer is irradiated with KrF rays; formation of a dot pattern consisting of multiple dots by heating and developing the exposed photosensitive layer; and formation of a microlens-shaped pattern consisting of multiple microlens-shaped dots by heating and deforming the dots, it is possible to form a microlens-shaped pattern that is excellent in sensitivity and stability over time after exposure, has a uniform shape, and is excellent in chemical resistance.

Claims

1. A method comprising KrF exposure, in which a photosensitive layer is irradiated with KrF rays; formation of a dot pattern consisting of multiple dots by heating and developing the exposed photosensitive layer; and formation of a microlens-shaped pattern consisting of multiple microlens-shaped dots by heating and deforming the dots, wherein a negative-type photopolymerizable composition for forming a microlens-shaped pattern is used for forming the photosensitive layer, A negative-type photopolymerizable composition for forming microlens-shaped patterns, comprising a photopolymerizable compound (A) and a photosensitive agent (B).

2. The aforementioned microlens-shaped dots Forming an etching mask on a resin film with a shape corresponding to the shape of multiple microlenses, Together with the etching mask, a plurality of microlenses are formed by etching the resin film, thereby transferring the shape of the etching mask. The negative-type photopolymerizable composition according to claim 1, which is the etching mask in a method for manufacturing microlenses.

3. The negative-type photopolymerizable composition according to claim 2, wherein the plurality of microlenses comprises two or more types of microlenses.

4. The negative-type photopolymerizable composition according to claim 1, wherein the negative-type photopolymerizable composition comprises metal oxide fine particles (C).

5. The negative-type photopolymerizable composition according to claim 1, wherein the photopolymerizable compound (A) comprises a resin (A1).

6. The photopolymerizable compound (A) includes a resin (A1) and a polyfunctional (meth)acrylate (A2). The resin (A1) is an alkali-soluble resin (A1-1), The alkali-soluble resin (A1-1) contains epoxy group-containing units, The negative-type photopolymerizable composition according to claim 5, wherein the photosensitive agent (B) is a photoradical polymerization initiator (B1).

7. The negative-type photopolymerizable composition according to claim 6, wherein the photoradical polymerization initiator (B1) is an oxime ester compound (B1-1).

8. The negative-type photopolymerizable composition according to claim 1, comprising an alkali-soluble resin (D) that does not fall under the category of the photopolymerizable compound (A).

9. The photopolymerizable compound (A) is an epoxy group-containing compound (A3) and / or a methylol-type compound (A4), The photosensitive agent (B) is a photoacid generator (B2), The negative-type photopolymerizable composition according to claim 8, wherein the alkali-soluble resin (D) is a resin (D1) having structural units derived from hydroxystyrene.

10. The negative-type photopolymerizable composition according to claim 9, wherein the photoacid generator (B2) is an onium salt (B2-1).

11. The negative-type photopolymerizable composition according to claim 1, wherein the viscosity measured by a Canon-Fenske viscometer at 1 atmosphere and 20°C is 0.5 cP or more and 10 cP or less.

12. A negative-type photopolymerizable composition according to claim 1, satisfying the following [Requirement 1]. [Requirement 1] The residual film percentage X1 (%), determined by the following steps 1-1) to 1-11), is between 95% and 110%. 1-1) In a silicon substrate having a 0.16 μm thick anti-reflective underlayer film and a 1 μm thick cured film of thermosetting acrylic resin on its surface, the negative-type photopolymerizable composition is applied onto the cured film of thermosetting acrylic resin, and then heated at 100°C for 60 seconds to obtain a coating film with a thickness of 600 nm. 1-2) The coated film is exposed to a KrF excimer laser through a mask for forming a dot pattern with a dot diameter of 0.40 μm and a dot spacing of 0.30 μm, at the optimal exposure dose which forms a dot pattern according to the mask dimensions, under the conditions of NA / s = 0.68 / 0.

