Positive photosensitive resin composition

Abstract

[Problem] To provide a novel positive photosensitive resin composition. [Solution] A positive photosensitive resin composition: containing the following component (A), component (B), component (C), and component (D), or the following component (A'), component (B), component (C), component (D), and component (E); and further containing a solvent. Component (A): an alkali-soluble resin having an acid-crosslinkable group. Component (A'): an alkali-soluble resin that does not have an acid-crosslinkable group. Component (B): a quinone diazide compound. Component (C): a photoacid generator. Component (D): a PED stability improver. Component (E): a compound having at least two acid-crosslinkable groups in the molecule.

Description

Positive photosensitive resin composition

[0001] The present invention relates to a positive-type photosensitive resin composition, a cured film obtained from the resin composition, a microlens, and a method for producing the same.

[0002] To improve performance, minute lenses called microlenses are often used in imaging devices such as CCD image sensors and CMOS image sensors, and in display devices such as liquid crystal displays and organic EL displays. For example, providing a microlens in an image sensor has the effect of improving the light collection rate and increasing the sensitivity of the sensor.

[0003] One known method for producing microlenses is the etch-back method (see, for example, Patent Document 1). Specifically, a microlens resin layer is formed on a color filter, a positive resist is applied to the resin layer, a lens pattern is formed by exposing and developing a portion of the resist and, if necessary, heating the resist, and then etching back the microlens using the lens pattern as an etching mask to transfer the lens pattern shape to the microlens resin layer, thereby producing a microlens.

[0004] On the other hand, from the viewpoint of reducing manufacturing costs, a method has been proposed in which the positive resist is used directly as a lens. In this case, it is necessary to have both the properties of a resist and the properties of a microlens. Therefore, a photosensitive resin composition is required that not only enables positive patterning but also allows the formed microlenses to have excellent transparency and chemical resistance. Here, the shape of the microlens varies depending on the design of the element, and various shapes such as a prism, a cylinder, a truncated pyramid, a truncated cone, and a spherical indentation may be required. When producing a spherical indentation-shaped microlens, a known method involves forming a pattern such as a prism or a truncated pyramid and then reflowing (fluidizing by heating, also known as melt flow or thermal flow).

[0005] For example, Patent Document 2 proposes a photosensitive resin composition containing an alkali-soluble copolymer and a quinone diazide group-containing compound. By using this composition, a resin pattern can be formed by exposure and development, and then the phenolic hydroxyl groups and epoxy groups can be crosslinked by heating to obtain a microlens.

[0006] However, in recent years, the increasing use of devices with low heat resistance, such as organic devices and flexible devices, has led to an increasing demand for lower process temperatures. Accordingly, there is a demand for positive-type photosensitive resin compositions that can produce microlenses with good performance even in low-temperature processes. When producing microlenses with a spherical sag shape, sufficient reflow is required even at low temperatures. The photosensitive resin composition described in Patent Document 2 employs thermal curing of phenolic hydroxy groups and epoxy groups, but this thermal curing reaction typically requires high-temperature conditions exceeding 150°C, and therefore is not suitable for low-temperature processes below 150°C.

[0007] Therefore, Patent Documents 3 and 4 propose radiation-sensitive resin compositions containing an alkali-soluble polymer, a quinone diazide compound, and a photoacid generator. By using such compositions, after forming a resin pattern by exposure and development, a strong acid can be generated within the resin pattern by re-exposure, thereby promoting cationic polymerization, thereby enabling a lower-temperature process. However, such compositions have the risk of PED causing changes in the film properties (sensitivity characteristics, patterning characteristics, etc.) of the exposed area. Here, PED stands for Post-Exposure Delay, and refers to the interval between the exposure step and the next step (e.g., development step). When fabricating microlenses using large equipment, time is required for wafer transport, etc., so from a practical standpoint, a material with high PED stability (PED resistance) that can tolerate PED for at least two hours is usually required. In light of this background, photosensitive resin compositions containing an alkali-soluble resin, a quinone diazide compound, and a photoacid generator, as described in Patent Documents 3 and 4, have the advantage of being able to produce microlenses in a low-temperature process. However, they have poor PED stability (PED resistance). In addition, the cause of changes in the film properties of exposed areas due to PED is unknown. Therefore, there has been a need to improve PED stability (PED resistance) and to investigate the cause of changes in the film properties due to PED.

[0008] Furthermore, Patent Document 4 describes an acid diffusion controller that prevents the diffusion of acid generated in exposed areas into unexposed areas in order to suppress changes in the film properties of unexposed areas. For example, Patent Document 5 describes a chemically amplified positive resist in which a base can be added as an acid diffusion controller. However, this acid diffusion controller is different from the one that prevents changes in the film properties of exposed areas.

[0009] Japanese Patent Application Laid-Open No. 1-10666 Japanese Patent Application Laid-Open No. 2007-33518 Japanese Patent Application Laid-Open No. 2009-75329 Japanese Patent Application Laid-Open No. 2020-101659 International Publication No. 2007 / 007176

[0010] The present invention has been made in light of the above circumstances, and an object of the present invention is to provide a positive photosensitive resin composition that is capable of positive patterning, capable of forming microlenses having a desired shape even in a low-temperature process at 150°C or less, and that allows the formed microlenses to have excellent transparency and chemical resistance while suppressing changes in the film properties of exposed areas due to PED (Post Exposure Delay).

[0011]

[0005] As a result of intensive investigations aimed at solving the above-mentioned problems, the present inventors have discovered an additive known as a PED stability (PED resistance) improver. Specifically, they have clarified that in a positive-tone photosensitive resin composition containing an alkali-soluble resin, a quinone diazide compound, and a photoacid generator, the cause of changes in the film properties in exposed areas due to PED is cationic polymerization in the exposed areas, and have found that PED stability (PED resistance) can be improved by adding a component that inhibits the initiation reaction or propagation reaction of cationic polymerization in the exposed areas, thereby completing the present invention.

[0012] A first aspect of the present invention is a positive photosensitive resin composition comprising the following components (A), (B), (C), and (D), or the following components (A'), (B), (C), (D), and (E), and further comprising a solvent: Component (A): an alkali-soluble resin having an acid crosslinkable group Component (A'): an alkali-soluble resin not having an acid crosslinkable group Component (B): a quinone diazide compound Component (C): a photoacid generator Component (D): a PED stability improver Component (E): a compound having at least two acid crosslinkable groups in the molecule

[0013] The component (A) and the component (A') are, for example, alkali-soluble resins having a carboxy group.

[0014] The components (A) and (A') are, for example, alkali-soluble resins having a phenolic hydroxy group.

[0015] The components (A) and (A') are, for example, alkali-soluble resins having a structural unit represented by the following formula (1). (In the formula, R ０represents a hydrogen atom or a methyl group, X represents an —O— group or an —NH— group, R １ represents a single bond or an alkylene group having 1 or 2 carbon atoms, R ２ represents a methyl group, a represents 1 or 2, and b represents an integer of 0 to 2.

[0016] In the structural unit represented by the formula (1), X represents, for example, an —NH— group.

[0017] The acid crosslinkable group is, for example, a functional group containing an epoxy ring or an oxetane ring.

[0018] The weight average molecular weight of the component (A) and the component (A') in terms of polystyrene is, for example, 1,000 to 100,000.

[0019] The component (C) is, for example, a nonionic photoacid generator. The nonionic photoacid generator is, for example, a photoacid generator represented by the following formula (2): (In the formula, R ３ is a hydrocarbon group or a perfluoroalkyl group having 1 to 10 carbon atoms, and R ４ is a linear alkyl or alkoxy group having 1 to 8 carbon atoms, or a branched alkyl or alkoxy group having 3 to 8 carbon atoms.

[0020] The component (D) is, for example, a photobase generator or a basic compound.

[0021] The component (D) is, for example, an amine.

[0022] The content of the component (D) is, for example, 0.1 to 3 parts by mass per 100 parts by mass of the component (A).

[0023] The positive photosensitive resin composition of the present invention may further contain the following component (F): Component (F): Sensitizer

[0024] The positive photosensitive resin composition of the present invention is used for producing, for example, a microlens.

[0025] A second aspect of the present invention is a cured film obtained from the positive photosensitive resin composition.

[0026] A third aspect of the present invention is a microlens made from the positive photosensitive resin composition.

[0027] A fourth aspect of the present invention is a method for producing a microlens, comprising: a coating step of coating the positive photosensitive resin composition on a substrate to form a resin film; a first exposure step of exposing at least a portion of the resin film to light after the coating step; a development step of removing the exposed portions of the resin film with a developer after the first exposure step to form a pattern of unexposed portions of the resin film; a second exposure step of further exposing the pattern after the development step; and a post-bake step of heating the pattern at a temperature of 150°C or less after the second exposure step.

