WO2023223670A1

WO2023223670A1 - Polymer and resin composition for optical lens

Info

Publication number: WO2023223670A1
Application number: PCT/JP2023/011733
Authority: WO
Inventors: 翔太今井; 勲安達; 拓加藤; 利彦神山; 崇洋坂口
Original assignee: 日産化学株式会社
Priority date: 2022-05-18
Filing date: 2023-03-24
Publication date: 2023-11-23
Also published as: TW202411306A

Abstract

Provided is a polymer which has both a high refractive index and excellent lens moldability and contains a structural unit represented by formula (1) (however, a structural unit represented by formula (1a) is excluded). (In the formula, X each independently represents a methyl group, an ethyl group, a methoxy group, an ethoxy group or a hydroxy group, and n represents an integer of 1-6.)

Description

Polymers and resin compositions for optical lenses

The present invention relates to a polymer, a resin composition for an optical lens, and a microlens obtained from the resin composition.

In recent years, in the field of electronic devices such as liquid crystal displays, organic EL displays, light emitting diodes, solar cells, and CCD/CMOS image sensors, protective films, planarization films, insulating films, antireflection films, refractive index control films, microlenses, Resin compositions employing polymeric materials having a high refractive index are often used for optical members such as intralayer lenses, optical waveguides, and film substrates. For example, by applying a high refractive index material to a microlens for a CCD/CMOS image sensor, improvement in sensor performance can be expected.

An etchback method is known as one of the methods for manufacturing microlenses for CCD/CMOS image sensors (Patent Document 1 and Patent Document 2). That is, a resist pattern is formed on the microlens resin layer formed on the color filter layer, and this resist pattern is reflowed by heat treatment to form a lens pattern. Using a lens pattern formed by reflowing this resist pattern as an etching mask, the underlying microlens resin layer is etched back, and the lens pattern shape is transferred to the microlens resin layer to produce a microlens.

In the etch-back method, lens moldability by dry etching is important. For example, when transferring the lens pattern shape to the lower microlens resin layer, the dry etching rate X of the lens pattern and the dry etching rate Y of the microlens resin layer are equivalent (X:Y=1:0.8 to 1 .2) is required (Patent Document 3). Additionally, in order to improve light collection efficiency, it is desirable that the gap between adjacent microlenses be narrow. That is, a material is required that allows the width of the microlens formed after dry etching to be larger than the width of the lens pattern before dry etching. Such lens moldability largely depends on the material of the microlens resin layer.

On the other hand, as a means of increasing the refractive index of a polymer material, it is known to introduce aromatic rings, halogen atoms other than fluorine atoms, sulfur atoms, metal atoms, hydrogen bonds, etc. into the molecules of the polymer material. ing. For example, it has recently been discovered that polyphenylene sulfide having a phenolic hydroxy group is a polymeric material with a high refractive index due to the effect of introducing an aromatic ring, a sulfur atom, and a hydrogen bond (Patent Document 4 and Patent Document 1).

Japanese Unexamined Patent Publication No. 1-10666 Japanese Patent Application Publication No. 6-112459 International Publication No. 2013/005619 International Publication No. 2022/065381 Japanese Patent Application Publication No. 2015-168790 JP2017-52834A

However, as a result of experiments conducted by the present inventors, it was found that although polyphenylene sulfide having a phenolic hydroxyl group certainly has a high refractive index, it is not necessarily a suitable material from the viewpoint of lens moldability. It has been desired to develop a material that exhibits a high refractive index and has excellent lens moldability.

The present invention was made based on the above circumstances, and an object of the present invention is to provide a polymer and a resin composition that have both a high refractive index and excellent lens moldability.

As a result of intensive studies to solve the above problems, the present inventors discovered that the above problems could be solved by employing polynaphthylene sulfide resin, and completed the present invention.

That is, the present invention provides the following [1] to [11].
[1] A polymer containing a structural unit represented by the following formula (1) (excluding the structural unit represented by the following formula (1a)).

(In the formula, X independently represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, and n represents an integer of 1 to 6.)

[2] The polymer of [1], in which n represents 1 in the structural unit represented by formula (1).
[3] The polymer of [1] or [2] in which in the structural unit represented by formula (1), X represents a methyl or ethyl group.
[4] The polymer of [1] or [2] in which in the structural unit represented by formula (1), X represents a methoxy group or an ethoxy group.
[5] The polymer of [1] or [2], wherein in the structural unit represented by formula (1), X represents a hydroxy group.
[6] A method for producing a polymer containing a structural unit represented by the formula (1) above, comprising a disulfide monomer represented by the following formula (2) (provided that a disulfide monomer represented by the following formula (2a)) ) and/or a step of oxidatively polymerizing a thiol monomer represented by the following formula (3) (however, excluding a thiol monomer represented by the following formula (3a)) [1] or [2] ] A method for producing a polymer.

(In the formula, X and n have the same meanings as defined in formula (1) above.)

[7] A resin composition for an optical lens, comprising (A) the polymer of [1] or [2] and/or a polymer containing a structural unit represented by the following formula (4), and (B) an organic solvent.

[8] Component (B) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl lactate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-heptanone , cyclopentanone, cyclohexanone, γ-butyrolactone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone [7] ] Resin composition for optical lenses.
[9] The resin composition for an optical lens according to [7], further containing (C) a polyfunctional epoxy compound.
[10] The resin composition for optical lenses according to [7], which is used for producing microlenses.
[11] A microlens obtained from the resin composition for optical lenses of [10].

According to the present invention, a resin film containing a polynaphthylene sulfide resin exhibits a high refractive index of 1.75 or more at a wavelength of 550 nm, and forms microlenses with a narrow gap between adjacent lenses by an etch-back method. Is possible.

