TW202319411A - Positive Photosensitive Resin Composition Containing Specific Copolymer - Google Patents

Abstract

To provide a novel positive photosensitive resin composition. A positive photosensitive resin composition containing the following component (A), the following component (B), the following component (C), and a solvent. Component (A): A copolymer of (a1) a monomer represented by the following formula (1), (a2) a monomer including an epoxy ring, and (a3) a monomer including a hydroxy group that has an acid dissociation constant pKa of 14 or above. Component (B): a quinone diazide compound. Component (C): a photoacid generator. (In the formula, R0 represents a hydrogen atom or a methyl group, R1 represents a single bond or an alkylene group having 1 or 2 carbon atoms, R2 represents a methyl group, a represents 1 or 2, and b represents an integer from 0 to 2).

Description

Positive Photosensitive Resin Composition Containing Specific Copolymer

The present invention relates to a positive-type photosensitive resin composition, a cured film obtained from the resin composition, a microlens and a manufacturing method thereof.

Image elements such as CCD image sensors and CMOS image sensors, or display elements such as liquid crystal displays and organic EL displays, sometimes use tiny lenses called microlenses in order to improve performance. For example, the aforementioned image sensor is provided with microlenses to increase etendue, which has the effect of increasing the sensitivity of the sensor.

One of the fabrication methods of the microlens is known as the etch back method (for example, Patent Document 1). That is, a resin layer for microlenses is formed on a color filter, a positive resist is coated on the resin layer, a part of the resist is exposed and developed, and a lens pattern is formed by heating if necessary. The lens pattern is used as an etching mask to etch back, and the shape of the lens pattern is transferred to the resin layer for microlenses to produce microlenses.

In addition, from the viewpoint of production cost reduction, a method of using the positive resist as it is as a microlens has been proposed. At this time, it is necessary to have both the characteristics of a resist and the characteristics of a microlens. Therefore, it must be a photosensitive resin composition that can not only be patterned positively, but also have excellent transparency and chemical resistance for the formed microlens. . Here, the shape of the microlens varies depending on the design of the device, and various shapes such as prism, cylinder, truncated pyramid, truncated cone, and spherical segment can be required. When producing truncated spherical microlenses, after forming a pattern such as a prism or a truncated pyramid, there is a known method of reflowing (fluidizing by heating. Also called melt flow or heat flow).

For example, Patent Document 2 proposes a photosensitive resin composition containing an alkali-soluble copolymer and a quinonediazide group-containing compound. By using this composition, a resin pattern is formed by exposure and development, and then heat is used to cross-link the phenolic hydroxyl group and the epoxy group to obtain a microlens.

However, in recent years, devices with low heat resistance, such as organic devices and flexible devices, have begun to be used, and therefore, the lowering of the temperature of the required steps has increased. Along with this, it is desired to produce a positive-type photosensitive resin composition that can produce a microlens with good performance even if it is produced in a low-temperature process. When producing a truncated spherical microlens, sufficient reflow is required even at low temperature. The upper limit temperature of specific steps requires 150°C, especially 130°C recently. The photosensitive resin composition described in Patent Document 2 uses thermal curing of phenolic hydroxyl groups and epoxy groups, but this thermal curing reaction usually requires high temperature conditions exceeding 150°C, so it is not suitable for low temperature processes below 130°C.

Therefore, Patent Document 3 proposes a radiation-sensitive resin composition containing a compound that generates an acid by radiation exposure, in addition to an alkali-soluble copolymer and a 1,2-quinonediazide compound. By using this composition, after forming a resin pattern by exposure and development, by re-exposure, a strong acid is generated inside the resin pattern, and cationic polymerization can be performed, so the process can be lowered in temperature. However, the monomers of the alkali-soluble copolymer used to form this composition contain carboxylic acid or carboxylic acid anhydride, and there is a possibility of residues when the copolymer is patterned. If part of the resin remains in the space between patterns, it will have a significant adverse effect on device characteristics, so a photosensitive resin composition that can be positively patterned without residue is required.

Also, Patent Document 4 proposes a radiation-sensitive resin composition containing, in addition to an alkali-soluble polymer and a quinonediazide compound, a compound that generates an acid having a pKa of 4.0 or less. The alkali-soluble polymer does not mention storage stability. Long-term reliability (HTS test, THS test, xenon arc test, etc.), this characteristic is unknown. The above-mentioned organic devices or flexible devices do not have practical reliability. Therefore, it is desired to manufacture long-term reliability tests such as HTS test (high temperature test), THS test (high temperature and high humidity test), xenon arc test, etc. After that, it will not deteriorate, and it is a photosensitive resin composition of microlens with good performance. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 1-10666 [Patent Document 2] Japanese Patent Laid-Open No. 2007-33518 [Patent Document 3] Japanese Patent Laid-Open No. 2009-75329 [Patent Document 4] Japanese Patent Laid-Open No. 2020-101659

[Problem to be Solved by the Invention]

The present invention is completed based on the above circumstances. The purpose of the present invention is to provide no residue, positive patterning, and microlenses with desired truncated spherical or hemispherical shapes can be formed even in a low temperature process below 130°C. , The formed microlens has excellent transparency, drug resistance and long-term reliability positive photosensitive resin composition. [Means to solve the problem]

(式中，R ⁰表示氫原子或甲基，R ¹表示單鍵或碳原子數1或2之伸烷基，R ²表示甲基，a表示1或2，b表示0至2之整數)。 The inventors of the present invention have completed the present invention as a result of intensive examinations in order to solve the aforementioned problems. The first aspect of the present invention is a positive-type photosensitive resin composition containing the following (A) component, the following (B) component, the following (C) component, and a solvent. (A) Component: Copolymerization of (a1) a monomer represented by the following formula (1), (a2) an epoxy ring-containing monomer, and (a3) a hydroxyl-containing monomer having an acid dissociation constant pKa of 14 or more Copolymer without carboxyl group and carboxylic acid anhydride group, (B) component: quinone diazide compound (C) component: photoacid generator

(In the formula, R ⁰ represents a hydrogen atom or a methyl group, R ¹ represents a single bond or an alkylene group with 1 or 2 carbon atoms, R ² represents a methyl group, a represents 1 or 2, and b represents an integer from 0 to 2) .

(式中，R ⁰各自獨立表示氫原子或甲基，R ³表示下述式(I)表示之2價有機基，R ⁴表示下述式(4)或下述式(5)表示之1價有機基，R ⁵表示下述式(I’)表示之1價有機基)

(式中，c表示0至3之整數，d表示1至3之整數，e各自獨立表示2至6之整數，＊表示與前述式(2)或前述式(3)表示之單體之烯基之鍵結鍵，・表示與前述式(4)或前述式(5)表示之1價有機基之鍵結鍵)。 The aforementioned (a2) monomer containing an epoxy ring is a monomer represented by the following formula (2), and the aforementioned (a3) monomer containing a hydroxyl group having an acid dissociation constant pKa of 14 or more is, for example, represented by the following formula (3) of monomer.