[0028] After the developing step and before the second exposure step, a reflow step of heating the pattern at a temperature of 150° C. or less may be included.

[0029] The base material is, for example, a substrate on which a color filter is formed.

[0030] In a positive-tone photosensitive resin composition containing an alkali-soluble resin, a quinone diazide compound, and a photoacid generator, the mechanism by which PED causes changes in the film properties of exposed areas is as follows. That is, during the first exposure step for positive patterning, not only is a carboxylic acid generated from the quinone diazide compound in the exposed areas, but a small amount of strong acid is also generated from the photoacid generator. This strong acid initiates a cationic polymerization reaction of a cationically polymerizable group (e.g., an epoxy group, an epoxycycloalkyl group, or an oxetanyl group) contained in the alkali-soluble resin having an acid crosslinking group or in the compound having an acid crosslinking group, leading to changes in the film properties of the exposed areas. Therefore, by adding the component (D) to the positive-tone photosensitive resin composition of the present invention, the initiation reaction or growth reaction of cationic polymerization that occurs in the exposed areas during the first exposure step for positive patterning can be inhibited, thereby improving PED stability (PED resistance). Here, the component (D) has different problems and effects from the acid diffusion controller described in Patent Document 4.

[0031] According to the present invention, it is possible to provide a positive photosensitive resin composition that is capable of positive patterning, capable of forming microlenses having a desired shape even in a low-temperature process at 150°C or less, and capable of forming microlenses that have excellent transparency and chemical resistance while suppressing changes in the film properties of exposed areas due to PED.

[0032] The positive photosensitive resin composition of the present invention will be described in more detail. [Component (A) / Component (A')] Component (A) or (A') contained in the positive photosensitive resin composition of the present invention is a resin soluble in an alkaline developer and is clearly distinguished from the alkali-insoluble resins used in chemically amplified positive resists, such as those described in Patent Document 5. Component (A) or (A') is not particularly limited as long as it is a resin soluble in an alkaline developer, and examples thereof include polysiloxane resins, novolak resins, polyvinyl alcohol resins, methacrylic acid resins, acrylic resins such as methacrylic acid esters, polyimide resins, polyamic acid resins, polybenzoxazole resins, hydroxystyrene resins, and cyclic olefin resins. The alkali-soluble groups contained in these alkali-soluble resins are typically functional groups with an acid dissociation constant pKa (the lowest value in the case of polyvalent acids) of 13 or less. From the viewpoint of development margin, functional groups with an acid dissociation constant pKa of preferably 0 to 13, more preferably 4 to 12, can be used. Specific examples include a silanol group, a fluoroalcohol group, a maleimide group, a carboxy group, a phenolic hydroxy group, etc. The alkali-soluble resin may contain only one type of these alkali-soluble groups, or two or more types of these alkali-soluble groups.

[0033] Furthermore, component (A) has an acid crosslinkable group in its partial structure. Here, the acid crosslinkable group is not particularly limited as long as it is a functional group capable of forming a covalent bond with itself or with another functional group under acidic conditions, and examples thereof include an N-methylol group, an N-methoxymethyl group, an N-vinyl group, a styryl group, a vinyl ether group, an epoxy group, an epoxycycloalkyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group. From the viewpoint of low-temperature curing properties, cationically polymerizable groups are particularly preferred as the acid crosslinkable group, and among these, epoxy groups and epoxycycloalkyl groups, which are functional groups containing an epoxy ring, and an oxetanyl group, which is a functional group containing an oxetane ring, are particularly preferred. Component (A) may contain only one type of these acid crosslinkable groups, or two or more types. By having component (A) have an acid crosslinkable group in its partial structure, chemical resistance can be further improved. On the other hand, component (A') does not have an acid crosslinkable group in its partial structure.

[0034] Component (A) or (A') can be synthesized by a polymerization reaction (addition polymerization, ring-opening polymerization, condensation polymerization, addition-condensation, polyaddition) of a monomer having at least one alkali-soluble group or alkali-soluble group precursor and, if necessary, other monomers. Furthermore, a polymer reaction may optionally be carried out following the polymerization reaction. Various known methods can be used for these polymerization and polymer reactions. The alkali-soluble resin of component (A) or (A') may be used alone or in combination of two or more.

[0035] Among the alkali-soluble resins, copolymers obtained by copolymerizing radically polymerizable monomers are particularly preferred. Examples of alkali-soluble group-containing radically polymerizable monomers used as polymerization components for the copolymers include the following monomers: (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride, fumaric anhydride, citraconic anhydride, mesaconic anhydride, itaconic anhydride, vinylbenzoic acid, o-carboxyphenyl(meth)acrylate, m-carboxyphenyl(meth)acrylate, p-carboxyphenyl(meth)acrylate, o-carboxyphenyl(meth)acrylamide, m-carboxyphenyl(meth)acrylamide, p-carboxyphenyl(meth)acrylamide, mono[2-(meth)acryloyloxyethyl] succinate, and mono[2-(meth)acryloyloxyethyl] phthalate. Monomers containing a carboxy group or a carboxylic acid anhydride group, such as ω-carboxypolycaprolactone mono(meth)acrylate, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;o-Hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, α-methyl-o-hydroxystyrene, α-methyl-m-hydroxystyrene, α-methyl-p-hydroxystyrene, 2-hydroxyphenyl (meth)acrylate, 3-hydroxyphenyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 4-hydroxybenzyl (meth)acrylate, 4-hydroxyphenethyl (meth)acrylate, 3,5-dimethyl-4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl (meth)acrylate, 3,5-dimethyl-4-hydroxyphen Phenolic hydroxy group-containing monomers such as ethyl (meth)acrylate, N-(2-hydroxyphenyl)(meth)acrylamide, N-(3-hydroxyphenyl)(meth)acrylamide, N-(4-hydroxyphenyl)(meth)acrylamide, N-(4-hydroxybenzyl)(meth)acrylamide, N-(4-hydroxyphenethyl)(meth)acrylamide, N-(3,5-dimethyl-4-hydroxyphenyl)(meth)acrylamide, N-(3,5-dimethyl-4-hydroxybenzyl)(meth)acrylamide, and N-(3,5-dimethyl-4-hydroxyphenethyl)(meth)acrylamide. In the present invention, (meth)acrylic acid refers to both acrylic acid and methacrylic acid.

[0036] As the phenolic hydroxy group-containing monomer, from the viewpoint of heat resistance etc., a monomer that forms a structural unit represented by the above formula (1) is particularly preferred, and among these, (meth)acrylamide is particularly preferred. These monomers may be used alone or in combination of two or more.

[0037] In the case of component (A), in addition to the alkali-soluble group-containing radical polymerizable monomer, an acid-crosslinkable group-containing radical polymerizable monomer is contained as a polymerization component. On the other hand, in the case of component (A'), an acid-crosslinkable group-containing radical polymerizable monomer is not contained as a polymerization component. Examples of the acid-crosslinkable group-containing radical polymerizable monomer include the following monomers: functional group-containing monomers containing an epoxy ring, such as glycidyl (meth)acrylate, α-ethyl glycidyl acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, α-ethyl-6,7-epoxyheptyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, isopropenyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and vinylcyclohexene monoxide; 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxymethyl)-2-phenyloxetane, 3-(2-(meth)acryloyloxyethyl)oxetane, 3-(2-(meth)acryloyloxyethyl)-2-ethyloxetane, 3-(2-(meth)acryloyloxyethyl)-3-ethyloxetane, 3-(2-(meth)acryloyloxyethyl)-2-phenyloxetane, 2-((meth)acryloyloxyethyl) functional group-containing monomers containing an oxetane ring, such as 2-((meth)acryloyloxymethyl)oxetane, 2-((meth)acryloyloxymethyl)-3-methyloxetane, 2-((meth)acryloyloxymethyl)-4-ethyloxetane, 2-((meth)acryloyloxymethyl)-3-phenyloxetane, 2-(2-(meth)acryloyloxyethyl)oxetane, 2-(2-(meth)acryloyloxyethyl)-3-ethyloxetane, 2-(2-(meth)acryloyloxyethyl)-4-ethyloxetane, and 2-(2-(meth)acryloyloxyethyl)-3-phenyloxetane.These acid crosslinkable group-containing radical polymerizable monomers may be used alone or in combination of two or more.