Hereinafter, the polymer and the resin composition for optical lenses of the present invention will be explained in more detail. The resin composition for an optical lens of the present invention is characterized by containing a component (A) and a component (B), which will be described later. In addition, in the following description, solid content means components other than the solvent that constitute the resin composition.

[Polymer]
The polymer of the present invention is not particularly limited as long as it contains a structural unit represented by the following formula (1) (excluding the structural unit represented by the following formula (1a)).

Examples of the structural units of the polymer include the following formulas (1ba) to (1bn), formulas (1ca) to (1cn), formulas (1da) to (1dn), and formulas (1ea) to (1en). ), and structural units represented by formulas (1fn) to (1fn).

(In the formula, OMe represents a methoxy group.)

(In the formula, OEt represents an ethoxy group.)

(In the formula, Me represents a methyl group.)

(In the formula, Et represents an ethyl group.)

The proportion of the structural unit represented by the formula (1) (excluding the structural unit represented by the formula (1a)) in the polymer is preferably 10 mol% or more, more preferably 30 mol%. % or more, even more preferably 50 mol% or more, still more preferably 80 mol% or more. By setting the proportion of the structural units within the above range, it becomes possible to produce microlenses with narrower gaps between adjacent lenses.

X in the formula (1) represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, and among them, a methyl group, a methoxy group, and a hydroxy group are preferable, and X represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group. From this point of view, a hydroxy group is particularly preferred. Further, from the viewpoint of ease of synthesis, n in the formula (1) is preferably 1.

The molecular weight of the polymer is preferably 500 to 100,000, more preferably 1,000 to 30,000, even more preferably 1,000 as a polystyrene equivalent weight average molecular weight calculated by gel permeation chromatography (GPC). ~10,000.

The polymer can be produced, for example, by applying various known polyarylene sulfide production methods (polycondensation with an aromatic halogen compound and sodium sulfide, oxidative polymerization of an aromatic thiol compound or an aromatic disulfide compound, etc.) to naphthalene derivatives. It can be synthesized by Polymers having hydroxy groups can be synthesized by applying various known polyarylene sulfide production methods to naphthol derivatives with protected hydroxy groups, and then deprotecting some or all of the protecting groups. good.

As a method for producing the polymer, an oxidative polymerization method is preferable, and in particular, from the viewpoint that it can be produced at room temperature and normal pressure without using a metal catalyst, the quinone-based polymer described in Patent Document 5 and Patent Document 6 An oxidative polymerization method using an oxidizing agent and an acid is preferably used. A specific method for producing the polymer includes an aromatic thiol compound containing a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group; A method of oxidative polymerization using an aromatic disulfide compound containing as a monomer using a quinone oxidizing agent and an acid, an aromatic thiol compound containing a protected hydroxy group, or an aromatic disulfide compound containing a protected hydroxy group. An example of a method is to perform oxidative polymerization using a quinone oxidizing agent and an acid as a monomer, and then deprotect some or all of the protecting groups. The protected hydroxy group is not particularly limited as long as polymerization proceeds, but from the viewpoint of stability that does not interfere with quinone oxidizing agents or acids, an alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and in the case of a methoxy group is particularly preferable since the deprotection reaction can proceed more easily. The alkoxy group can be converted into a hydroxy group by removing the alkyl group by applying an acid or the like. Examples of the acid include trisubstituted boron compounds (boron tribromide, etc.) and Lewis acids such as aluminum chloride, and thiol compounds (dodecanethiol, etc.) and Bronsted acids such as hydrogen bromide. It is not particularly limited as long as it is an acid that can be converted into. All of the protecting groups may be removed or some may remain. Optical properties and solubility can be controlled by appropriately adjusting the deprotection rate.

When using the oxidative polymerization method, the disulfide monomer represented by the above formula (2) (excluding the disulfide monomer represented by the above formula (2a)) and/or the thiol monomer represented by the above formula (3) (However, the thiol monomer represented by the above formula (3a) is excluded.) can be suitably used.

The monomers used in the synthesis of the polymer may be used alone or in combination of two or more. From the viewpoint of adjusting optical properties and solubility in organic solvents, a disulfide monomer not represented by the above formula (2) or a thiol monomer not represented by the above formula (3) may be used as necessary. That is, the polymer only needs to contain at least one kind of structural unit represented by the above formula (1), and may be a homopolymer or a copolymer. When the polymer is a copolymer, its repeating structure is not particularly limited, and it may be any of an alternating copolymer, a block copolymer, a gradient copolymer, and a random copolymer. Moreover, the polymer can be branched depending on the polymerization conditions.

[(A) Component]
Component (A) is a polymer containing a structural unit represented by the above formula (1) (excluding the structural unit represented by the above formula (1a)) and/or a polymer containing a structural unit represented by the above formula (4). It is not particularly limited as long as it is a polymer containing a structural unit. Moreover, other structural units other than the structural unit represented by the formula (1) and the structural unit represented by the formula (4) may be included within a range that does not impair the effects of the present invention. Examples of other structural units include structural units represented by the following formulas (5) to (17).

(In the formula, OMe represents a methoxy group.)

(A) The structural unit represented by the above formula (1) (excluding the structural unit represented by the above formula (1a)) and/or the structural unit represented by the above formula (4) in the component (A) The proportion is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, even more preferably 80 mol% or more. By setting the proportion of the structural units within the above range, it becomes possible to produce microlenses with narrower gaps between adjacent lenses.