(In the formula, R ⁰ each independently represents a hydrogen atom or a methyl group, R ³ represents a divalent organic group represented by the following formula (I), R ⁴ represents 1 represented by the following formula (4) or the following formula (5) Valence organic group, R ⁵ represents the monovalent organic group represented by the following formula (I')

(wherein, c represents an integer from 0 to 3, d represents an integer from 1 to 3, e each independently represents an integer from 2 to 6, * represents the alkene compound with the monomer represented by the aforementioned formula (2) or the aforementioned formula (3) The bonding bond of the group, · represents the bonding bond with the monovalent organic group represented by the aforementioned formula (4) or the aforementioned formula (5).

(式中，R ⁰各自獨立表示氫原子或甲基，R ¹表示表示單鍵或碳原子數1或2之伸烷基，R ²表示甲基，b表示0至2之整數，R ⁴表示下述式(4)或下述式(5)表示之1價有機基，e表示2至6之整數)。

The aforementioned (A) component, for example, a copolymer having a structural unit represented by the following formula (1a), a structural unit represented by the following formula (2a), and a structural unit represented by the following formula (3a),

(In the formula, R ⁰ each independently represents a hydrogen atom or a methyl group, R ¹ represents a single bond or an alkylene group with 1 or 2 carbon atoms, R ² represents a methyl group, b represents an integer from 0 to 2, R ⁴ represents A monovalent organic group represented by the following formula (4) or the following formula (5), e represents an integer of 2 to 6).

The polystyrene conversion weight average molecular weight of the said (A) component is 5,000-30,000, for example.

(式中，R ⁶表示碳原子數1至10之烴基或全氟烷基，R ⁷表示碳原子數1至8之直鏈狀之烷基或烷氧基，或碳原子數3至8之支鏈鏈狀之烷基或烷氧基)。 The aforementioned (C)component is, for example, a nonionic photoacid generator. This nonionic photoacid generator is, for example, a photoacid generator represented by the following formula (6).

(wherein, R ⁶ represents a hydrocarbon group or perfluoroalkyl group with 1 to 10 carbon atoms, R ⁷ represents a linear alkyl or alkoxy group with 1 to 8 carbon atoms, or a perfluoroalkyl group with 3 to 8 carbon atoms branched chain alkyl or alkoxy).

The positive photosensitive resin composition of the present invention may further contain the following (D) component, (D) Component: polyfunctional epoxy compound.

The positive photosensitive resin composition of the present invention may further contain the following (E) component, (E) component: a sensitizer.

The positive photosensitive resin composition of the present invention is, for example, used for making microlenses.

The second aspect of the present invention is a cured film obtained from the aforementioned positive photosensitive resin composition.

The third aspect of the present invention is a microlens made of the aforementioned positive photosensitive resin composition.

The fourth aspect of the present invention is a method of manufacturing a microlens, which includes the following steps, A coating step of coating the aforementioned positive-type photosensitive resin composition on a substrate to form a resin film, after the aforementioned coating step, a first exposure step of exposing at least a part of the resin film, after the aforementioned first exposure step , a developing step of removing the exposed portion of the aforementioned resin film by a developing solution to form a pattern of the unexposed portion of the resin film, after the aforementioned developing step, a second exposing step of further exposing the aforementioned pattern, and the aforementioned second exposing After the step, the aforementioned pattern is heated at a temperature below 130° C. and then baked.

After the aforementioned developing step and before the aforementioned second exposure step, a reflow step of heating the aforementioned pattern at a temperature below 130° C. may be included.

The above-mentioned substrate is, for example, a substrate on which color filters are formed. [Invention effect]

According to the present invention, since the component (A) of the specific copolymer, the component (B) of the quinone diazide compound, and the component (C) of the photoacid generator are contained at the same time, no residue can be provided, and positive patterning can be provided. , Even at a low temperature process below 130°C, microlenses with desired truncated spherical or hemispherical shapes can be formed, and the formed microlenses have excellent transparency, chemical resistance and long-term reliability. Positive photosensitive resin Composition. [Mode of Implementing the Invention]

(式中，R ⁰表示氫原子或甲基，R ¹表示單鍵或碳原子數1或2之伸烷基，R ²表示甲基，a表示1或2，b表示0至2之整數)。 The positive photosensitive resin composition of the present invention will be described in more detail. [Component (A)] The component (A) contained in the positive-type photosensitive resin composition of the present invention is (a1) a monomer represented by the following formula (1), (a2) a monomer containing an epoxy ring, and (a3) Copolymers of monomers containing hydroxyl groups with an acid dissociation constant pKa of 14 or more, and copolymers free of carboxyl groups and carboxylic acid anhydride groups. Here, the carboxylic acid anhydride group is a divalent group represented by -CO-O-CO-.

(In the formula, R ⁰ represents a hydrogen atom or a methyl group, R ¹ represents a single bond or an alkylene group with 1 or 2 carbon atoms, R ² represents a methyl group, a represents 1 or 2, and b represents an integer from 0 to 2) .

(a1) The monomer represented by the aforementioned formula (1) includes, for example, N-(2-hydroxyphenyl)(meth)acrylamide, N-(3-hydroxyphenyl)(meth)acrylamide, N-(4-hydroxyphenyl)(meth)acrylamide, N-(4-hydroxybenzyl)(meth)acrylamide, N-(4-hydroxyphenylethyl)(meth)acrylamide Amine, N-(3,5-Dimethyl-4-hydroxyphenyl)(meth)acrylamide, N-(3,5-Dimethyl-4-hydroxybenzyl)(meth)acrylamide amine, and N-(3,5-dimethyl-4-hydroxyphenethyl)(meth)acrylamide. These monomers may be used alone or in combination of two or more.

When relative to 100 parts by mass of the monomers of (a1), (a2) and (a3) above, the proportion of the monomer represented by (a1) the aforementioned formula (1) is 5 parts by mass to 60 parts by mass, preferably 8 to 50 parts by mass, more preferably 10 to 40 parts by mass.

此等之單體可1種單獨使用，也可組合2種以上使用。 (a2) Monomer containing epoxy ring A monomer having at least one epoxy ring in its molecule. Specific examples thereof include monomers represented by the following formulas (2-1) to (2-16).

These monomers may be used alone or in combination of two or more.

When relative to 100 parts by mass of the monomers of (a1), (a2) and (a3) above, the ratio of (a2) the monomer containing an epoxy ring is 20 to 80 parts by mass, preferably 30 parts by mass Parts to 70 parts by mass, more preferably 40 parts to 60 parts by mass.