[0038] Furthermore, component (A) or component (A') may contain other radically polymerizable monomers as polymerization components, if necessary. Examples of other radically polymerizable monomers include the following monomers: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and methyl (meth)acrylate. Acrylate, 1-adamantyl (meth)acrylate, phenyl (meth)acrylate, o-methoxyphenyl (meth)acrylate, m-methoxyphenyl (meth)acrylate, p-methoxyphenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, naphthyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl peroxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, trifluoromethyl (meth)acrylate, (meth)acrylamide, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-tert-butylstyrene,1-vinylnaphthalene, 2-vinylnaphthalene, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, vinyl acetate. These other radical polymerizable monomers may be used alone or in combination of two or more.

[0039] The molecular weight of the component (A) or (A') is determined by the weight average molecular weight M in terms of polystyrene calculated by gel permeation chromatography (GPC) or the like. Ｗ as a molecular weight, is 1,000 to 100,000, preferably 2,000 to 50,000, and more preferably 5,000 to 30,000. By setting the molecular weight within the above range, a good pattern can be formed after development without impairing chemical resistance.

[0040] When producing a microlens having a sagittal or hemispherical shape, the glass transition temperature of component (A) or component (A') is 70° C. to 150° C. By keeping the glass transition temperature within this range, good reflowability can be achieved even in a low-temperature process at 150° C. or less, and microlenses having the desired sagittal or hemispherical shape can be produced.

[0041] [Component (B)] The component (B) contained in the positive photosensitive resin composition of the present invention is not particularly limited as long as it is a compound having a 1,2-quinonediazide group, and for example, a condensate of a hydroxy group-containing compound with 1,2-naphthoquinonediazide sulfonic acid halide can be used. Specifically, a compound in which 10 mol % to 100 mol %, preferably 20 mol % to 95 mol %, of the hydroxy groups of the hydroxy group-containing compound are esterified with the 1,2-naphthoquinonediazide sulfonic acid halide can be used. For the condensation reaction, various known methods can be used.

[0042] Examples of the hydroxy group-containing compound include the following compounds: dihydroxybenzophenones such as 2,4-dihydroxybenzophenone; trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; tetrahydroxybenzophenones such as 2,4,2',4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, and 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone; pentahydroxybenzophenones such as 2,3,4,2',4'-pentahydroxybenzophenone and 2,3,4,2',6'-pentahydroxybenzophenone; Hexahydroxybenzophenones such as 2,4,6,3',4',5'-hexahydroxybenzophenone and 3,4,5,3',4',5'-hexahydroxybenzophenone; 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,3,3-tris(4-hydroxyphenyl)butane, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5 (polyhydroxyphenyl)alkanes such as 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobiindene-5,6,7,5',6',7'-hexanol, and 2,2,4-trimethyl-7,2',4'-trihydroxyflavan;Other compounds such as phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 1-[1-(3-{1-(4-hydroxyphenyl)-1-methylethyl}-4,6-dihydroxyphenyl)-1-methylethyl]-3-(1-(3-{1-(4-hydroxyphenyl)-1-methylethyl}-4,6-dihydroxyphenyl)-1-methylethyl)benzene, and 4,6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1,3-dihydroxybenzene. Among these compounds, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris(p-hydroxyphenyl)ethane, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol are preferred.

[0043] The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride, more preferably 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride and 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride, and even more preferably 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride.

[0044] The compound of component (B) may be used alone or in combination of two or more.

[0045] The content of component (B) in the positive photosensitive resin composition of the present invention is 5 to 100 parts by mass, preferably 10 to 60 parts by mass, and more preferably 15 to 40 parts by mass, per 100 parts by mass of component (A). By setting the content of component (B) within the above range, the difference in solubility in an alkaline developer between exposed and unexposed areas can be increased without significantly reducing sensitivity, and positive patterning becomes possible with a relatively low exposure dose.

[0046] [Component (C)] The component (C) contained in the positive photosensitive resin composition of the present invention is not particularly limited as long as it is a compound that can generate an acid having an acid dissociation constant pKa of 4 or less upon exposure, and examples of the component (C) include ionic photoacid generators and nonionic photoacid generators.

[0047] Examples of the ionic photoacid generator that can be used include the following commercial products and compounds: ADEKA ARCLES (registered trademark) SP-056 and SP-171 (manufactured by ADEKA Corporation), CPI (registered trademark) -100B(40), -100P, -101A, -110A, -110B, -110P, -200K, -210S, -300, -310B, -310FG, -400, -410B, -410S, VC-1FG, and ES-1B (manufactured by San-Apro Co., Ltd.), TPS-TF, TPS-CS, and TPS-PFBS (manufactured by Toyo Gosei Co., Ltd.), and TPS arylsulfonium salts such as TPS-102, TPS-103, TPS-105, TPS-106, TPS-109, TPS-200, TPS-300, TPS-1000, HDS-109, MDS-103, MDS-105, MDS-109, MDS-205, MDS-209, BDS-109, MNPS-109, DTS-102, DTS-103, DTS-105, DTS-200, NDS-103, NDS-105, NDS-155, and NDS-165 (all manufactured by Midori Chemical Co., Ltd.); Aryliodonium salts such as ADEKA Arcles (registered trademark) SP-140 (manufactured by ADEKA Corporation), IK-1, IK-1PC (80), IK-1FG (manufactured by San-Apro Co., Ltd.), DTBPI-PFBS (manufactured by Toyo Gosei Co., Ltd.), DPI-105, DPI-106, DPI-109, DPI-201, BI-105, MPI-105, MPI-106, MPI-109, BBI-102, BBI-103, BBI-105, BBI-106, BBI-109, BBI-110, BBI-200, BBI-201, BBI-300, and BBI-301 (manufactured by Midori Chemical Co., Ltd.).

[0048] Examples of the nonionic photoacid generator that can be used include the following commercial products and compounds: N-sulfonyloxyimides such as ADEKA ARCLES (registered trademark) SP-082 and SP-606 (both manufactured by ADEKA Corporation), NA-CS1, NP-TM2, and NP-SE10 (both manufactured by San-Apro Co., Ltd.), SI-105, SI-106, PI-106, NDI-101, NDI-105, NDI-106, NDI-109, NDI-1001, NDI-1004, NAI-100, NAI-101, NAI-105, NAI-106, NAI-109, NAI-1002, NAI-1003, and NAI-1004 (all manufactured by Midori Chemical Industry Co., Ltd.); Oxime sulfonates such as IRGACURE (registered trademark) PAG103, PAG121, and PAG203 (all manufactured by BASF Japan Ltd.), PAI-01, PAI-101, PAI-106, PAI-1001, PAI-1002, PAI-1003, and PAI-1004 (all manufactured by Midori Chemical Industry Co., Ltd.); TAZ-100, TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-107, TAZ-108, TAZ-109, TAZ-110, TAZ- Triazines such as 113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-203, and TAZ-204 (all manufactured by Midori Kagaku Co., Ltd.).

[0049] Among these ionic and nonionic photoacid generators, nonionic photoacid generators are preferred from the viewpoint of storage stability and sensitivity, N-sulfonyloxyimides are more preferred, and the compounds represented by formula (2) are even more preferred. Specific examples of the compounds represented by formula (2) include compounds represented by the following formulas (2-1) to (2-28).

[0050]

[0051] The compound of component (C) may be used alone or in combination of two or more.

[0052] The content of component (C) in the positive-type photosensitive resin composition of the present invention is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A). By setting the content of component (C) within the above range, chemical resistance can be improved without impairing transparency.

[0053] [Component (D)] The component (D) contained in the positive photosensitive resin composition of the present invention is not particularly limited as long as it is a compound that can inhibit the initiation reaction or propagation reaction of cationic polymerization in the exposed area, and examples thereof include photobase generators and basic compounds (amines, quaternary ammoniums, inorganic bases), etc.

[0054] The photobase generator is not particularly limited as long as it is a compound that can generate a base upon exposure to light, and for example, the following commercial products can be used: WPBG-018, WPBG-027, WPBG-140, WPBG-165, WPBG-266, WPBG-300, and WPBG-345 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), NBC-101, and ANC-101 (all manufactured by Midori Chemical Industry Co., Ltd.).