The structural unit represented by the formula (1) has reduced crystallinity due to the presence of the substituent, and therefore is superior to the structural unit represented by the formula (4) from the viewpoint of solubility in organic solvents. X in the formula (1) represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, and among them, a methyl group, a methoxy group, and a hydroxy group are preferable, and X represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group. From this point of view, a hydroxy group is particularly preferred. Further, from the viewpoint of ease of synthesis, n in the formula (1) is preferably 1.

The molecular weight of component (A) is preferably 500 to 100,000, more preferably 1,000 to 30,000, even more preferably 1. 000 to 10,000.

For component (A), for example, various known polyarylene sulfide production methods (polycondensation with aromatic halogen compounds and sodium sulfide, oxidative polymerization of aromatic thiol compounds or aromatic disulfide compounds, etc.) are applied to naphthalene derivatives. It can be synthesized by Polymers having hydroxy groups can be synthesized by applying various known polyarylene sulfide production methods to naphthol derivatives with protected hydroxy groups, and then deprotecting some or all of the protecting groups. good.

As a method for producing component (A), an oxidative polymerization method is preferable, and in particular, from the viewpoint that it can be produced at room temperature and normal pressure without using a metal catalyst, the quinone described in Patent Document 5 and Patent Document 6 An oxidative polymerization method using an oxidizing agent and an acid is preferably used. As a specific method for producing component (A), an aromatic thiol compound that may contain a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, or an aromatic thiol compound that may contain a methyl group, an ethyl group, a methoxy group, or an ethoxy group. Alternatively, a method of oxidative polymerization using an aromatic disulfide compound that may contain a hydroxy group as a monomer using a quinone oxidizing agent and an acid, or an aromatic thiol compound containing a protected hydroxy group or a protected hydroxy group. An example of a method is to perform oxidative polymerization using an aromatic disulfide compound containing as a monomer using a quinone oxidizing agent and an acid, and then deprotect some or all of the protecting groups. The protected hydroxy group is not particularly limited as long as polymerization proceeds, but from the viewpoint of stability that does not interfere with quinone oxidizing agents or acids, an alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and in the case of a methoxy group is particularly preferable since the deprotection reaction can proceed more easily. The alkoxy group can be converted into a hydroxy group by removing the alkyl group by applying an acid or the like. Examples of the acid include trisubstituted boron compounds (boron tribromide, etc.) and Lewis acids such as aluminum chloride, and thiol compounds (dodecanethiol, etc.) and Bronsted acids such as hydrogen bromide. It is not particularly limited as long as it is an acid that can be converted into. All of the protecting groups may be removed or some may remain. Optical properties and solubility can be controlled by appropriately adjusting the deprotection rate.

When synthesizing a polymer containing the structural unit represented by the above formula (1) (excluding the structural unit represented by the above formula (1a)) using the oxidative polymerization method, the above formula (2) (However, the disulfide monomer represented by the above formula (2a) is excluded.) and/or the thiol monomer represented by the above formula (3) (However, the thiol represented by the above formula (3a) is (excluding monomers) can be suitably used. In addition, when synthesizing a polymer containing a structural unit represented by the formula (4) using an oxidative polymerization method, a disulfide monomer represented by the following formula (18) and/or a disulfide monomer represented by the following formula (19) is synthesized. Thiol monomers can be suitably used.

The monomers used in the synthesis of component (A) may be used alone or in combination of two or more. From the viewpoint of adjusting optical properties and solubility in organic solvents, disulfide monomers not represented by the above formula (2) and the above formula (18) (for example, the following formulas (20) to (38)) may be used as necessary. ) or thiol monomers not represented by the formula (3) or formula (19) (for example, thiol monomers represented by the following formulas (39) to (57)). ) may be used. That is, the polymer only needs to contain at least one structural unit represented by the above formula (1) or the above formula (4), and may be a homopolymer or a copolymer. . When the polymer is a copolymer, its repeating structure is not particularly limited, and it may be any of an alternating copolymer, a block copolymer, a gradient copolymer, and a random copolymer. Further, the polymer may be branched depending on the polymerization conditions.

(In the formula, OMe represents a methoxy group.)

(In the formula, OMe represents a methoxy group.)

[(B) Component]
Component (B) is not particularly limited as long as it is an organic solvent that dissolves component (A), but an organic solvent having a melting point of 15° C. or lower and a boiling point of 85° C. or higher is particularly desirable. Here, the melting point and boiling point refer to those under 1 atmosphere. Since the melting point is 15° C. or lower, the resin composition has excellent handling properties at room temperature. The melting point is preferably 10°C or lower, more preferably 5°C or lower, from the viewpoint of storage stability in a cool place. Further, the lower limit of the melting point is not particularly limited, but is preferably -150°C or higher, for example. On the other hand, when the boiling point is 85° C. or higher, the coating film formed by applying the resin composition onto a substrate becomes less likely to whiten. The boiling point is preferably 100°C or higher, more preferably 115°C or higher, particularly from the viewpoint of easily forming a homogeneous coating film. Further, from the viewpoint of organic solvent removability, the upper limit of the boiling point is preferably 300°C or less, more preferably 250°C or less, and even more preferably 220°C or less.