此等之單體，可1種單獨使用，也可組合2種以上使用。 (a3) The acid dissociation constant pKa is 14 or more monomers containing hydroxyl groups, and the acid dissociation constant pKa (in the case of polyacids, the lowest value) is 14 or more monomers with at least one hydroxyl group. Specific examples include the following Monomers represented by formula (3-1) to formula (3-25). The mono-systemic acid dissociation constant pKa of functional groups below 13 does not include, for example, silanol groups, fluoroalcohol groups, maleimide groups, carboxyl groups, and phenolic hydroxyl groups.

These monomers may be used alone or in combination of two or more.

The ratio of (a3) the hydroxyl group-containing monomer having an acid dissociation constant pKa of 14 or more relative to 100 parts by mass of the monomers of (a1), (a2) and (a3) above is 5 parts by mass to 60 parts by mass , preferably 8 to 50 parts by mass, more preferably 10 to 40 parts by mass.

(A) The weight average molecular weight of a component is 5,000-30,000, Preferably it is 5,000-20,000, _More preferably, it is 5,000-15,000. When the weight average molecular weight of the component (A) is within the aforementioned range, the chemical resistance is not impaired, and a good pattern can be formed after development.

The glass transition temperature of the component (A) is 70°C to 130°C. By adjusting the glass transition temperature of component (A) within the aforementioned range, even at a low-temperature process below 130°C, it has good reflowability, and can produce desired truncated spherical or hemispherical microlenses.

[(B) component] The (B) component 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. For example, a hydroxyl-containing compound and a 1,2-quinonediazide group can be used. - Condensates of naphthoquinonediazidesulfonic acid halides. Specifically, 10 mol% to 100 mol%, preferably 20 mol% to 95 mol%, of the hydroxyl groups of the aforementioned hydroxyl-containing compounds are halogenated with the aforementioned 1,2-naphthoquinonediazidesulfonic acid Esterified compounds. Various well-known methods can be used for the aforementioned condensation reaction.

Examples of the aforementioned hydroxyl group-containing compound include the compounds shown below. Dihydroxybenzophenones such as 2,4-dihydroxybenzophenone; Trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; 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, etc. Methyl ketones; Pentahydroxybenzophenones such as 2,3,4,2’,4’-pentahydroxybenzophenone and 2,3,4,2’,6’-pentahydroxybenzophenone; Hexahydroxybenzophenone such as 2,4,6,3',4',5'-hexahydroxybenzophenone and 3,4,5,3',4',5'-hexahydroxybenzophenone Ketones; 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,3,3-tri(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-dimethyl-4-hydroxy Phenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol, bisphenol (2,5-Dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobiindene (spirobiindene)-5 ,6,7,5',6',7'-hexanol, and 2,2,4-trimethyl-7,2',4'-trihydroxyflavan (trihydroxyflavan) etc. (polyhydroxyphenyl ) alkanes; 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 (Chromane), 1-[1-(3-{1-(4-hydroxyphenyl) -1-methylethyl}-4,6-dihydroxyphenyl)-1-methylethyl]-3-(1-(3-{1-(4-hydroxyphenyl)-1-methyl Ethyl}-4,6-dihydroxyphenyl)-1-methylethyl)benzene, and 4,6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1, Other compounds such as 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]ethylene]bisphenol.

The aforementioned 1,2-naphthoquinonediazidesulfonic acid halide, preferably 1,2-naphthoquinonediazidesulfonic acid chloride, more preferably 1,2-naphthoquinone-2-diazide-4- Sulfonic acid chloride and 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride, more preferably 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride.

(B) The compound of a component may be used individually by 1 type, and may use it in combination of 2 or more types.

With respect to 100 parts by mass of component (A), 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, more preferably 15 to 40 parts by mass. When the content of component (B) is within the above range, the sensitivity will not be significantly reduced, and the solubility difference between the exposed part and the unexposed part to the alkali developer can be large, and the positive pattern can be formed with a relatively low exposure change.

[(C) ingredient] The component (C) contained in the positive-type photosensitive resin composition of the present invention is not particularly limited as long as it is a compound that can generate an acid with an acid dissociation constant pKa of 4 or less by exposure, and examples thereof include ionic photoacid generators and non-ionic photoacid generators.

As the ionic photoacid generator, for example, the products and compounds shown below can be used. Adeka Arkls (registered trademark) SP-056, Dom SP-171 (above, manufactured by ADEKA), CPI (registered trademark)-100B(40), Dom-100P, Dom-101A, Dom-110A, Dom-110B , Same-110P, Same-200K, Same-210S, Same-300, Same-310B, Same-310FG, Same-400, Same-410B, Same-410S, VC-1FG, ES-1B (above, san-apro (stock)), TPS-TF, TPS-CS, TPS-PFBS (above, Toyo Gosei Kogyo Co., Ltd.), 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 (above, manufactured by Midori Chemical Co., Ltd.), etc.; Adeka Arkls (registered trademark) SP-140 (above, manufactured by ADEKA), IK-1, IK-1PC(80), IK-1FG, (above, manufactured by san-apro), DTBPI-PFBS ( Above, Toyo Gosei Kogyo 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 (above, manufactured by Midori Chemical Co., Ltd.), etc. .

As the nonionic photoacid generator, for example, the products and compounds shown below can be used. Adeka Arkls (registered trademark) SP-082, SP-606 (above, manufactured by ADEKA), NA-CS1, NP-TM2, NP-SE10 (above, manufactured by san-apro), 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 N-sulfonyloxyimides such as -109, NAI-1002, NAI-1003, and NAI-1004 (above, manufactured by Midori Chemical Co., Ltd.); IRGACURE (registered trademark) PAG103, PAG121, PAG203 (above, manufactured by BASF JAPAN), PAI-01, PAI-101, PAI-106, PAI-1001, PAI-1002, PAI-1003, and PAI- Oxime sulfonates such as 1004 (above, manufactured by Midori Chemical Co., Ltd.); TAZ-100, TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-107, TAZ-108, TAZ-109, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ- 122. Triazines such as TAZ-123, TAZ-203, and TAZ-204 (the above, manufactured by Midori Chemical Co., Ltd.).

Among these ionic photoacid generators and nonionic photoacid generators, a nonionic photoacid generator is preferred from the standpoint of storage stability or sensitivity, and N-sulfonyloxyacid is more preferred. The imines are more preferably compounds represented by the aforementioned formula (6). Specific examples of the compound represented by the aforementioned formula (6) include compounds represented by the following formula (6-1) to the following formula (6-28).

(C) The compound of a component may be used individually by 1 type, and may use it in combination of 2 or more types.

With respect to 100 parts by mass of component (A), the content of component (C) in the positive photosensitive resin composition of the present invention is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass. When the content of the component (C) is within the above range, the drug resistance can be improved without impairing the transparency.