[0055] Examples of the basic compound include the following compounds: ethylamine, n-propylamine, isopropylamine, cyclopropylamine, n-butylamine, isobutylamine, cyclobutylamine, n-pentylamine, isopentylamine, cyclopentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, oleylamine, 2-ethylhexylamine, aniline, benzylamine, ethanolamine, and propanolamine. primary amines such as butanolamine, 3-ethoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 1-amino-2-propanol and ethylenediamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, diallylamine, di-n-butylamine, diisobutylamine, di-n-pentylamine, dicyclopentylamine, di-n-hexylamine, dicyclohexylamine, diphenylamine, dibenzylamine, di-n-heptylamine, di-n-oct ... diethylamine, di-n-nonylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, di-n-tridecylamine, N-methyl-n-butylamine, N-methylcyclohexylamine, N-ethylmethylamine, N-ethyl-n-propylamine, N-ethylisopropylamine, N-ethyl-n-butylamine, N-ethylcyclohexylamine, N-ethyl-n-heptylamine, N-isopropylcyclohexylamine, N-phenylbenzylamine, N-(2-methoxyethyl)isopropylamine secondary amines such as diethanolamine, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, 2-(n-propylamino)ethanol, 2-(isopropylamino)ethanol, 2-(n-butylamino)ethanol, 2-(isobutylamino)ethanol, diethanolamine and dibutanolamine, triethylamine, tri-n-propylamine, triallylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-n-pentylamine, tri-n-hexylamine, triphenylamine,Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-undecylamine, N-methyldiphenylamine, N-methyldicyclohexylamine, N-methyldidecylamine, N,N-diethylmethylamine, N,N-diethylcyclohexylamine, N,N-dimethylbutylamine, N-ethyldi-n-propylamine, N-ethyldiisopropylamine, N,N-dimethylethanolamine, N,N-dimethyl-n-propanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methyl amines such as tertiary amines such as n-butyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, triethanolamine, tri-n-propanolamine, triisopropanolamine, tetramethylethylenediamine, and tetraethylethylenediamine, and heterocyclic amines such as pyrrolidine, methylpyrrolidine, piperidine, methylpiperidine, piperazine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, pyridine, and imidazole; quaternary ammoniums such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; inorganic bases such as ammonia, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium phosphate, and potassium phosphate.

[0056] From the viewpoint of solubility, among these photobase generators and basic compounds, amines are particularly preferred. The compound of component (D) may be used alone or in combination of two or more.

[0057] The content of component (D) in the positive photosensitive resin composition of the present invention is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of component (A). By setting the content of component (D) within the above range, it is possible to achieve both PED stability (PED resistance) and chemical resistance.

[0058] In general, when the quinone diazide compound of component (B) is mixed with a basic compound such as an amine, it has the property of discoloring due to interaction. However, this does not significantly impair the transparency of the cured film obtained from the positive photosensitive resin composition of the present invention or the transparency of the microlens produced from the positive photosensitive resin composition of the present invention.

[0059] [Component (E)] When the positive photosensitive resin composition of the present invention contains the component (A'), it contains the component (E) as an essential component, and when it contains the component (A), it contains the component (E) as an optional component. The component (E) is not particularly limited as long as it is a compound having at least two of the acid crosslinkable groups in the molecule, and for example, the following products and compounds can be used. EPICLON (registered trademark) 830, 830-S, 835, 840, 840-S, 850, 850-S, 850-LC, and HP-820 (all manufactured by DIC Corporation), DENACOL (registered trademark) EX-201, EX-211, EX-212, EX-252, EX-810, EX-811, EX-821, EX-830, EX-832, EX-841, EX-850, EX-851, EX-861, EX-920, and EX-9 31, EX-991L, EX-313, EX-314, EX-321, EX-321L, EX-411, EX-421, EX-512, EX-521, EX-612, EX-614, EX-614B, and EX-622 (all manufactured by Nagase ChemteX Corporation), jER (registered trademark) 152, jER 630, jER 825, jER 827, jER 828, jER 828EL, jER 828US, and jER 828XA (all manufactured by Mitsubishi Chemical Corporation), and TETRAD (registered trademark)-C , and -X (all manufactured by Mitsubishi Gas Chemical Company, Inc.), Celloxide (registered trademark) 2021P, Celloxide (registered trademark) 2081, Epolead (registered trademark) GT401 (all manufactured by Daicel Corporation), Epotohto (registered trademark) YD-115, YD-115CA, YD-127, YD-128, YD-128G, YD-128S, YD-128CA, YD-8125, YD-825GS, YDF-170, YDF-170N, YDF-8170C, YDF-870GS, and ZX- 1059, YH-404, YH-434, YH-434L, YH-513, YH-523, ST-3000 (all manufactured by Nippon Steel Chemical & Material Co., Ltd.), ADEKA RESIN (registered trademark) EP-4100, EP-4100G, EP-4100E, EP-4100TX, EP-4300E, EP-4400, EP-4520S, EP-4530, EP-4901, EP-4901E, EP-4000, EP-4005, EP-7001,EP-4080E, EPU-6, EPU-7N, EPU-11F, EPU-15F, EPU-1395, EPU-73B, EPU-17, EPU-17T-6, EPR-1415-1, EPR-2000, EPR-2007, ADEKA GLYCILOR (registered trademark) ED-503, ED-503G, ED-506, ED-523T, ED-505 (all manufactured by ADEKA Corporation), Sumiepoxy (registered trademark) ELM- 434, ELM-434L, ELM-434VL, ELM-100, ELM-100H (all manufactured by Sumitomo Chemical Co., Ltd.), Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 4000, Epolite 3002(N) (all manufactured by Kyoeisha Chemical Co., Ltd.), and polyfunctional epoxy resins such as Epocalic (registered trademark) THI-DE (manufactured by ENEOS Corporation); Polyfunctional oxetane resins such as ETERNACOLL (registered trademark) OXBP and OXIPA (both manufactured by Ube Industries, Ltd.), ARON OXETANE (registered trademark) OXT-121 and OXT-221 (both manufactured by Toagosei Co., Ltd.), etc.

[0060] The compound of component (E) may be used alone or in combination of two or more.

[0061] When the positive-type photosensitive resin composition of the present invention contains the component (E), the content of the component (E) is 5 to 100 parts by mass, preferably 10 to 50 parts by mass, per 100 parts by mass of the component (A) or the component (A'). By setting the content of the component (E) within the above range, chemical resistance can be improved.

[0062] [Component (F)] The component (F) contained as an optional component in the positive photosensitive resin composition of the present invention is not particularly limited as long as it is a substance that can transfer the energy of irradiated light to another substance, and examples thereof include p-toluquinone, 1-phenyl-1,2-propanedione, phenanthrene, anthracene, 9,10-diethoxyanthracene, 9,10-dipropyloxyanthracene, 9,10-dibutoxyanthracene, 9,10-dioctanoyloxyanthracene, 3,7-dimethoxyanthracene, pyrene, perylene, xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2-isopropylthioxanthone.

[0063] The compound of component (F) may be used alone or in combination of two or more.

[0064] When the positive-type photosensitive resin composition of the present invention contains component (F), the content of component (F) is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of component (A). By setting the content of component (F) within the above range, it is possible to effectively exhibit a sensitizing effect on the photoacid generator (C) without impairing transparency, and to improve chemical resistance.

[0065] [Solvent] The solvent contained in the positive photosensitive resin composition of the present invention is not particularly limited as long as it dissolves the components (A) to (D) or the components (A′) to (E), as well as any optional components added as needed. For example, all organic solvents such as hydrocarbons, halogenated hydrocarbons, ethers, alcohols, aldehydes, ketones, esters, amides, and nitriles can be used.

[0066] Examples of the hydrocarbons include n-pentane, cyclopentane, methylcyclopentane, n-hexane, isohexane, cyclohexane, methylcyclohexane, ethylcyclohexane, n-heptane, benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene.

[0067] Examples of the halogenated hydrocarbons include dichloromethane, chloroform, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, hexachloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, hydrofluorocarbons, and perfluorocarbons.

[0068] Examples of the ethers include diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, di-tert-butyl ether, di-n-pentyl ether, diisopentyl ether, di-n-hexyl ether, methyl-n-propyl ether, methyl isopropyl ether, ethyl-n-propyl ether, ethyl isopropyl ether, n-butyl methyl ether, isobutyl methyl ether, tert-butyl methyl ether, n-butyl ethyl ether, isobutyl ethyl ether, tert-butyl ethyl ether, methyl-n-pentyl ether, cyclopentyl methyl ether, n-hexyl methyl ether, cyclohexyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, methyl-n-pentyl ether, cyclopentyl methyl ether, n-hexyl methyl ether, cyclohexyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3 ...methyl-n-pentyl ether, methyl-n-pentyl ether, cyclopentyl methyl ether, n-hexyl methyl ether, cyclohexyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, methyl-n-pentyl ether, methyl Examples of the olefin copolymer include olefin copolymers such as olefin copolymers, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripropylene glycol dibutyl ether.

[0069] Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, cyclopentanol, methylcyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, methylcyclohexanol, 1-heptanol, and 2-heptanol. alcohol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether Monohydric alcohols such as glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and tripropylene glycol monobutyl ether; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol,Examples include dihydric alcohols such as 3-pentanediol and 1,2-hexanediol, and trihydric alcohols such as glycerin.