Specific examples of component (B) include methylcyclohexane, ethylcyclohexane, n-heptane, toluene, o-xylene, m-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, anisole, phenetol, di- n-propyl ether, di-n-butyl ether, diisobutyl ether, di-n-pentyl ether, diisopentyl ether, di-n-hexyl ether, n-butyl ethyl ether, methyl-n-pentyl ether, cyclopentyl methyl ether, Tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, Cyclopentanol, benzyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene Glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, n-butyl formate, isobutyl formate, n-pentyl formate, isopentyl formate, n-propylacetate, isopropylacetate, n-butyl acetate , isobutyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, n-hexyl acetate, isohexyl acetate, n-heptyl acetate, isoheptyl acetate, n-octyl acetate, isooctyl Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, triacetin, ethyl propionate, n-propyl propionate, isopropyl propionate, n -butyl propionate, isobutyl propionate, tert-butyl propionate, propylene glycol monomethyl ether 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, 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 tert, isopropylacetoacetate, n-butylacetoacetate, isobutylacetoacetate, tert-butylacetoacetate, dimethylmalonate, diethylmalonate, methyl glycolate, ethyl glycolate, methyl pyruvate, ethyl pyruvate, Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, dimethyl carbonate, diethyl carbonate, 2-pentanone, 3-pentanone, cyclopentanone, 2,4-pentanedione, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, 2-hexanone, 3-hexanone, 3-methyl-2-hexanone, 5-methyl-2-hexanone , 2-methyl-3-hexanone, 5-methyl-3-hexanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl- 3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, cycloheptanone, γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, δ-caprolactone, ε- Caprolactone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylisobutyramide, N-methyl-2-pyrrolidone and N-ethyl- Examples include 2-pyrrolidone.

Component (B) may include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene, from the viewpoint of improving the leveling properties of the coating film formed by applying the resin composition onto a substrate. Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl lactate, pyruvic acid Methyl, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, γ-butyrolactone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and N -Ethyl-2-pyrrolidone is preferred, and in consideration of the solubility of component (A), cyclopentanone and γ-butyrolactone are particularly preferred.

The component (B) may be used alone or in combination of two or more. In addition, it may be mixed with a solvent other than component (B) as appropriate. In that case, the content of component (B) is 50% to 100% by mass of the entire solvent including component (B) and other solvents. It is preferably 60% to 100% by weight, even more preferably 70% to 100% by weight.

Specific examples of the other solvents include methanol, ethanol, 2-propanol, dichloromethane, 1,2-dichloroethane, chloroform, acetone, 2-butanone, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), ethyl acetate, and Examples include acetonitrile.

[(C) Polyfunctional epoxy compound]
The resin composition of the present invention may further contain (C) a polyfunctional epoxy compound for the purpose of improving chemical resistance. The component (C) is not particularly limited as long as it is a compound having at least two oxirane rings in the molecule, and for example, the following products and compounds can be used.
TEPIC (registered trademark)-G, TEPIC-L, TEPIC-VL, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP (manufactured by Nissan Chemical Co., Ltd.), Marproof (registered trademark) G- 01100, G-0105SA, G-0130SF, G-0130SP, G-0150M, G-0250SF, G-0250SP, G-05100, G-2050M, G-017581. OGSOL (registered trademark) PG-100, CG-500, EG-200, EG-280 (manufactured by Osaka Gas Chemical Co., Ltd.), GTR-1800 (registered trademark) EPICLON (registered trademark) 830, 830-S, 835, 840, 840-S, 850, 850-S, 850-LC, HP-820 (manufactured by Yakuhin Co., Ltd.), 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, EX-931, EX-991L, EX-313, EX-314 , EX-321, EX-321L, EX-411, EX-421, EX-512, EX-521, EX-612, EX-614, EX-614B, EX-622 (manufactured by Nagase ChemteX Co., Ltd.), jER (registered trademark) 152, jER (registered trademark) 152, jER (registered trademark) 604, jER (registered trademark) 630, jER (registered trademark) 806, jER (registered trademark) 806H, jER (registered trademark) 807, jER (registered trademark) 825, jER (registered trademark) 825, jER (registered trademark) 827, jER (registered trademark) 828, jER (registered trademark) 828EL, jER (registered trademark) 828US, jER (registered trademark) 828XA, 834, 890, 1031S, 1032H60, 1750, YL980, YL983U, YL6121HA, YL6677, YL6810, YX4000, YX4000H, YX4000HS, YX7700, YX8000 , same YX8034, TETRAD (registered trademark) YX8800 (manufactured by Mitsubishi Chemical Corporation), TETRAD (registered trademark) -C, TETRAD (registered trademark) -X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), Celoxide (registered trademark) 2021P, 2081, Epolead (registered trademark) ) GT401, EHPE (registered trademark) 3150, EHPE (registered trademark) 3150CE (manufactured by Daicel Corporation), EHPE (registered trademark) YD-115, EHPE (registered trademark) YD-115CA, EHPE (registered trademark) YD-127, EHPE (registered trademark) YD-128, EHPE (registered trademark) YD-128G , YD-128S, YD-128CA, YD-8125, YD-825GS, YDF-170, YDF-170N, YDF-8170C, YDF-870GS, ZX-1059, YH-404 , YH-434, YH-434L, YH-513, YH-523, ST-3000 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), Adekal Resin (registered trademark) EP-4100, EP -4100G, EP-4100E, EP-4100TX, EP-4300E, EP-4100, 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 Glycilol (registered trademark) ED-503, ED-503G, ED-506, ED -523T, ED-505 (manufactured by ADEKA Co., Ltd.), Sumiepoxy (registered trademark) ELM-434, ELM-434L, ELM-434VL, ELM-100, ELM-100H (manufactured by Sumitomo Chemical) Epolite M-1230, 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 1600, 80MF, 4000, 3002 (N) ( The above-mentioned polyfunctional epoxy resins include Kyoeisha Kagaku Co., Ltd.) and THI-DE (ENEOS Co., Ltd.).