[(D) ingredient] The positive-type photosensitive resin composition of the present invention contains component (D) as an optional component, and it is not particularly limited as long as it is a compound having at least two epoxy rings in the molecule. For example, the products and compounds shown below can be used . EPICLON (registered trademark) 830, same 830-S, same 835, same 840, same 840-S, same 850, same 850-S, same 850-LC, same HP-820 (above, DIC (stock) system), DENACOL (registered trademark) EX-201, same EX-211, same EX-212, same EX-252, same EX-810, same EX-811, same EX-821, same EX-830, same EX-832, same EX-841, same EX-850, same EX-851, same EX-861, same EX-920, same EX-931, same EX-991L, same EX-313, same EX-314, same EX-321, same EX-321L, same EX-411, same EX-421, same EX-512, same EX-521, same EX-612, same EX-614, same EX-614B, same EX-622 (above, nagase chemtex (stock ) system), jER (registered trademark) 152, same 630, same 825, same 827, same 828, same 828EL, same 828US, same 828XA (above, Mitsubishi Chemical (stock) system), TETRAD (registered trademark)-C, Same-X (above, manufactured by Mitsubishi Gas Chemical Co., Ltd.), CELLOXID (registered trademark) 2021P, same 2081, EPOLEAD (registered trademark) GT401 (above, manufactured by DAICEL), EPOTOHTO (registered trademark) YD-115, Same as YD-115CA, same as YD-127, same as YD-128, same as YD-128G, same as YD-128S, same as YD-128CA, same as YD-8125, same as YD-825GS, same as YDF-170, same as YDF-170N, Same as YDF-8170C, same YDF-870GS, same ZX-1059, same YH-404, same YH-434, same YH-434L, same YH-513, same YH-523, same ST-3000 (above, NIPPON STEEL Chemical & Material (stock) system), ADEKA RESIN (registered trademark) EP-4100, same EP-4100G, same EP-4100E, same EP-4100TX, same EP-4300E, same EP-4100, same EP-4400, same EP -4520S, Same as EP-4530, Same as EP-4901, Same as EP-4901E, Same as EP-4000, Same as EP-4005, Same as EP-7001, Same as EP-4080E, Same as EPU-6, Same as EPU-7N, Same as EPU -11F, same EPU-15F, same EPU-1395, same EPU-73B, same EPU-17, same EPU-17T-6, same EPR-1415-1, same EPR-2000, same EPR-2007, ADEKA GLYCIROL ( Registered trademark) ED-503, Same as ED-503G, Same as ED-506, Same as ED-523T, Same as ED-505 (above, manufactured by ADEKA), SUMI-EPOXY (registered trademark) ELM-434, Same as ELM- 434L, same as ELM-434VL, same as ELM-100, same as ELM-100H (above, manufactured by Sumitomo Chemical), EpoliteM-1230, same as 40E, same as 100E, same as 200E, same as 400E, same as 70P, same as 200P, same 400P, same as 1500NP, same as 1600, same as 80MF, same as 4000, same as 3002(N) (above, manufactured by Kyoeisha Chemical Co., Ltd.) and THI-DE (manufactured by ENEOS Co., Ltd.) etc. multifunctional epoxy resin.

(D) The compound of a component may be used individually by 1 type, and may use it in combination of 2 or more types.

When the positive photosensitive resin composition of the present invention contains component (D), the content of component (D) is 5 to 100 parts by mass, preferably 10 to 100 parts by mass relative to 100 parts by mass of component (A). 50 parts by mass. (D) When the content of the component is within the above-mentioned range, drug resistance can be improved.

[(E) component] The (E) component contained as an optional component in the positive-type photosensitive resin composition of the present invention is not particularly limited as long as it is a substance capable of transmitting the energy of irradiated light to other substances, and examples thereof include p-tolylquinone ( Toluquinone), 1-phenyl-1,2-propanedione, phenanthrene, anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dioctyloxyanthracene, 3,7-dimethoxyanthracene, pyrene, perylene, xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-di Ethylthioxanthone, and 2-isopropylthioxanthone, etc.

(E) The compound of a component may be used individually by 1 type, and may use it in combination of 2 or more types.

When the positive-type photosensitive resin composition of the present invention contains component (E), the content of component (E) is 0.01 to 5 parts by mass, preferably 0.05 to 5 parts by mass relative to 100 parts by mass of component (A). 3 parts by mass, more preferably 0.1 to 1 part by mass. When the content of the component (E) was within the above-mentioned range, it was found that the component (C) effectively sensitizes the photoacid generator without impairing the transparency, and improves the resistance to chemicals.

[solvent] The solvent contained in the positive-type photosensitive resin composition of the present invention is not particularly limited as long as it dissolves (A) component to (C) component, and any component added if necessary. For example, hydrocarbons, halogenated All organic solvents of hydrocarbons, ethers, alcohols, aldehydes, ketones, esters, amides, and nitriles.

The aforementioned hydrocarbons include, for example, n-pentane, cyclopentane, methylcyclopentane, n-hexane, isohexane, cyclohexane, methylcyclohexane, ethylcyclohexane, n-heptane , Benzene, toluene, о-xylene, m-xylene, p-xylene and mesitylene, etc.

The aforementioned halogenated hydrocarbons include, for example, dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, dichloroethane, trichloroethane, tetrachloroethane, hexachloroethane, dichloroethylene, trichloroethylene , tetrachloroethylene, chlorobenzene, hydrofluorocarbons and perfluorocarbons.

The aforementioned ethers include, for example, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, di-tert-butyl ether, di-n-pentyl ether, diisopropyl ether, Amyl 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 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, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol di 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 di Methyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether and tripropylene glycol dibutyl ether, etc.

The aforementioned alcohols include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, tert-butanol, 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, 2-heptanol, 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 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 and other alcohols, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol Alcohol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,2-pentanediol, Dihydric alcohols such as 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, and 1,2-hexanediol, and trihydric alcohols such as glycerin Alcohols, etc.

The aforementioned aldehydes include, for example, acetaldehyde (ethanal), propionaldehyde, 2-methyl-1-propionaldehyde, butyraldehyde, 3-methylbutyraldehyde, valeraldehyde, and benzaldehyde.

The aforementioned ketones include, for example, 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, etc.

The aforementioned esters include, for example, 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, isohexyl Acetate, cyclohexyl acetate, n-heptyl acetate, isoheptyl acetate, n-octyl acetate, isooctyl acetate, benzyl acetate, ethylene glycol mono Methyl 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 glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate 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 ester, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl butyl 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, methyl isobutyrate, ethyl isobutyrate, n-propyl isobutyrate butyrate, isopropyl isobutyrate, n-butyl isobutyrate, isobutyl isobutyrate, tert-butyl isobutyrate, methyl lactate (lactate), ethyl lactate , n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, tert-butyl lactate, methyl acetyl acetate, ethyl acetyl acetate, n-Propyl acetyl acetate, isopropyl acetyl acetate, n-butyl acetyl acetate, isobutyl acetyl acetate, tert-butyl acetyl acetate, dimethyl Malonate, diethylmalonate, glycerol triacetate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, δ-caprolactone Esters and ε-caprolactone, etc.