[0070] Examples of the aldehydes include ethanal, propanal, 2-methyl-1-propanal, butanal, 3-methylbutanal, pentanal, and benzaldehyde.

[0071] Examples of the ketones include acetone, 2-butanone, 2-pentanone, 3-pentanone, cyclopentanone, 2,4-pentanedione, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone, and 2-heptanone.

[0072] Examples of the esters include methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, tert-butyl formate, n-pentyl formate, isopentyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, cyclopentyl acetate, n-hexyl acetate, and isopropyl acetate. Hexyl acetate, cyclohexyl acetate, n-heptyl acetate, isoheptyl acetate, n-octyl acetate, isooctyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene ethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, triplyl glycol propylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, tert-butyl butyrate,Examples of the acetoacetate include methyl isobutyrate, ethyl isobutyrate, n-propyl isobutyrate, isopropyl isobutyrate, n-butyl isobutyrate, isobutyl isobutyrate, tert-butyl isobutyrate, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, tert-butyl lactate, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate, tert-butyl acetoacetate, dimethyl malonate, diethyl malonate, triacetin, γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, δ-caprolactone, and ε-caprolactone.

[0073] Examples of the amides include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, and N-ethylpyrrolidone.

[0074] Examples of the nitriles include acetonitrile, propionitrile, and butyronitrile.

[0075] These solvents may be used alone or in combination of two or more.

[0076] Among these solvents, from the viewpoint of improving the leveling properties of a cured film formed by applying the positive photosensitive resin composition of the present invention onto a substrate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, ethyl lactate, n-butyl lactate, cyclopentanone, and cyclohexanone are preferred.

[0077] [Surfactant and Other Additives] The positive photosensitive resin composition of the present invention may optionally contain a surfactant for the purpose of improving coatability. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; Nonionic surfactants such as polyethylene sorbitan fatty acid esters, Eftop (registered trademark) EF301, EF303, EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F-171, F-173, R-30, R-40, R-40-LM (all manufactured by DIC Corporation), Fluorad FC430, FC431 (all manufactured by Sumitomo 3M Limited), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, Surflon SC1 Fluorine-based surfactants such as Ftergent series (manufactured by Neos Corporation), including FTX-01, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Corporation), FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, and FTX-240G, and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned. These surfactants may be used alone or in combination of two or more.

[0078] When the positive photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is 0.001 to 3 parts by mass, preferably 0.005 to 1 part by mass, and more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the total solid content excluding the solvent in the positive photosensitive resin composition.

[0079] The positive photosensitive resin composition of the present invention may contain additives such as curing aids, antioxidants, ultraviolet absorbers, plasticizers, and adhesion aids as needed, as long as the effects of the present invention are not impaired.

[0080] [Method for preparing positive-type photosensitive resin composition] The method for preparing the positive-type photosensitive resin composition of the present invention is not particularly limited, but may be, for example, a method in which components (A) to (D) or components (A') to (E), and optionally other components, are dissolved in a solvent to prepare a homogeneous solution. If necessary, the solution may be filtered using a filter having a pore size of 0.1 μm to 10 μm.

[0081] [Method for Producing Microlenses] An example of producing a microlens using the positive photosensitive resin composition of the present invention will be described. <Coating Step> The positive photosensitive resin composition of the present invention is coated onto a substrate (e.g., a semiconductor substrate, a glass substrate, a quartz substrate, a plastic substrate, a silicon wafer, or a substrate having various metal films or elements such as color filters formed on the surface thereof) using an appropriate coating method such as a spinner or coater, and then prebaked using a heating means such as an oven or a hot plate to remove the solvent, thereby forming a resin film. Prebaking conditions are appropriately selected from the ranges of a baking temperature of 60°C to 130°C and a baking time of 20 seconds to 30 minutes. The thickness of the formed resin film is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.

[0082] <First Exposure Step> After the coating step, at least a portion of the formed resin film is exposed to light through a predetermined mask. Examples of light rays that can be used for exposure include g-line, i-line, KrF excimer laser, and ArF excimer laser. The exposure dose is 20 mJ / cm. ２ ~2000mJ / cm ２The range is appropriately selected.

[0083] <Development Step> After the first exposure step, the exposed portions of the resin film are removed with a developer to form a pattern in the unexposed portions of the resin film. The development method is not particularly limited, but examples include dipping, puddling, and spraying. The development conditions are appropriately selected from the range of a development temperature of 5°C to 50°C and a development time of 10 to 300 seconds. The developer used is not particularly limited as long as it can remove the exposed portions, but examples include alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium phosphate, potassium phosphate, ammonia, tetramethylammonium hydroxide (TMAH), and tetraethylammonium hydroxide (TEAH). Alternatively, an alkaline aqueous solution to which an appropriate amount of surfactant or organic solvent has been added may be used as the developer. These developers may be used alone or in combination of two or more.

[0084] After development, the film may be rinsed with a rinse solution to wash away the developer. After development or rinsing, the film may be dried by spinning with a spinning device such as a spinner or coater, or by blowing compressed air or compressed nitrogen onto the film to remove any remaining developer or rinse solution.

[0085] <Reflow Process> When producing a microlens having a spherical or hemispherical shape, a reflow process may be included in which the pattern formed after the development process is heated using a heating means such as an oven or a hot plate before the second exposure process described later. The reflow conditions are appropriately selected from the ranges of a baking temperature of 80°C to 150°C and a baking time of 1 minute to 90 minutes. Here, the reflow temperature is T Ｒ [°C], the glass transition temperature of the alkali-soluble resin is T ｇ When the reflow temperature T is expressed as [°C], it is preferable that the following formula (3) and the following formula (4) are satisfied, more preferably the following formula (3) and the following formula (5), and even more preferably the following formula (3) and the following formula (6). Ｒ is the glass transition temperature T of the alkali-soluble resin ｇ Even if the following is true, (T ｇ−10)≦T Ｒ The pattern may reflow if the following formula (3): 80≦T Ｒ ≦150 Formula (4): (T ｇ −10)≦T Ｒ ≦(T ｇ +60) Formula (5):T ｇ ≦T Ｒ ≦(T ｇ +50) Formula (6): (T ｇ +10)≦T Ｒ ≦(T ｇ +40) By satisfying the above relational expression, the pattern exhibits good reflowability, and adjacent patterns are prevented from fusing together due to excessive reflow, thereby obtaining microlenses with the desired sagittal or hemispherical shape. Although sagittal or hemispherical microlenses can be produced even if the reflow step is omitted, including the reflow step makes it possible to produce sagittal or hemispherical microlenses at a lower temperature.

[0086] <Second Exposure Step> After the development step or the reflow step, the pattern is further exposed to light. Examples of light rays that can be used for exposure include g-line, i-line, KrF excimer laser, and ArF excimer laser. The exposure dose is 100 mJ / cm. ２ ~5000mJ / cm ２ The range is appropriately selected.

[0087] <Post-baking step> After the second exposure step, the pattern is heated using a heating means such as an oven or a hot plate. The post-baking conditions are appropriately selected from the ranges of a baking temperature of 80° C. to 150° C. and a baking time of 1 minute to 90 minutes.

[0088] Microlenses such as prisms, cylinders, truncated pyramids, or truncated cones may be fabricated without reflowing the pattern. In this case, the post-baking temperature is set to T Ｐ [°C], the glass transition temperature of the alkali-soluble resin is T ｇ When expressed as [°C], the following formula (7) and the following formula (8) are preferably satisfied, more preferably the following formula (7) and the following formula (9), and even more preferably the following formula (7) and the following formula (10). Formula (7): 80≦TＰ ≦150 Formula (8): T Ｐ ≦T ｇ Formula (9): T Ｐ ≦(T ｇ -10) Formula (10): T Ｐ ≦(T ｇ -20) By satisfying the above relational expression, the pattern can be prevented from reflowing, and a microlens having a desired prismatic, cylindrical, truncated pyramidal, or truncated conical shape can be obtained.

[0089] When manufacturing a microlens having a spherical or hemispherical shape, if a reflow process is not included, the post-bake temperature is set to T Ｐ [°C], the glass transition temperature of the alkali-soluble resin is T ｇ When expressed as [°C], preferably the above formula (7) and the following formula (11) are satisfied, more preferably the above formula (7) and the following formula (12), and even more preferably the above formula (7) and the following formula (13). Formula (11): T ｇ ≦T Ｐ ≦(T ｇ +70) Formula (12): (T ｇ +10)≦T Ｐ ≦(T ｇ +60) Formula (13): (T ｇ +20)≦T Ｐ ≦(T ｇ +50) By satisfying the above relational expression, the pattern exhibits good reflowability without performing a reflow process, and adjacent patterns are prevented from fusing together due to excessive reflow, thereby obtaining microlenses with the desired spherical or hemispherical shape.