The component (C) may be used alone or in combination of two or more. When the resin composition of the present invention contains component (C), the content of component (C) is preferably 5 parts by mass to 50 parts by mass, more preferably 10 parts by mass, based on 100 parts by mass of component (A). parts to 30 parts by mass. By setting the content of component (C) within the above range, further improvement in chemical resistance is possible without impairing the refractive index.

[Surfactant]
The resin composition of the present invention may optionally contain a surfactant for the purpose of improving coating properties. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether and polyoxyethylene Polyoxyethylene alkylaryl ethers such as nonylphenyl ether; polyoxyethylene/polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan triolate, and sorbitan tri Sorbitan fatty acid esters such as stearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan triolate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters; EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F-171 , F-173, R-30, R-40, R-40-LM (manufactured by DIC Corporation), Florado FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, Surflon (registered trademark) SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Corporation), FTX-206D, FTX-212D, FTX- 218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, and other fluorine-based surfactants such as the Ftergent series (manufactured by NEOS Co., Ltd.), 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.

When the resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 parts by mass to 3 parts by mass, more preferably 0.005 parts by mass based on 100 parts by mass of total solids. part to 1 part by weight, even more preferably 0.01 part to 0.5 part by weight.

[Other additives]
The resin composition of the present invention may optionally contain curing aids, antioxidants, light stabilizers (HALS), ultraviolet absorbers, plasticizers, adhesion aids, etc., as long as the effects of the present invention are not impaired. The composition may further include an agent.

[Method for preparing resin composition]
The method for preparing the resin composition of the present invention is not particularly limited, but includes, for example, a method of mixing components (A) and (B), and optionally component (C) and other components to form a uniform solution. It will be done. Further, if necessary, the obtained solution may be filtered using a filter with a pore size of 0.1 μm to 10 μm. The solid content concentration of the resin composition thus obtained is usually 1% by mass to 50% by mass from the viewpoint of applicability to a substrate.

[Method for producing resin film]
A suitable method such as a spinner or a coater is applied onto a base material (for example, a PET film, a TAC film, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer, and a substrate on which various metal films or color filters are formed on the surface). After applying the resin composition of the present invention by a coating method, a resin film is produced by baking using a heating means such as a hot plate or an oven. The baking conditions are appropriately selected from baking temperatures of 50° C. to 300° C. and baking times of 0.1 minutes to 360 minutes. Baking when producing the resin film may be performed in two or more steps. The thickness of the resin film formed is 0.001 μm to 1,000 μm, preferably 0.01 μm to 100 μm, and more preferably 0.1 μm to 10 μm.

[Production method of microlens]
A resist is applied onto the resin film produced through the above [Resin film production method], the resist is exposed through a predetermined mask, and if necessary, post-exposure heating (PEB) is performed, and further alkaline development, A resist pattern is formed on the resin film by rinsing and drying. As the light beam for exposure, for example, g-line, i-line, KrF excimer laser, and ArF excimer laser can be used. Next, the resist pattern is reflowed by heat treatment to form a lens pattern. Using the lens pattern as an etching mask, the resin film below the lens pattern is etched back, and the shape of the lens pattern is transferred to the resin film, thereby producing a microlens. In this method, when transferring the lens pattern shape to the underlying resin film (microlens resin layer), the dry etching rate X of the resist pattern and the dry etching rate Y of the microlens resin layer are set to be equivalent (X:Y= 1:0.8 to 1.2).

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[Measurement of polystyrene equivalent weight average molecular weight of polymer]
Equipment: GPC system manufactured by JASCO Corporation Column: Shodex (registered trademark) KF-804L and KF-803L
Column oven: 40℃
Flow rate: 1 mL/min Eluent: Tetrahydrofuran Sample concentration: 10 mg/mL
Sample injection volume: 20μL
Standard material: Monodisperse polystyrene Detector: Differential refractometer

[Manufacture of monomer]
<Monomer synthesis example 1>
Into a flask containing a stirring bar under an ice bath, 44.4 g of 2-methoxynaphthalene, 800 mL of tetrahydrofuran, and 184 mL of a hexane solution of n-butyllithium (1.6 mol/L) were added in this order and stirred for 1 hour. It was cooled to -80°C and 9.0 g of sulfur was added. Thereafter, the mixture was stirred at room temperature for 20 hours and subjected to liquid separation treatment with a saturated aqueous ammonium chloride solution. The obtained organic layer was dehydrated with sodium sulfate, filtered, and the filtrate was evaporated to obtain 53.5 g of 2-methoxy-1-naphthalenethiol as a yellow-green solid.

Subsequently, 53.5 g of the obtained 2-methoxy-1-naphthalenethiol and 500 mL of chloroform were placed in a flask containing a stirring bar, and then a solution of 35.7 g of iodine dissolved in 250 mL of methanol was added dropwise. and stirred at room temperature for 20 hours. Next, the organic layer was separated using 1M hydrochloric acid, 1M aqueous sodium hydroxide solution, and brine in this order, and the resulting organic layer was dehydrated with sodium sulfate and filtered, and the filtrate was evaporated to obtain a yellow oil. After dissolving the oil in 200 mL of chloroform, 200 mL of methanol was added to cause crystallization, and the resulting solid was dried under reduced pressure at 50°C for 3 hours to obtain a white solid monomer [bis(2-methoxynaphthyl)]. disulfide] was obtained.