The aforementioned amides include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone and N - Ethylpyrrolidone and the like.

The aforementioned nitriles include, for example, acetonitrile, propionitrile, and butyronitrile.

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

Among these solvents, propylene glycol monomethyl ether and propylene glycol monomethyl ether are preferred from the viewpoint of improving the flatness of the cured film formed by coating the positive-type photosensitive resin composition of the present invention on the substrate. Ester, Propylene Glycol Monoethyl Ether, Propylene Glycol Monopropyl Ether, 2-Heptanone, Ethyl Lactate, n-Butyl Lactate, Cyclopentanone and Cyclohexanone.

[Surfactant, other additives] The positive photosensitive resin composition of the present invention may optionally contain a surfactant in order to improve coatability. Surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene octylphenyl ether. Polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitol Sorbitan fatty acid esters such as sugar alcohol monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, polyoxyethylene Sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan tristearate, EFTOP (registered trademark) EF301, same EF303, same EF352 (above, Mitsubishi Materials Electronic Chemicals ( share) system), Megafac (registered trademark) F-171, same as F-173, same as R-30, same as R-40, same as R-40-LM (above, DIC (stock) system), FluoradFC430, same as FC431 ( Above, Sumitomo 3M (stock)), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, same as SC101, same as SC102, same as SC103, same as SC104, same as SC105, same as SC106 (AGC (stock)) , FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, etc. ) and other fluorine-based surfactants, and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more.

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 relative to 100 parts by mass of the total solid content of the positive photosensitive resin composition except the solvent. The mass part is preferably 0.005 mass part to 1 mass part, more preferably 0.01 mass part to 0.5 mass part.

The positive-type photosensitive resin composition of the present invention may further contain additives such as curing aids, antioxidants, ultraviolet absorbers, plasticizers, and adhesion aids, if necessary, within the range that does not impair the effects of the present invention.

[Preparation Method of Positive Photosensitive Resin Composition] The preparation method of the positive photosensitive resin composition of the present invention is not particularly limited, for example, a method of dissolving components (A) to (C) and any other components in a solvent to form a homogeneous solution. Also, if necessary, the solution may be filtered using a filter having a pore size of 0.1 μm to 10 μm.

[Manufacturing method of microlens] A fabrication example of a microlens using the positive photosensitive resin composition of the present invention will be described. ＜Coating procedure＞ The positive-type photosensitive resin composition of the present invention is coated on a substrate (such as a semiconductor substrate, a glass substrate, a quartz substrate, a plastic substrate, a silicon substrate, etc.) by an appropriate coating method such as a spin coater or a coater. Wafers, and substrates with various metal films or color filters formed on the surface of these substrates), preferably after that, pre-baking is performed using heating means such as an oven or a heating plate, and the solvent is removed to form a resin membrane. The pre-baking conditions can be suitably selected from the range of baking temperature from 60°C to 130°C and baking time from 20 seconds to 30 minutes. The film thickness of the formed resin film is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.

<First Exposure Step> After the aforementioned coating step, at least a part of the formed resin film is exposed through a specific mask. As the light for exposure, for example, g-line, i-line, KrF excimer laser and ArF excimer laser can be used. The exposure amount is suitably selected from the range of 20mJ/cm ² to 2000mJ/cm ² .

＜Development step＞ After the aforementioned first exposure step, the exposed portion of the resin film is removed by a developer to form a pattern of the unexposed portion of the resin film. The image development method is not particularly limited, and examples thereof include a dipping method, a paddle method, and a spray method. The developing conditions are suitably selected from the range of a developing temperature of 5° C. to 50° C. and a developing time of 10 seconds to 300 seconds. The developing solution used is not particularly limited as long as it can remove the exposed part, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium phosphate, potassium phosphate, ammonia, tetramethyl hydroxide Aqueous alkali solutions such as ammonium (TMAH) and tetraethylammonium hydroxide (TEAH). In addition, it can also be used as a developing solution by adding an appropriate amount of a surfactant or an organic solvent to an alkaline aqueous solution. These developers may be used alone or in combination of two or more.

After development, in order to wash off the developing solution, it can be washed with a cleaning solution. After development or cleaning, in order to remove residual developer or cleaning solution, it can be dried by rotating a rotatable device such as a spin coater or a coater, or by blowing compressed air or nitrogen.

＜Reflow process＞ Before the second exposure step described later, the pattern formed after the aforementioned development step may also include a reflow step of heating using heating means such as an oven or a heating plate. The reflow conditions are suitably selected from the range of baking temperature of 80°C to 130°C and baking time of 1 minute to 90 minutes. Also, even if the reflow step is omitted, a spherical or hemispherical microlens can be manufactured, but by including the reflow step, a spherical or hemispherical microlens can be manufactured at a lower temperature.

<Second Exposure Step> After the aforementioned developing step, or after the aforementioned reflow step, the aforementioned pattern is further exposed. As the light for exposure, for example, g-line, i-line, KrF excimer laser and ArF excimer laser can be used. The exposure amount is suitably selected from the range of 100 mJ/cm ² to 5000 mJ/cm ² .

＜Post-baking step＞ After the aforementioned second exposure step, the aforementioned pattern is heated using heating means such as an oven or a heating plate. Post-baking conditions are suitably selected from the range of a baking temperature of 80° C. to 130° C. and a baking time of 1 minute to 90 minutes.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

The apparatus and conditions for measuring the polystyrene conversion weight average molecular weight M _W of a copolymer are as follows. Device: GPC system made by JASCO Co., Ltd. Column: Shodex (registered trademark) KF-804L and KF-803L Column oven: 40°C Flow rate: 1mL/min Eluent: THF Sample concentration: 10mg/mL Sample injection volume: 20 μL Standard substance: Monodisperse polystyrene Detector: Differential refractometer

The compounds used in Examples and Comparative Examples are as follows. ＜Component (B)＞ B-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol 1 mol with 1,2- Condensate of naphthoquinone-2-diazide-5-sulfonic acid chloride 1.5 moles ＜(C)Ingredient＞ C-1: Adeka Arkls (registered trademark) SP-606 (made by ADEKA) C-2: CPI-110P (san-apro (stock) system) ＜(D)Ingredient＞ D-1: EPOLEAD (registered trademark) GT401 (made by DAICEL) ＜Component (E)＞ E-1: 2-isopropylthioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.) ＜Surfactant＞ R-40: Megafac (registered trademark) R-40 (manufactured by DIC Co., Ltd.)