[0090] When manufacturing a microlens having a spherical or hemispherical shape, if a reflow process is included, the post-bake temperature is set to T Ｐ [°C], reflow temperature is T Ｒ [°C], preferably the above formula (3), the above formula (7), and the following formula (14), more preferably the above formula (3), the above formula (7), and the following formula (15), and even more preferably the above formula (3), the above formula (7), and the following formula (16), are satisfied. Ｐ ≦(T Ｒ +40) Formula (15): T Ｐ ≦(T Ｒ +30) Formula (16): TＰ ≦(T Ｒ +20) By satisfying the above relational expression, it becomes easier to control the shape of the spherically-depressed or hemispherical microlens.

[0091] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0092] Weight average molecular weight M of alkali-soluble resin in terms of polystyrene Ｗ The apparatus and conditions used for the measurement are as follows: Apparatus: GPC system manufactured by JASCO Corporation Column: Shodex (registered trademark) KF-804L and KF-803L Column oven: 40°C Flow rate: 1 mL / min Eluent: tetrahydrofuran Sample concentration: 10 mg / mL Sample injection amount: 20 μL Standard substance: monodisperse polystyrene Detector: differential refractometer

[0093] The compounds used in the examples and comparative examples are as follows. <Component (B)> B-1: Condensate of 1 mole of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1.5 moles of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride <Component (C)> C-1: ADEKA ARCLES (registered trademark) SP-606 (manufactured by ADEKA Corporation) C-2: CPI-110P (manufactured by San-Apro Co., Ltd.) <Component (D)> D-1: Tripentylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) D-2: N-ethyldiisopropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) D-3: Potassium hydroxide (manufactured by Junsei Chemical Co., Ltd.) D-4: Tetramethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.) D-5: WPBG-018 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) <Component (E)> E-1: Epolead (registered trademark) GT401 (manufactured by Daicel Corporation) <Component (F)> F-1: 2-isopropylthioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.) <Surfactant> R-40: Megafac (registered trademark) R-40 (manufactured by DIC Corporation)

[0094] Synthesis of Component (A) Synthesis Example 1 A flask was charged with a stirrer and 90 g of propylene glycol monomethyl ether as a solvent, and the flask was immersed in a heated oil bath and maintained at 70°C. Next, a solution containing 20 g of methacrylic acid, 40 g of methyl methacrylate, and 40 g of styrene as monomers, 5.0 g of 2,2'-azobisisobutyronitrile as a thermal radical generator, and 105 g of propylene glycol monomethyl ether as a solvent was placed in a dropping funnel and connected to the flask. After purging with nitrogen, the mixture was added dropwise over 3 hours with stirring. After completion of the dropping, the mixture was allowed to react for an additional 15 hours, yielding a copolymer solution (solids concentration 35% by mass). The solution was poured into 3 L of hexane with stirring, and the precipitate was collected and dried using a vacuum dryer to obtain a copolymer powder. The polystyrene-equivalent weight average molecular weight M of the resulting copolymer was 0.015 g. Ｗ The viscosity was 14,000. This copolymer was designated as alkali-soluble resin A'-1.

[0095] Synthesis Example 2 A flask was charged with a stirrer and 90 g of propylene glycol monomethyl ether as a solvent, and the flask was immersed in a heated oil bath and maintained at 70°C. Next, a solution containing 10 g of acrylic acid, 30 g of 4-hydroxybutyl acrylate, and 60 g of styrene as monomers, 4.5 g of 2,2'-azobisisobutyronitrile as a thermal radical generator, and 105 g of propylene glycol monomethyl ether as a solvent was placed in a dropping funnel and connected to the flask. After the atmosphere was replaced with nitrogen, the mixture was added dropwise over 3 hours with stirring. After the dropwise addition was completed, the reaction was continued for a further 15 hours, yielding a copolymer solution (solids concentration 35% by mass). The polystyrene-equivalent weight average molecular weight M of the obtained copolymer was 10 g. Ｗ The viscosity was 18,000. This copolymer was designated as alkali-soluble resin A'-2.

[0096] Synthesis Example 3 A flask was charged with a stirrer and 90 g of propylene glycol monomethyl ether as a solvent, and the flask was immersed in a heated oil bath and maintained at 80°C. Next, a solution containing 52 g of 4-hydroxyphenyl methacrylate, 20 g of 3,4-epoxycyclohexylmethyl methacrylate, and 28 g of butyl methacrylate as monomers, 4.9 g of 2,2'-azobisisobutyronitrile as a thermal radical generator, and 105 g of propylene glycol monomethyl ether as a solvent was placed in a dropping funnel and connected to the flask. After purging with nitrogen, the mixture was added dropwise over 3 hours with stirring. After completion of the dropping, the mixture was allowed to react for an additional 15 hours, yielding a copolymer solution (solids concentration 35% by mass). The polystyrene-equivalent weight average molecular weight M of the resulting copolymer was 1.0 g. Ｗ The viscosity was 17,000. This copolymer was designated as alkali-soluble resin A-3.

[0097] Synthesis Example 4 A flask was charged with a stirrer and 88 g of propylene glycol monomethyl ether as a solvent, and the flask was immersed in a heated oil bath and maintained at 75°C. Next, a solution containing 50 g of 4-hydroxyphenyl methacrylate and 50 g of 3,4-epoxycyclohexylmethyl methacrylate as monomers, 2.6 g of 2,2'-azobisisobutyronitrile as a thermal radical generator, and 103 g of propylene glycol monomethyl ether as a solvent was placed in a dropping funnel and connected to the flask. After purging with nitrogen, the mixture was added dropwise over 3 hours with stirring. After completion of the dropping, the mixture was allowed to react for an additional 15 hours, yielding a copolymer solution (solids concentration 35% by mass). The polystyrene-equivalent weight average molecular weight M of the obtained copolymer was 1.0 g. Ｗ The viscosity was 32,000. This copolymer was designated as alkali-soluble resin A-4.

[0098] Synthesis Example 5 A flask was charged with a stirrer and 89 g of propylene glycol monomethyl ether as a solvent, and the flask was immersed in a heated oil bath and maintained at 80°C. Next, a solution containing 42 g of 4-hydroxyphenyl methacrylate and 58 g of 3,4-epoxycyclohexylmethyl methacrylate as monomers, 4.4 g of 2,2'-azobisisobutyronitrile as a thermal radical generator, and 104 g of propylene glycol monomethyl ether as a solvent was placed in a dropping funnel and connected to the flask. After purging with nitrogen, the mixture was added dropwise over 3 hours with stirring. After completion of the dropping, the mixture was allowed to react for an additional 15 hours, yielding a copolymer solution (solids concentration 35% by mass). The polystyrene-equivalent weight average molecular weight M of the obtained copolymer was 1.0 g. Ｗ The viscosity was 14,000. This copolymer was designated as alkali-soluble resin A-5.

[0099] Synthesis Example 6 A flask was charged with a stirrer and 90 g of propylene glycol monomethyl ether as a solvent, and the flask was immersed in a heated oil bath and maintained at 80°C. Next, a solution containing 40 g of 4-hydroxyphenyl methacrylate and 60 g of 3-(methacryloyloxymethyl)-3-ethyloxetane as monomers, 4.5 g of 2,2'-azobisisobutyronitrile as a thermal radical generator, and 105 g of propylene glycol monomethyl ether as a solvent was placed in a dropping funnel and connected to the flask. After purging with nitrogen, the mixture was added dropwise over 3 hours with stirring. After completion of the dropping, the mixture was allowed to react for an additional 15 hours, yielding a copolymer solution (solids concentration 35% by mass). The polystyrene-equivalent weight average molecular weight M of the obtained copolymer was 1.0 g. Ｗ The viscosity was 11,000. This copolymer was designated as alkali-soluble resin A-6.

[0100] Synthesis Example 7 A flask was charged with a stirrer and 50 g of propylene glycol monomethyl ether as a solvent, and the flask was immersed in a heated oil bath and maintained at 80°C. Next, a solution containing 40 g of N-(4-hydroxyphenyl)methacrylamide and 60 g of 3,4-epoxycyclohexylmethyl methacrylate as monomers, 4.4 g of 2,2'-azobisisobutyronitrile as a thermal radical generator, and 194 g of propylene glycol monomethyl ether as a solvent was placed in a dropping funnel and connected to the flask. After purging with nitrogen, the mixture was added dropwise over 3 hours with stirring. After completion of the dropping, the mixture was allowed to react for an additional 15 hours to obtain a copolymer solution (solids concentration 30% by mass). The polystyrene-equivalent weight average molecular weight M of the obtained copolymer was 1.0 g. Ｗ The viscosity was 11,000. This copolymer was designated as alkali-soluble resin A-7.