<Monomer synthesis example 2>
After putting 22.4 g of 2-methoxybenzenethiol and 300 mL of chloroform into a flask containing a stirring bar, a solution of 20.7 g of iodine dissolved in 150 mL of methanol was added dropwise, and the mixture was stirred at room temperature for 1 hour. Next, 20 mL of 1N sodium thiosulfate aqueous solution was added to remove remaining iodine, followed by liquid separation treatment in the order of 1M hydrochloric acid, 1M sodium hydroxide aqueous solution, and brine, and the resulting organic layer was dehydrated with sodium sulfate. After filtration, the filtrate was evaporated to obtain a pale yellow solid monomer [bis(2-methoxyphenyl)disulfide].

<Monomer synthesis example 3>
After putting 25.0 g of 2-naphthalenethiol and 300 mL of chloroform into a flask containing a stirring bar, a solution of 20.2 g of iodine dissolved in 150 mL of methanol was added dropwise, and the mixture was stirred at room temperature for 2 hours. The obtained precipitate was washed with methanol and dried under reduced pressure at 50° C. for 3 hours to obtain a pale yellow solid monomer (di-2-naphthyl disulfide).

<Monomer synthesis example 4>
16.0 g of sulfur and 497 mL of tetrahydrofuran were placed in a flask containing a stirring bar and stirred in an ice bath. Next, a solution of 12.1 g of magnesium and 100 g of 1-bromo-2-methylnaphthalene dissolved in 452 mL of tetrahydrofuran was added dropwise in an ice bath, stirred for 1 hour, and then stirred at room temperature for 20 hours. The liquid was separated. The obtained organic layer was dehydrated with sodium sulfate, filtered, and the filtrate was evaporated to obtain 78.8 g of 2-methyl-1-naphthalenethiol.

Subsequently, 78.8 g of the obtained 2-methyl-1-naphthalenethiol and 680 mL of chloroform were placed in a flask containing a stirring bar, and then a solution of 57.4 g of iodine dissolved in 340 mL of methanol was added dropwise. and stirred at room temperature for 1 hour. Next, the organic layer was separated using 1M hydrochloric acid, 1M aqueous sodium hydroxide solution, and brine in this order, and the resulting organic layer was dehydrated with sodium sulfate and filtered, and the filtrate was evaporated to obtain a yellow oil. After dissolving the oil in 450 mL of chloroform, 900 mL of methanol was added to cause crystallization, and the resulting solid was dried at 50°C under reduced pressure for 3 hours to obtain a yellow solid monomer [bis(2-methylnaphthyl)]. disulfide] was obtained.

[Production of polymer or copolymer]
<Polymer synthesis example 1>
4.6 g (20 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2.2 g (20 mmol) of trifluoroacetic acid, and 10 mL of chloroform were placed in a flask containing a stirring bar and stirred. Thereafter, 7.6 g (20 mmol) of the monomer obtained in Monomer Synthesis Example 1 was added and stirred for 40 hours. Next, 20.6 g (180 mmol) of trifluoroacetic acid and 190 mL of chloroform were added to the reaction solution, and the mixture was further stirred for 24 hours. After removing the precipitate by filtration, the filtrate was dropped into 2000 mL of stirred ethanol/12N hydrochloric acid=95/5 (volume ratio). The precipitate generated by the dropping was collected and washed with ethanol, methanol, a 3% by mass aqueous potassium hydroxide solution, and pure water in this order. Next, the obtained precipitate was dissolved again in 100 mL of chloroform and added dropwise into 1000 mL of stirred methanol/12N hydrochloric acid=95/5 (volume ratio). The precipitate generated by the dropping was collected, washed in the order of methanol, a 3% by mass potassium hydroxide aqueous solution, and pure water, and then dried at 80°C under reduced pressure to obtain the precipitate expressed by the formula (1ca) above. 5.8 g of the polymer of the present invention [poly(2-methoxynaphthylene sulfide)] containing a structural unit of The weight average molecular weight M _W of the obtained polymer was 1,300 in terms of polystyrene.

<Polymer synthesis example 2>
In a flask containing a stirring bar, 5.8 g of the polymer obtained in Polymer Synthesis Example 1 and 75 mL of dichloromethane were placed in a nitrogen atmosphere, and after cooling to 0°C in an ice bath, boron tribromide was added. 60 mL of dichloromethane solution (1 mol/L) was added dropwise and stirred for 20 hours. Thereafter, 60 mL of pure water was added dropwise to quench the reaction, and the precipitate was washed with dichloromethane and pure water, and then dried at 50°C under reduced pressure, thereby containing the structural unit represented by the formula (1ba). 3.6 g of the polymer of the present invention [poly(2-hydroxynaphthylene sulfide)] was obtained.

<Polymer synthesis example 3>
4.6 g (20 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 0.8 g (7 mmol) of trifluoroacetic acid, and 7 mL of chloroform were placed in a flask containing a stirring bar and stirred. Thereafter, 5.6 g (20 mmol) of the monomer obtained in Monomer Synthesis Example 2 was added and stirred for 40 hours. Next, 73 mL of chloroform was added to the reaction solution, and the precipitate was removed by filtration, and then the filtrate was dropped into 800 mL of stirred ethanol/12N hydrochloric acid=95/5 (volume ratio). The precipitate generated by the dropwise addition was collected and washed in the order of ethanol, methanol, a 3% by mass aqueous potassium hydroxide solution, and pure water, and then dissolved again in 80 mL of chloroform and stirred with methanol/12N hydrochloric acid = 95/ 5 (volume ratio) into 800 mL. The precipitate generated by the dropping is collected, washed in the order of methanol, a 3% by mass aqueous potassium hydroxide solution, and pure water, and then dried at 80°C under reduced pressure to obtain a structural unit represented by the following formula. 4 g of a polymer containing [poly(2-methoxyphenylene sulfide)] was obtained. The weight average molecular weight M _W of the obtained polymer was 3,000 in terms of polystyrene.