[Synthesis of Component (A)] <Synthesis Example 1> A stirrer and 50 g of propylene glycol monomethyl ether as a solvent were placed in a flask, immersed in a heated oil bath, and kept at 87°C. Next, mix 30 g of N-(4-hydroxyphenyl)methacrylamide as (a1) the monomer represented by the aforementioned formula (1), and 3,4 - 60 g of epoxy cyclohexyl methyl methacrylate (the aforementioned formula (2-6)), 2-hydroxyethyl methacrylate as (a3) a monomer containing a hydroxyl group with an acid dissociation constant pKa of 14 or more (Aforementioned formula (3-5)) 10g, 2,2'- azobisisobutyronitrile 4.5g as thermal free radical generating agent, and the solution of propylene glycol monomethyl ether 194g as solvent, put in the dropping funnel, and The said flask was connected, and after nitrogen substitution, it dripped over 3 hours, stirring. After completion|finish of dripping, it was made to react for 15 more hours, and the solution (solid content concentration: 30 mass %) of a copolymer was obtained. The polystyrene conversion weight average molecular weight _Mw of the obtained copolymer was 8,000. Hereinafter, in this specification, the copolymer obtained in Synthesis Example 1 is represented by A-1.

<Synthesis Example 2> 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 same method as in Synthesis Example 1 was used to obtain a copolymer solution (solid content concentration: 30% by mass). The polystyrene conversion weight average molecular weight _Mw of the obtained copolymer was 8,000. Hereinafter, in this specification, the copolymer obtained in Synthesis Example 2 is represented by A-2.

<Synthesis Example 3> 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 same method as in Synthesis Example 1 was used to obtain a copolymer solution (solid content concentration: 30% by mass). The polystyrene conversion weight average molecular weight _Mw of the obtained copolymer was 8,000. Hereinafter, in this specification, the copolymer obtained in Synthesis Example 3 is represented by A-3.

<Synthesis Example 4> A stirring bar and 50 g of propylene glycol monomethyl ether as a solvent were placed in a flask, immersed in a heated oil bath, and maintained at 80°C. Next, 40 g of N-(4-hydroxyphenyl) methacrylamide and 60 g of 3,4-epoxycyclohexyl methyl methacrylate were mixed as monomers, and 2 , A solution of 4.4 g of 2'-azobisisobutyronitrile and 194 g of propylene glycol monomethyl ether as a solvent was placed in a dropping funnel, connected to the aforementioned flask, and dropped while stirring for 3 hours after nitrogen substitution. After completion|finish of dripping, it was made to react for 15 more hours, and the solution (solid content concentration: 30 mass %) of a copolymer was obtained. The polystyrene conversion weight average molecular weight _Mw of the obtained copolymer was 11,000. Hereinafter, in this specification, the copolymer obtained in Synthesis Example 4 is represented by A-4.

<Synthesis Example 5> A stirring bar and 90 g of propylene glycol monomethyl ether as a solvent were placed in a flask, immersed in a heated oil bath, and maintained at 70°C. Next, mix 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 propylene glycol as a solvent. A solution of 105 g of monomethyl ether was placed in a dropping funnel, connected to the aforementioned flask, and after nitrogen substitution, it was dropped over 3 hours while stirring. After completion|finish of dripping, it was made to react for 15 more hours, and the solution (solid content concentration: 35 mass %) of a copolymer was obtained. The polystyrene conversion weight average molecular weight _Mw of the obtained copolymer was 18,000. Hereinafter, in this specification, the copolymer obtained in Synthesis Example 5 is represented by A-5.

[Preparation of positive photosensitive resin composition] <Example 1> 70.0 g (solid content: 21.0 g) of copolymer A-1 obtained in Synthesis Example 1 as component (A) was prepared, 4.8 g of B-1 as component (B) was prepared, and C-1 as component (C) Prepare 0.2g, 6.3g of D-1 as component (D), 0.01g of R-40 as surfactant, 6.6g of propylene glycol monomethyl ether and 23.8g of propylene glycol monomethyl ether acetate as solvent , to become a homogeneous solution. Then, it filtered using the fine filter made of polyethylene with a pore diameter of 0.10 micrometers, and obtained the positive photosensitive resin composition (29 mass % of solid content concentration).

<Example 2> Blend 70.0 g (21.0 g of solid content) of copolymer A-1 obtained in Synthesis Example 1 as component (A), 4.8 g of B-1 as component (B), and C-2 as component (C) Prepare 0.3g, 6.3g of D-1 as component (D), 0.01g of R-40 as surfactant, 6.8g of propylene glycol monomethyl ether and 23.9g of propylene glycol monomethyl ether acetate as solvent , to become a homogeneous solution. Then, it filtered using the fine filter made of polyethylene with a pore diameter of 0.10 micrometers, and obtained the positive photosensitive resin composition (29 mass % of solid content concentration).

<Example 3> Blend 70.0 g (solid content: 21.0 g) of copolymer A-2 obtained in Synthesis Example 2 as component (A), 4.8 g of B-1 as component (B), and C-1 as component (C) Prepare 0.2g, 6.3g of D-1 as component (D), 0.01g of R-40 as surfactant, 6.6g of propylene glycol monomethyl ether and 23.8g of propylene glycol monomethyl ether acetate as solvent , to become a homogeneous solution. Then, it filtered using the fine filter made of polyethylene with a pore diameter of 0.10 micrometers, and obtained the positive photosensitive resin composition (29 mass % of solid content concentration).

<Example 4> Blend 70.0 g (21.0 g of solid content) of copolymer A-3 obtained in Synthesis Example 3 as component (A), 4.8 g of B-1 as component (B), and C-1 as component (C) Prepare 0.2g, 6.3g of D-1 as component (D), 0.01g of R-40 as surfactant, 30.2g of propylene glycol monomethyl ether and 79.2g of propylene glycol monomethyl ether acetate as solvent , to become a homogeneous solution. Then, it filtered using the fine filter made of polyethylene with a pore diameter of 0.10 micrometers, and obtained the positive type photosensitive resin composition (17 mass % of solid content concentration).

<Example 5> Blend 70.0 g (21.0 g of solid content) of copolymer A-3 obtained in Synthesis Example 3 as component (A), 4.8 g of B-1 as component (B), and C-1 as component (C) 0.2 g was prepared, 0.01 g of R-40 as a surfactant, 25.1 g of propylene glycol monomethyl ether as a solvent, and 74.1 g of propylene glycol monomethyl ether acetate were prepared to form a uniform solution. Then, it filtered using the fine filter made of polyethylene with a pore diameter of 0.10 micrometers, and obtained the positive photosensitive resin composition (solid content concentration: 15 mass %).