[0101] Synthesis Example 8 A flask was charged with a stirrer and 50 g of propylene glycol monomethyl ether as a solvent, and the flask was immersed in a heated oil bath and maintained at 87°C. Next, a solution containing 30 g of N-(4-hydroxyphenyl)methacrylamide, 60 g of 3,4-epoxycyclohexylmethyl methacrylate, and 10 g of 2-hydroxyethyl methacrylate as monomers, 4.5 g of 2,2'-azobisisobutyronitrile as a thermal radical generator, and 194 g of propylene glycol monomethyl ether as a solvent was placed in a dropping funnel and connected to the flask. After purging with nitrogen, the mixture was added dropwise over 3 hours with stirring. After completion of the dropping, the mixture was allowed to react for an additional 15 hours to obtain a copolymer solution (solids concentration 30% by mass). The polystyrene-equivalent weight average molecular weight M of the obtained copolymer was 1.0 g. Ｗ The viscosity was 8,000. This copolymer was designated as alkali-soluble resin A-8.

[0102] Synthesis Example 9 A copolymer solution (solid content concentration 30% by mass) was obtained in the same manner as in Synthesis Example 8, except that 25 g of N-(4-hydroxyphenyl)methacrylamide, 15 g of 2-hydroxyethyl methacrylate, and 4.6 g of 2,2′-azobisisobutyronitrile were used. The polystyrene-equivalent weight average molecular weight M ＷThe viscosity was 8,000. This copolymer was designated as alkali-soluble resin A-9.

[0103] Synthesis Example 10 A copolymer solution (solid content concentration 30% by mass) was obtained in the same manner as in Synthesis Example 8, except that 20 g of N-(4-hydroxyphenyl)methacrylamide, 20 g of 2-hydroxyethyl methacrylate, and 4.7 g of 2,2′-azobisisobutyronitrile were used. The polystyrene-equivalent weight average molecular weight M Ｗ The viscosity was 8,000. This copolymer was designated as alkali-soluble resin A-10.

[0104] [Preparation of Positive Photosensitive Resin Composition] Example 1 21.0 g of the alkali-soluble resin A'-1 obtained in Synthesis Example 1 as the component (A'), 6.3 g of B-1 as the component (B), 0.3 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 39.9 g of propylene glycol monomethyl ether and 39.9 g of propylene glycol monomethyl ether acetate as solvents were blended to form a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 29% by mass).

[0105] Example 2 60.0 g (21.0 g as solids) of the alkali-soluble resin A'-2 obtained in Synthesis Example 2 as the component (A'), 4.8 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 10.5 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 3.8 g of propylene glycol monomethyl ether and 35.1 g of propylene glycol monomethyl ether acetate as solvents were blended to prepare a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 32% by mass).

[0106] Example 3 60.0 g (21.0 g as solids) of the alkali-soluble resin A-3 obtained in Synthesis Example 3 as the component (A), 4.8 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 14.0 g of propylene glycol monomethyl ether and 22.7 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 30% by mass).

[0107] Example 4 60.0 g (21.0 g as solids) of the alkali-soluble resin A-4 obtained in Synthesis Example 4 as the component (A), 6.3 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 22.1 g of propylene glycol monomethyl ether and 26.2 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 28% by mass).

[0108] Example 5 60.0 g (21.0 g as solids) of the alkali-soluble resin A-5 obtained in Synthesis Example 5 as the component (A), 4.8 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 14.0 g of propylene glycol monomethyl ether and 22.7 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 30% by mass).

[0109] Example 6 60.0 g (21.0 g as solids) of the alkali-soluble resin A-6 obtained in Synthesis Example 6 as the component (A), 4.8 g of B-1 as the component (B), 0.4 g of C-1 as the component (C), 0.2 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 14.4 g of propylene glycol monomethyl ether and 22.9 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 30% by mass).

[0110] Example 7 70.0 g (21.0 g as solids) of the alkali-soluble resin A-7 obtained in Synthesis Example 7 as the component (A), 4.8 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 9.4 g of propylene glycol monomethyl ether and 25.0 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 28% by mass).

[0111] Example 8 70.0 g (21.0 g as solids) of the alkali-soluble resin A-8 obtained in Synthesis Example 8 as the component (A), 4.8 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 6.6 g of propylene glycol monomethyl ether and 23.8 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 29% by mass).

[0112] Example 9 70.0 g (21.0 g as solids) of the alkali-soluble resin A-8 obtained in Synthesis Example 8 as the component (A), 4.8 g of B-1 as the component (B), 0.3 g of C-2 as the component (C), 0.1 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 6.8 g of propylene glycol monomethyl ether and 23.9 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 29% by mass).

[0113] Example 10 70.0 g (21.0 g as solids) of the alkali-soluble resin A-9 obtained in Synthesis Example 9 as the component (A), 4.8 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 6.6 g of propylene glycol monomethyl ether and 23.8 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 29% by mass).

[0114] Example 11 70.0 g (21.0 g as solids) of the alkali-soluble resin A-10 obtained in Synthesis Example 10 as the component (A), 4.8 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 6.3 g of E-1 as the component (E), 0.01 g of R-40 as a surfactant, and 30.2 g of propylene glycol monomethyl ether and 79.2 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The mixture was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 17% by mass).

[0115] Example 12 A positive photosensitive resin composition (solid content concentration 17% by mass) was obtained in the same manner as in Example 11, except that 0.4 g of D-2 was used instead of D-1 as the component (D).

[0116] Example 13 A positive photosensitive resin composition (solid content concentration: 17% by mass) was obtained in the same manner as in Example 11, except that 0.02 g of D-3 was used instead of D-1 as the component (D).

[0117] Example 14 A positive photosensitive resin composition (solid content concentration: 17% by mass) was obtained in the same manner as in Example 11, except that 0.04 g of D-4 (actually, 0.4 g of a 10% by mass aqueous solution of tetramethylammonium hydroxide) was used instead of D-1 as the component (D).

[0118] Example 15 A positive photosensitive resin composition (solid content concentration 17% by mass) was obtained in the same manner as in Example 11, except that 0.2 g of D-5 was used instead of D-1 as the component (D).

[0119] Example 16 70.0 g (21.0 g as solids) of the alkali-soluble resin A-10 obtained in Synthesis Example 10 as the component (A), 4.8 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 0.01 g of R-40 as a surfactant, and 25.1 g of propylene glycol monomethyl ether and 74.1 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 15% by mass).

[0120] Example 17 84.0 g (25.2 g as solids) of the alkali-soluble resin A-10 obtained in Synthesis Example 10 as the component (A), 5.8 g of B-1 as the component (B), 0.2 g of C-1 as the component (C), 0.1 g of D-1 as the component (D), 7.6 g of E-1 as the component (E), 0.05 g of F-1 as the component (F), 0.01 g of R-40 as a surfactant, and 36.2 g of propylene glycol monomethyl ether and 95.0 g of propylene glycol monomethyl ether acetate as solvents were blended to obtain a homogeneous solution. The mixture was then filtered using a polyethylene microfilter with a pore size of 0.10 μm to obtain a positive photosensitive resin composition (solids concentration 17% by mass).

[0121] Comparative Example 1 A positive photosensitive resin composition (solid content concentration: 29% by mass) was obtained in the same manner as in Example 1, except that the component (D) was not blended.

[0122] Comparative Example 2 A positive photosensitive resin composition (solid content concentration: 17% by mass) was obtained in the same manner as in Example 11, except that the component (D) was not blended.

[0123] Comparative Example 3 A positive photosensitive resin composition (solid content concentration: 17% by mass) was obtained in the same manner as in Example 11, except that the component (C) was not blended.

[0124] Table 1 shows the components contained in the positive-type photosensitive resin compositions of Examples 1 to 17 and Comparative Examples 1 to 3, as well as the contents of components (B) to (F) per 100 parts by mass of component (A) or component (A′).