(In the formula, OMe represents a methoxy group.)

<Polymer synthesis example 4>
4 g of the polymer obtained in Polymer Synthesis Example 3 and 86 mL of dichloromethane were placed in a flask containing a stirrer under a nitrogen atmosphere, and after cooling to 0°C in an ice bath, a dichloromethane solution of boron tribromide was added. (1 mol/L) 86 mL was added dropwise and stirred for 18 hours. Thereafter, 100 mL of pure water was added dropwise to quench the reaction, and the precipitate was washed with dichloromethane and pure water, and then dried at 50°C under reduced pressure to obtain a polymer containing a structural unit represented by the following formula [ 3.6 g of poly(2-hydroxyphenylene sulfide) was obtained.

<Polymer synthesis example 5>
4.6 g (20 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2.2 g (20 mmol) of trifluoroacetic acid, and 20 mL of dichloromethane were placed in a flask containing a stirring bar and stirred. Thereafter, 2.8 g (10 mmol) of the monomer obtained in Monomer Synthesis Example 2 and 3.2 g (10 mmol) of the monomer obtained in Monomer Synthesis Example 3 were added and stirred for 70 hours. Next, 60 mL of chloroform was added to the reaction solution, and the precipitate was removed by filtration, and then the filtrate was dropped into 800 mL of stirred ethanol/12N hydrochloric acid=95/5 (volume ratio). The precipitate generated by the dropwise addition was collected and washed in the order of ethanol, methanol, a 3% by mass aqueous potassium hydroxide solution, and pure water, and then dissolved again in 80 mL of chloroform and stirred with methanol/12N hydrochloric acid = 95/ 5 (volume ratio) into 800 mL. The precipitate generated by the dropping is collected, washed in the order of methanol, a 3% by mass potassium hydroxide aqueous solution, and pure water, and then dried at 80°C under reduced pressure to form two types represented by the following formulas. 3.0 g of the copolymer of the present invention [poly(2-naphthylene sulfide/2-methoxyphenylene sulfide)] containing the structural unit was obtained. The weight average molecular weight M _W of the obtained copolymer was 1,300 in terms of polystyrene.

(In the formula, OMe represents a methoxy group.)

<Polymer synthesis example 6>
In a flask containing a stirring bar under a nitrogen atmosphere, 2.0 g of the copolymer obtained in Polymer Synthesis Example 5, 0.8 g of sodium hydroxide, 2.0 g of 1-dodecanethiol, and N-methyl- 14 mL of 2-pyrrolidone was added and stirred at 130°C for 3 hours. Next, after neutralizing the reaction solution by adding diluted hydrochloric acid, the precipitate was washed with pure water and hexane, and dried at 80°C under reduced pressure to obtain a book containing two types of structural units represented by the following formula. 1.8 g of the copolymer of the invention [poly(2-naphthylene sulfide/2-hydroxyphenylene sulfide)] was obtained.

<Polymer synthesis example 7>
4.6 g (20 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2.2 g (20 mmol) of trifluoroacetic acid, and 20 mL of dichloromethane were placed in a flask containing a stirring bar and stirred. Thereafter, 2.8 g (10 mmol) of the monomer obtained in Monomer Synthesis Example 2 and 3.5 g (10 mmol) of the monomer obtained in Monomer Synthesis Example 4 were added and stirred for 70 hours. Next, 60 mL of chloroform was added to the reaction solution, and the precipitate was removed by filtration, and then the filtrate was dropped into 800 mL of stirred ethanol/12N hydrochloric acid=95/5 (volume ratio). The precipitate generated by the dropwise addition was collected and washed in the order of ethanol, methanol, a 3% by mass aqueous potassium hydroxide solution, and pure water, and then dissolved again in 80 mL of chloroform and stirred with methanol/12N hydrochloric acid = 95/ 5 (volume ratio) into 800 mL. The precipitate generated by the dropping is collected, washed in the order of methanol, a 3% by mass potassium hydroxide aqueous solution, and pure water, and then dried at 80°C under reduced pressure to form two types represented by the following formulas. 2.0 g of the copolymer of the present invention [poly(2-methyl-1-naphthylene sulfide/2-methoxyphenylene sulfide)] containing the structural unit was obtained. The weight average molecular weight M _W of the obtained copolymer was 1,700 in terms of polystyrene.

(In the formula, Me represents a methyl group and OMe represents a methoxy group.)

<Polymer synthesis example 8>
In a flask containing a stirrer, under a nitrogen atmosphere, 2.0 g of the polymer obtained in Polymer Synthesis Example 7, 0.8 g of sodium hydroxide, 2.0 g of 1-dodecanethiol, and N-methyl-2 - 14 mL of pyrrolidone was added and stirred at 130°C for 3 hours. Next, after neutralizing the reaction solution by adding diluted hydrochloric acid, the precipitate was washed with pure water and hexane, and dried at 80°C under reduced pressure to obtain a book containing two types of structural units represented by the following formula. 1.7 g of the copolymer of the invention [poly(2-methyl-1-naphthylene sulfide/2-hydroxyphenylene sulfide)] was obtained.

(In the formula, Me represents a methyl group.)

[Preparation of resin composition]
<Example 1>
3.6 g of the polymer obtained in Polymer Synthesis Example 2 as component (A), 19.7 g of cyclopentanone as component (B), and 0.7 g of triglycidyl isocyanurate as component (C) (( 20 parts by weight per 100 parts by weight of component A) and 0.001 g of R-40 (manufactured by DIC Corporation) as a surfactant were blended to form a homogeneous solution. Thereafter, it was filtered using a polyethylene microfilter with a pore size of 0.2 μm to obtain a resin composition (solid content concentration: 18% by mass).