<Example 6> Blend 84.0 g (25.2 g of solid content) of copolymer A-3 obtained in Synthesis Example 3 as component (A), 5.8 g of B-1 as component (B), and C-1 as component (C) Prepare 0.2g, 7.6g of D-1 as component (D), 0.05g of E-1 as component (E), 0.01g of R-40 as surfactant, and propylene glycol monomethyl ether as solvent 36.2g and propylene glycol monomethyl ether acetate were formulated into 95.0g to form a homogeneous solution. Then, it filtered using the fine filter made of polyethylene with a pore diameter of 0.10 micrometers, and obtained the positive type photosensitive resin composition (17 mass % of solid content concentration).

＜Comparative example 1＞ Blend 70.0 g (solid content: 21.0 g) of copolymer A-4 obtained in Synthesis Example 4 that does not correspond to (A) component, blend 4.8 g as (B) component B-1, and mix as (C) component C 0.2g of -1, 6.3g of D-1 as component (D), 0.01g of R-40 as a surfactant, 9.4g of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate as a solvent 25.0g to become a homogeneous solution. Then, it filtered using the fine filter made of polyethylene with a pore diameter of 0.10 micrometers, and obtained the positive photosensitive resin composition (28 mass % of solid content concentration).

＜Comparative example 2＞ Blend 60.0 g (solid content: 21.0 g) of copolymer A-5 obtained in Synthesis Example 5 that does not correspond to (A) component, blend 4.8 g of B-1 as (B) component, and blend C as (C) component 0.2g of -1, 10.5g of D-1 as component (D), 0.01g of R-40 as a surfactant, 3.8g of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate as a solvent 35.1 g, becoming a homogeneous solution. Then, it filtered using the fine filter made of polyethylene with a pore diameter of 0.10 micrometers, and obtained the positive photosensitive resin composition (32 mass % of solid content concentration).

Table 1 shows the contents of (B) to (E) components with respect to each component contained in the positive photosensitive resin composition of Examples 1 to 6, and 100 parts by mass of (A) component.

[Graphical Evaluation] The positive-type photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were coated on silicon wafers using a spin coater, and prebaked on a heating plate at 80°C For 90 seconds, a resin film having the film thickness described in Table 2 was formed. Next, the resin film was subjected to the first exposure at the exposure amount described in Table 2 through a specific mask using an i-line stepper (NSR-2205i12D, NA=0.63, manufactured by Nikon Corporation). exposure. Here, as the mask, a mask formed with a square dot pattern of 4 μm×4 μm/4 μm pitch was used for the resin film with a film thickness of 4 μm (Examples 1 to 3 and Comparative Examples 1 and 2), or For resin films with a film thickness of 1 μm (Example 4 to Example 6), a mask forming a square dot pattern of 1 μm×1 μm/1 μm pitch was used. Then, within 10 minutes from the aforementioned first exposure, develop using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution to form a square dot pattern of 4 μm×4 μm for a resin film with a film thickness of 4 μm. A resin film with a film thickness of 1 μm forms a square dot pattern of 1 μm×1 μm. Observe the formed square dot pattern with a scanning electron microscope at a magnification of 5000 times. When the distance between adjacent square dot patterns can clearly identify the residue of the aforementioned resin film, the patternability evaluation is "×". , when the residue of the aforementioned resin film could not be recognized, the patternability evaluation was "◯". The evaluation results are shown in Table 2.

[Evaluation of lens shape] Using the positive-type photosensitive resin composition prepared in Examples 1 to 6 and Comparative Examples 1 and 2, by the procedure described in the aforementioned [Patternability Evaluation], for a film thickness of 4 μm For the resin film, a square dot pattern of 4 μm×4 μm is formed, and for a resin film with a film thickness of 1 μm, a square dot pattern of 1 μm×1 μm is formed on a silicon wafer. Next, for the aforementioned square dot pattern, bake for 5 minutes on the heating plate at the reflow temperature listed in Table 2. Further, using the above-mentioned i-ray stepper, for the above-mentioned square dot pattern on the whole surface, after the second exposure is performed at 500 mJ/cm ² , bake for 10 minutes on the heating plate at the post-baking temperature recorded in Table 2, Make microlenses. Further, for the 1 μm × 1 μm square dot pattern formed by using the positive-type photosensitive resin composition prepared in Example 4, it was not baked at the reflow temperature (in Table 2, the reflow temperature is represented by "none") ), using the aforementioned i-ray stepper, with 500mJ/cm After the ^second exposure, on the heating plate, with the post-baking temperature listed in Table 2, bake for 10 minutes to make a microlens. The shape of the prepared microlens was a square prism or a square truncated pyramid, and the evaluation was "□", and the shape of a truncated sphere or a hemispherical shape was "o". The evaluation results are shown in Table 2.

[Evaluation of drug resistance] The positive-type photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were coated on a silicon wafer using a spin coater, and placed on a heating plate with Prebaking was performed at 80°C for 90 seconds to form a resin film having the film thickness described in Table 2. Next, for the entire surface of the resin film, use the aforementioned i-ray stepper to expose at 500 mJ/cm ² , then bake for 10 minutes on a hot plate at the post-baking temperature listed in Table 2 to form a cured film. Dip the silicon wafer with the cured film into propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, and 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C for 5 minutes . The film thickness of the said cured film before and after immersion was measured, and the film thickness change before and after immersion was computed. Among the above-mentioned solvents used for immersion, if even one of the solvents used for immersion has a film thickness increase or decrease of more than 10% with respect to the film thickness before immersion, the chemical resistance evaluation is "×", and for all solvents, the film thickness increase or decrease does not reach 10%. , and the drug resistance evaluation was "◯". The evaluation results are shown in Table 2.

[Transparency Evaluation] The positive-type photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were coated on a quartz substrate using a spin coater, and heated on a heating plate at 80 °C prebaking for 90 seconds to form a resin film having the film thickness described in Table 2. Next, for the entire surface of the resin film, use the aforementioned i-ray stepper to expose at 500 mJ/cm ² , then bake for 10 minutes on a hot plate at the post-baking temperature listed in Table 2 to form a cured film. The transmittance at a wavelength of 400 nm was measured for the quartz substrate on which the cured film was formed using an ultraviolet-visible spectrophotometer UV-2550 (manufactured by Shimadzu Corporation). When the transmittance at a wavelength of 400 nm is less than 90%, the transparency evaluation is "x", and when it is more than 90%, the transparency evaluation is "○". The evaluation results are shown in Table 2.