75. 1-3) Heat the exposed coated film at 100°C for 90 seconds. 1-4) After heating, develop by contacting with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at room temperature (23°C) for 60 seconds. 1-5) After development, the silicon substrate (M1) on which microlenses are formed is heated at 200°C for 5 minutes. 1-6) After applying KrF resist (TDUR-P3435, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to a silicon substrate on which microlenses are formed using a spin coater, the mixture is heated at 100°C for 60 seconds to obtain a coated film with a thickness of 550 nm. 1-7) The coated film obtained in 1-6) above was exposed to a KrF excimer laser at an exposure dose of 50 mJ / cm². ２ Full-surface exposure is performed under the condition NA / s = 0.68 / 0.

75. 1-8) The coated film after exposure as described in 1-7) is heated at 100°C for 90 seconds. 1-9) After heating as described in 1-8) above, develop by contacting with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds at room temperature (23°C). 1-10) After development as described in 1-9) above, heat at 150°C for 5 minutes to obtain a silicon substrate (M2) on which microlenses are formed. 1-11) The residual film percentage X1 is calculated from the average height T1 of the microlens of M1 and the average height T2 of the microlens of M2 based on the following formula. Remaining film rate X1 (%) = T2 / T1 x 100

13. A negative-type photopolymerizable composition according to claim 1, satisfying the following [Requirement 2]. [Requirement 2] The residual film percentage X2 (%), determined by the following steps 2-1) to 2-4), is between 95% and 110%. 2-1) After applying the negative-type photopolymerizable composition onto a silicon substrate, it is heated at 90°C for 90 seconds to dry and form a resin layer with a thickness of 1 μm. 2-2) The formed resin layer is heated at 200°C for 5 minutes to cure it and obtain a cured layer. 2-3) Immerse the resulting hardened layer in acetone at room temperature (23°C) for 5 minutes. 2-4) The residual film percentage X2 is calculated based on the following formula, using the thickness U1 of the hardened layer before acetone immersion and the thickness U2 of the hardened layer after acetone immersion. Remaining film rate X2 (%) = U2 / U1 x 100

14. A method for manufacturing an optical element comprising a plurality of microlenses, including n types of microlenses, on a substrate, Un is an integer greater than or equal to 2, The aforementioned manufacturing method Forming a resin film on the aforementioned substrate, Forming an etching mask on the resin film having a shape corresponding to the shape of the plurality of microlenses, The process includes etching the resin film together with the etching mask to form the plurality of microlenses on which the shape of the etching mask has been transferred, The etching mask is as follows (i) to (iii): (i) Applying the m-th photosensitive composition onto the resin film to form the m-th photosensitive layer, (ii) KrF exposure by irradiating the m-th photosensitive layer with KrF rays, heating and developing after the KrF exposure to form the m-th dot at a position corresponding to the position where the m-th microlens is formed on the substrate, (iii) By heating the m-th dot, the m-th dot is deformed into a shape corresponding to the shape of the m-th microlens, This is formed by repeating the operation n times. The aforementioned m is an integer between 1 and n, The first to nth photosensitive compositions used in forming the etching mask may be the same or different. A method for manufacturing an optical element, wherein at least one of the first to nth photosensitive compositions is a negative-type photopolymerizable composition according to any one of claims 1 to 13.

15. The method for manufacturing an optical element according to claim 14, wherein n is 2.

16. A method for manufacturing an optical element comprising a plurality of microlenses, including n types of microlenses, on a substrate, Un is an integer greater than or equal to 2, The aforementioned multiple microlenses are as follows: (iv) to (vi): (iv) Applying the m-th photosensitive composition to the substrate to form the m-th photosensitive layer, (v) KrF exposure by irradiating the m-th photosensitive layer with KrF rays, heating and developing after the KrF exposure to form the m-th dot at a position corresponding to the position where the m-th microlens is formed on the substrate, (vi) Heating the m-th dot to deform it into a shape corresponding to the shape of the m-th microlens, The process involves repeating an operation having n times to form the desired result. The aforementioned m is an integer between 1 and n, The first to nth photosensitive compositions used in the formation of the plurality of microlenses may be the same or different. A method for manufacturing an optical element, wherein at least one of the first to nth photosensitive compositions is a negative-type photopolymerizable composition according to any one of claims 1 to 13.

17. The method for manufacturing an optical element according to claim 16, wherein n is 2.

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