<Comparative example 1>
A resin composition (solid content concentration 18% by mass) was obtained in the same manner as in Example 1, except that the polymer obtained in Polymer Synthesis Example 4 was used as the polymer that did not fall under component (A). Ta.

<Example 2>
A resin composition (solid content concentration: 18% by mass) was obtained in the same manner as in Example 1, except that the copolymer obtained in Polymer Synthesis Example 6 was used as the component (A).

<Example 3>
A resin composition (solid content concentration: 18% by mass) was obtained in the same manner as in Example 1 except that the copolymer obtained in Polymer Synthesis Example 8 was used as the component (A).

[Refractive index evaluation]
The resin compositions prepared in Examples 1 to 3 and Comparative Example 1 were each applied onto a silicon wafer using a spin coater, and baked on a hot plate at 100° C. for 1 minute. Thereafter, it was baked at 200° C. for 5 minutes to form a resin film with a thickness of 200 nm. The refractive index of these resin films at a wavelength of 550 nm was measured using a spectroscopic ellipsometer M-2000 (manufactured by JA Woollam Japan Co., Ltd.). The results are shown in Table 1.

[Dry etching rate evaluation]
A resist solution THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto a silicon wafer using a spin coater, and heated on a hot plate at 90°C for 1.5 minutes, at 110°C for 1.5 minutes, and then at 180°C. C. for 1 minute to form a resist film with a thickness of 1 μm. The resist film was dry etched using a dry etching apparatus RIE-10NR (manufactured by Samco Co., Ltd.) (etching gas: CF ₄ ), and the dry etching rate of the resist film was measured. Next, each of the resin compositions prepared in Examples 1 to 3 and Comparative Example 1 was applied onto a silicon wafer using a spin coater, and baked on a hot plate at 100° C. for 1 minute. Thereafter, it was baked at 200° C. for 5 minutes to form a resin film with a thickness of 1 μm, and the dry etching rate was similarly measured. Then, the dry etching rate of the resin films obtained from the resin compositions prepared in Examples 1 to 3 and Comparative Example 1 with respect to the resist film was calculated. The results are shown in Table 1.

[Lens moldability evaluation]
The resin compositions prepared in Examples 1 to 3 and Comparative Example 1 were each applied onto a silicon wafer using a spin coater, and baked on a hot plate at 100° C. for 1 minute. Thereafter, it was baked at 200° C. for 5 minutes to form a resin film with a thickness of 1.2 μm. Next, a resist solution THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto the resin film using a spin coater, and baked on a hot plate at 90° C. for 1.5 minutes. Thereafter, using an i-line stepper (NSR-2205i12D, NA=0.63, manufactured by Nikon Corporation), it was exposed to light through a mask forming a 1 μm x 1 μm square dot pattern, and baked at 110°C for 1.5 minutes. After that, development was performed using an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 2.38% by mass. Further, it was baked at 180° C. for 1 minute to form a lens pattern on the resin film, and the width of the lens pattern was measured. Then, using a dry etching device 2300 Versys (registered trademark) Kiyo (registered trademark) 45 (manufactured by Lam Research Co., Ltd.) (etching gas: CHF ₃ ), the lens pattern is removed as an etching mask. After dry-etching the resin film until the end, the width of the formed microlens was measured.

If the width of the microlens after dry etching is larger than or the same as the width of the lens pattern before dry etching, the lens formability is "○". Lens formability was evaluated as "x" when it was smaller than the width. The results are shown in Table 1.

The resin film obtained from the resin composition containing the polynaphthylene sulfide resin of the present invention has a high refractive index of 1.75 or more at a wavelength of 550 nm and exhibits excellent lens moldability by an etch-back method. was confirmed.
From the above results, the polymer and the resin composition for optical lenses of the present invention are useful for optical lenses, especially microlenses.

Claims

A polymer containing a structural unit represented by the following formula (1) (excluding the structural unit represented by the following formula (1a)).

(In the formula, X independently represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, and n represents an integer of 1 to 6.)
The polymer according to claim 1, wherein n represents 1 in the structural unit represented by formula (1).
The polymer according to claim 1 or 2, wherein in the structural unit represented by the formula (1), X represents a methyl group or an ethyl group.
The polymer according to claim 1 or 2, wherein in the structural unit represented by formula (1), X represents a methoxy group or an ethoxy group.
The polymer according to claim 1 or 2, wherein in the structural unit represented by the formula (1), X represents a hydroxy group.
A method for producing a polymer containing a structural unit represented by the formula (1) above, comprising a disulfide monomer represented by the following formula (2) (excluding a disulfide monomer represented by the following formula (2a)). ) and/or the thiol monomer represented by the following formula (3) (however, the thiol monomer represented by the following formula (3a) is excluded). manufacturing method.

(In the formula, X and n have the same meanings as defined in formula (1) above.)
A resin composition for an optical lens, comprising (A) the polymer according to claim 1 or 2 and/or a polymer containing a structural unit represented by the following formula (4), and (B) an organic solvent.
The component (B) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, Ethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl lactate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-heptanone, cyclopenta 8. The organic solvent according to claim 7, which contains at least one organic solvent selected from the group consisting of non, cyclohexanone, γ-butyrolactone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. Resin composition for optical lenses.
The resin composition for an optical lens according to claim 7, further comprising (C) a polyfunctional epoxy compound.
The resin composition for an optical lens according to claim 7, which is used for producing a microlens.
A microlens obtained from the resin composition for optical lenses according to claim 10.