[Long-term reliability evaluation] ＜HTS Test＞ Using the positive-type photosensitive resin composition prepared in Examples 1 to 6, a cured film was formed on a quartz substrate by the procedure described in the aforementioned [Transparency Evaluation]. After heating the quartz substrate with the cured film at 100°C for 1,000 hours in an oven, the transmittance at a wavelength of 400 nm was measured using the aforementioned UV-visible spectrophotometer. The transmittance at a wavelength of 400 nm before heating for 1,000 hours is given by When the transmittance increased or decreased by more than 5%, the evaluation was "×", and when the transmittance increased or decreased by less than 5%, the evaluation was "○". The evaluation results are shown in Table 2.

＜THS Test＞ Using the positive-type photosensitive resin composition prepared in Examples 1 to 6, a cured film was formed on a quartz substrate by the procedure described in the aforementioned [Transparency Evaluation]. After storing the quartz substrate with a cured film in a constant temperature and humidity chamber at 85°C and a relative humidity of 85% for 1,000 hours, use the aforementioned UV-visible spectrophotometer to measure the transmittance at a wavelength of 400nm. For 1,000 hours of storage For the previous transmittance at a wavelength of 400nm, when the transmittance increased or decreased by more than 5%, it was evaluated as "×", and when the transmittance increased or decreased by less than 5%, it was evaluated as "○". The evaluation results are shown in Table 2.

＜Xenon-arc test＞ Using the positive-type photosensitive resin composition prepared in Examples 1 to 6, a cured film was formed on a quartz substrate by the procedure described in the aforementioned [Transparency Evaluation]. A cutoff filter (cutoff filter) (L38, manufactured by Shibuya Optical Co., Ltd.) was installed on the quartz substrate on which the cured film was formed, and a xenon arc light tester (Q-SUN Xe-1, manufactured by Q-Lab Co., Ltd.) After exposure to 25 million [lx·h], use the aforementioned UV-visible spectrophotometer to measure the transmittance at a wavelength of 400nm. Regarding the transmittance at a wavelength of 400nm before exposure by the aforementioned xenon arc light tester, if the transmittance increased or decreased by more than 5%, it was evaluated as "×", and when the transmittance increased or decreased by less than 5%, it was evaluated as "○" ".

From the results in Table 2, by using the positive-type photosensitive resin composition of the present invention, there can be no residue and positive-type patterning, and even in a low-temperature process below 130°C, microspheres in the shape of truncated spherical or hemispherical can be formed. Lenses, these microlenses exhibit excellent transparency, drug resistance and long-term reliability.

Claims (14)

A positive-type photosensitive resin composition, which contains the following (A) component, the following (B) component, the following (C) component and a solvent, (A) component: (a1) represented by the following formula (1) monomers, (a2) monomers containing epoxy rings, and (a3) copolymers of monomers containing hydroxyl groups with an acid dissociation constant pKa of 14 or more, and copolymers that do not contain carboxyl groups and carboxylic acid anhydride groups, (B ) component: quinone diazide compound (C) component: photoacid generator

(In the formula, R ⁰ represents a hydrogen atom or a methyl group, R ¹ represents a single bond or an alkylene group with 1 or 2 carbon atoms, R ² represents a methyl group, a represents 1 or 2, and b represents an integer from 0 to 2) . The positive-type photosensitive resin composition as in Claim 1, wherein the aforementioned (a2) monomer containing an epoxy ring is a monomer represented by the following formula (2), and the aforementioned (a3) monomer having an acid dissociation constant pKa of 14 or more The monomer of hydroxyl group is a monomer represented by the following formula (3),

(In the formula, R ⁰ each independently represents a hydrogen atom or a methyl group, R ³ represents a divalent organic group represented by the following formula (I), R ⁴ represents 1 represented by the following formula (4) or the following formula (5) Valence organic group, R ⁵ represents the monovalent organic group represented by the following formula (I')

(wherein, c represents an integer from 0 to 3, d represents an integer from 1 to 3, e each independently represents an integer from 2 to 6, * represents the alkene compound with the monomer represented by the aforementioned formula (2) or the aforementioned formula (3) The bonding bond of the group, * represents the bonding bond with the monovalent organic group represented by the aforementioned formula (4) or the aforementioned formula (5)). The positive-type photosensitive resin composition of claim 1 or claim 2, wherein the aforementioned component (A) has a structural unit represented by the following formula (1a), a structural unit represented by the following formula (2a) and the following formula Copolymers of structural units represented by (3a),

(In the formula, R ⁰ each independently represents a hydrogen atom or a methyl group, R ¹ represents a single bond or an alkylene group with 1 or 2 carbon atoms, R ² represents a methyl group, b represents an integer from 0 to 2, R ⁴ represents A monovalent organic group represented by the following formula (4) or the following formula (5), e represents an integer from 2 to 6)

. The positive-type photosensitive resin composition according to any one of claim 1 to claim 3, wherein the polystyrene-equivalent weight average molecular weight of the aforementioned component (A) is 5,000 to 30,000. The positive-type photosensitive resin composition according to any one of claim 1 to claim 4, wherein the aforementioned component (C) is a nonionic photoacid generator. The positive-type photosensitive resin composition as in Claim 5, wherein the aforementioned nonionic photoacid generator is a photoacid generator represented by the following formula (6),

(wherein, R ⁶ represents a hydrocarbon group or perfluoroalkyl group with 1 to 10 carbon atoms, R ⁷ represents a linear alkyl or alkoxy group with 1 to 8 carbon atoms, or a perfluoroalkyl group with 3 to 8 carbon atoms branched chain alkyl or alkoxy). The positive-type photosensitive resin composition according to any one of claim 1 to claim 6, which further contains the following (D) component, (D) Component: polyfunctional epoxy compound. The positive-type photosensitive resin composition according to any one of claim 1 to claim 7, which further contains the following (E) component, (E) component: a sensitizer. The positive-type photosensitive resin composition according to any one of claim 1 to claim 8, which is used for making microlenses. A cured film obtained from the positive-type photosensitive resin composition according to any one of claim 1 to claim 9. A microlens made of the positive-type photosensitive resin composition according to any one of claim 1 to claim 9. A method of making a microlens, which comprises the following steps, Coating the positive-type photosensitive resin composition according to any one of claim 1 to claim 9 on the substrate to form a coating step of a resin film, after the aforementioned coating step, exposing at least a part of the resin film The first exposure step, after the aforementioned first exposure step, removes the exposed portion of the aforementioned resin film with a developing solution, and forms the developing step of the pattern of the unexposed portion of the resin film, after the aforementioned developing step, the aforementioned pattern is further The second exposure step of exposing, and the post-baking step of heating the aforementioned pattern at a temperature below 130° C. after the second exposure step. The method of making a microlens according to claim 12, wherein after the developing step and before the second exposure step, there is a reflow step of heating the pattern at a temperature below 130°C. The manufacturing method of a microlens as in Claim 12 or Claim 13, wherein the aforementioned substrate is a substrate on which a color filter is formed.