[0125] [Lens Shape Evaluation] Each of the positive photosensitive resin compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 3 was applied to a silicon wafer using a spin coater and prebaked on a hot plate at 80°C for 90 seconds to form a resin film having a thickness shown in Table 2. Next, the resin film was subjected to a first exposure using an i-line stepper (NSR-2205i12D, NA = 0.63, manufactured by Nikon Corporation) through a predetermined mask at an exposure dose shown in Table 2. Here, as the mask, a mask forming a 4 μm × 4 μm square dot pattern / 4 μm space was used for the 4 μm-thick resin film (Examples 1 to 10 and Comparative Example 1), and a mask forming a 1 μm × 1 μm square dot pattern / 1 μm space was used for the 1 μm-thick resin film (Examples 11 to 17 and Comparative Examples 2 and 3). Thereafter, within 10 minutes of exposure, development was carried out using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), forming a 4 μm×4 μm square dot pattern for the 4 μm-thick resin film, and a 1 μm×1 μm square dot pattern for the 1 μm-thick resin film. The square dot patterns were then baked on a hot plate for 5 minutes at the reflow temperature listed in Table 2. However, for Examples and Comparative Examples for which the reflow temperature is listed as "none" in Table 2, the square dot patterns were not baked at the reflow temperature. Furthermore, using the i-line stepper, 500 mJ / cm was applied to the entire surface of the square dot pattern. ２ After the second exposure, the microlenses were fabricated by baking on a hot plate for 10 minutes at the post-bake temperature shown in Table 2. The microlenses fabricated were rated as "□" if they had a square prism or a truncated square pyramid shape, and "◯" if they had a spherical or hemispherical shape. The evaluation results are shown in Table 2.

[0126]

[0127] [Evaluation of Chemical Resistance] Each of the positive photosensitive resin compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 3 was applied to a silicon wafer using a spin coater, and prebaked on a hot plate at 80°C for 90 seconds to form a resin film having a thickness shown in Table 2. Next, the entire surface of the resin film was irradiated with 500 mJ / cm using the i-line stepper. ２ After exposure to light, the wafer was baked on a hot plate for 10 minutes at the post-bake temperature listed in Table 2 to form a cured film. The silicon wafer on which the cured film was formed was immersed for 5 minutes at 23°C in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, and a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). The thickness of the cured film was measured before and after immersion, and the change in thickness before and after immersion was calculated. If the film thickness increased or decreased by 10% or more compared to the film thickness before immersion for even one of the solvents used for the immersion, the chemical resistance was evaluated as "×." If the film thickness increased or decreased by less than 10% for all solvents, the chemical resistance was evaluated as "○." The evaluation results are shown in Table 2.

[0128] [Transparency Evaluation] The positive photosensitive resin compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 3 were each applied to a quartz substrate using a spin coater, and prebaked on a hot plate at 80°C for 90 seconds to form a resin film having a thickness shown in Table 2. Next, the entire surface of the resin film was irradiated with 500 mJ / cm using the i-line stepper. ２ After exposure to light at 1000 W at 1000 W, the substrate was baked on a hot plate for 10 minutes at the post-bake temperature shown in Table 2 to form a cured film. The quartz substrate on which the cured film was formed was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer UV-2550 (manufactured by Shimadzu Corporation). When the transmittance at a wavelength of 400 nm was less than 90%, the transparency was evaluated as "×", and when it was 90% or higher, the transparency was evaluated as "○". The evaluation results are shown in Table 2.

[0129] [Evaluation of PED Stability (PED Resistance)] Each of the positive photosensitive resin compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 3 was applied to a silicon wafer using a spin coater and prebaked on a hot plate at 80°C for 90 seconds to form a resin film having a thickness shown in Table 2. Next, the resin film was subjected to a first exposure using the i-line stepper through a predetermined mask at an exposure dose shown in Table 2. Here, as the mask, a mask forming a 4 μm x 4 μm square dot pattern / 4 μm space was used for the 4 μm-thick resin film (Examples 1 to 10 and Comparative Example 1), and a mask forming a 1 μm x 1 μm square dot pattern / 1 μm space was used for the 1 μm-thick resin film (Examples 11 to 17 and Comparative Examples 2 and 3). Thereafter, within 10 minutes of the first exposure, development was carried out using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), forming a 4 μm x 4 μm square dot pattern for the 4 μm thick resin film and a 1 μm x 1 μm square dot pattern for the 1 μm thick resin film (Condition 1).

[0130] On the other hand, using the positive photosensitive resin compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 3, a 4 μm x 4 μm square dot pattern was formed on a silicon wafer for a 4 μm-thick resin film, and a 1 μm x 1 μm square dot pattern was formed for a 1 μm-thick resin film, following the same procedure as in Condition 1, except that a 2-hour interval was allowed at 23° C. between the first exposure and the next development (Condition 2). If positive patterning was possible under Condition 1 but not possible under Condition 2 because the exposed areas were not sufficiently dissolved in the developer, the PED stability (PED resistance) was evaluated as "x." If positive patterning was possible under both Conditions 1 and 2, the PED stability (PED resistance) was evaluated as "good." The evaluation results are shown in Table 2.

[0131] The results in Table 2 demonstrate that by using the positive photosensitive resin composition of the present invention, microlenses having a desired shape can be formed even in a low-temperature process at 150°C or less, and that these microlenses have high chemical resistance, high transparency, and high PED stability (PED resistance).

Claims

1. A positive photosensitive resin composition comprising the following component (A), the following component (B), the following component (C), and the following component (D), or the following component (A'), the following component (B), the following component (C), the following component (D), and the following component (E), and further comprising a solvent. Component (A): Alkali-soluble resin having an acid crosslinking group Component (A'): an alkali-soluble resin having no acid crosslinking groups Component (B): quinone diazide compound Component (C): Photoacid generator Component (D): A PED stability improver capable of inhibiting the initiation reaction or propagation reaction of cationic polymerization in exposed areas Component (E): a compound having at least two acid crosslinking groups in the molecule

2. 2. The positive photosensitive resin composition according to claim 1, wherein the component (A) and the component (A') are alkali-soluble resins having a carboxy group.

3. 2. The positive photosensitive resin composition according to claim 1, wherein the component (A) and the component (A') are alkali-soluble resins having a phenolic hydroxy group.

4. The positive photosensitive resin composition according to claim 3 , wherein the component (A) and the component (A′) are alkali-soluble resins having a structural unit represented by the following formula (1): 【Chemistry 1】 (In the formula, R ０ represents a hydrogen atom or a methyl group, X represents an -O- group or an -NH- group, R １ represents a single bond or an alkylene group having 1 or 2 carbon atoms; R ２ represents a methyl group, a represents 1 or 2, and b represents an integer of 0 to 2.

5. 5. The positive photosensitive resin composition according to claim 4, wherein in the structural unit represented by formula (1), X represents an --NH-- group.

6. The photosensitive resin composition according to claim 1 , wherein the acid crosslinkable group is a functional group containing an epoxy ring or an oxetane ring.

7. 5. The positive photosensitive resin composition according to claim 1, wherein the component (A) and the component (A') have a weight average molecular weight in terms of polystyrene of 1,000 to 100,000.

8. The positive photosensitive resin composition according to claim 1 , wherein the component (C) is a nonionic photoacid generator.

9. The positive photosensitive resin composition according to claim 8 , wherein the nonionic photoacid generator is a photoacid generator represented by the following formula (2): 【Chemistry 2】 (In the formula, R ３ is a hydrocarbon group or a perfluoroalkyl group having 1 to 10 carbon atoms; R ４ is a linear alkyl or alkoxy group having 1 to 8 carbon atoms, or a branched alkyl or alkoxy group having 3 to 8 carbon atoms.

10. The component (D) is a photobase generator or a basic compound.

3. The positive photosensitive resin composition according to claim 1.

11. The positive photosensitive resin composition according to claim 1 , wherein the component (D) is an amine.

12. 5. The positive photosensitive resin composition according to claim 1, wherein the content of the component (D) is 0.1 parts by mass to 3 parts by mass per 100 parts by mass of the component (A).

13. The positive photosensitive resin composition according to claim 1 , further comprising the following component (F): Component (F): Sensitizer

14. The positive photosensitive resin composition according to claim 1 , which is used for producing a microlens.

15. A cured film obtained from the positive photosensitive resin composition according to any one of claims 1 to 4.

16. A microlens produced from the positive-type photosensitive resin composition according to any one of claims 1 to 4.

17. 5. A method for producing a microlens, comprising: a coating step of coating a substrate with the positive photosensitive resin composition according to claim 1 to form a resin film; a first exposure step of exposing at least a portion of the resin film to light after the coating step; a development step of removing the exposed portion of the resin film with a developer after the first exposure step to form a pattern of the unexposed portion of the resin film; a second exposure step of further exposing the pattern after the development step; and a post-bake step of heating the pattern at a temperature of 150° C. or less after the second exposure step.

18. The method for producing a microlens according to claim 17 , further comprising a reflow step of heating the pattern at a temperature of 150° C. or less after the developing step and before the second exposure step.

19. The method for producing a microlens according to claim 17 , wherein the base material is a substrate on which a color filter is formed.

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