TWI786237B - Thermosetting resin composition - Google Patents

Abstract

(式中，Ar表示縮合環式烴基，R¹ 及R² 分別獨立表示氫原子或甲基，R³ 表示單鍵或伸烷基，A¹ 表示具有環氧乙烷環之基，R⁴ 表示烷基，A² 表示烷氧基)。The present invention provides a novel thermosetting resin composition. The thermosetting resin composition of the present invention contains a self-crosslinking copolymer having a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3) . A triazine-based ultraviolet absorber and an organic solvent, wherein the triazine-based ultraviolet absorber is contained in a ratio of 3% by mass to 20% by mass relative to the content of the self-crosslinkable copolymer,

(In the formula, Ar represents a condensed ring hydrocarbon group, R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ represents a single bond or an alkylene group, A ¹ represents a group with an oxirane ring, R ⁴ represents Alkyl, A ² represents alkoxy).

Description

thermosetting resin composition

The present invention relates to a self-crosslinking copolymer, an ultraviolet absorber having at least one triazine ring in one molecule, and an organic solvent, which can be used in the production of high-refractive-index planarization films and high-refractive-index microlenses. Resin composition.

In recent years, in the field of electronic displays such as liquid crystal displays, organic EL displays, light-emitting diodes, solar cells, CCD/CMOS image sensors, etc., protective films, planarizing films, insulating films, anti-reflective films, and refractive index Optical components such as control films, microlenses, in-layer lenses, optical waveguides, and film substrates are often made of resin compositions using polymer materials with excellent transparency in the visible light region. These optical members require not only transparency but also excellent heat resistance and light resistance. Furthermore, the optical member is often required to have a high refractive index in order to improve light extraction efficiency and light-gathering performance.

Generally, as a method of increasing the refractive index of a polymer material, it is used in the molecule of the polymer material to introduce, for example, an aromatic ring, a halogen atom other than a fluorine atom, a sulfur atom, a metal atom, or a hydrogen bond. Regarding the introduction of aromatic rings, compared with monocyclic hydrocarbon groups such as phenyl, the introduction of condensed ring hydrocarbon groups such as naphthalene rings and anthracene rings is more effective for increasing the refractive index of polymer materials (Patent Document 1 and Patent Document 2).

Moreover, the etch-back method is known as one of the manufacturing methods of the microlens for CCD/CMOS image sensors (patent document 3 and patent document 4). That is, a resist pattern is formed on the resin layer for microlenses formed on the color filter layer, and the resist pattern is reflowed by heat treatment to form a lens pattern. The lens pattern formed by reflowing the lens pattern is used as an etching mask, the underlying resin layer for microlenses is etched, and the shape of the lens pattern is transferred to the resin layer for microlenses, thereby producing a microlens. When using the etch-back method to faithfully transfer the shape of the lens pattern to the underlying resin layer for microlenses, the dry etching rate X of the resist pattern is required to be equal to the dry etching rate Y of the resin layer for microlenses (X: Y =1:0.8~1.2) (Patent Document 5). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 8-53517 [Patent Document 2] International Publication No. 2008/143095 [Patent Document 3] Japanese Patent Application Laid-Open No. 1-10666 [Patent Document 4] Japanese Patent Application Laid-Open No. 6-112459 [Patent Document 5] International Publication No. 2013/005619

[Problem to be solved by the invention]

When a condensed cyclic hydrocarbon group is introduced into the molecule of a polymer material, the polymer material is easily degraded by light such as ultraviolet rays because the wavelength of light absorption is increased to a longer wavelength. Therefore, the use of an optical member made of a resin composition using a polymer material introduced with a condensed cyclic hydrocarbon group is likely to cause quality deterioration such as discoloration, and it is difficult to achieve both high refractive index and high light resistance.

The present invention has been accomplished based on the aforementioned circumstances, and its object is to provide a thermosetting resin composition that can form a resin composition having a high refractive index while having excellent transparency, heat resistance, light resistance, solvent resistance, flatness, and corrosion resistance. The hardened film with the same dry etching rate as the agent. Also, another object of the present invention is to provide a planarized film and a microlens having a high refractive index and excellent transparency, heat resistance, light resistance, and solvent resistance. [Means to solve the problem]

(式中，Ar表示縮合環式烴基，R¹ 及R² 分別獨立表示氫原子或甲基，R³ 表示單鍵或伸烷基，A¹ 表示具有環氧乙烷環之基，R⁴ 表示烷基，A² 表示烷氧基)。The inventors of the present invention have completed the present invention as a result of vigorous examinations to solve the aforementioned problems. That is, the present invention is a thermosetting resin composition comprising a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3). A self-crosslinking copolymer, a triazine-based ultraviolet absorber, and an organic solvent, wherein the triazine-based ultraviolet absorber is contained in a ratio of 3% by mass to 20% by mass relative to the content of the self-crosslinkable copolymer,

(In the formula, Ar represents a condensed ring hydrocarbon group, R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ represents a single bond or an alkylene group, A ¹ represents a group with an oxirane ring, R ⁴ represents Alkyl, A ² represents alkoxy).

The aforementioned condensed ring hydrocarbon group is, for example, naphthyl, and the aforementioned group having an oxirane ring is, for example, epoxy group.

The aforementioned self-crosslinking copolymer contains, for example, at least 70 mol % of the structural unit represented by the aforementioned formula (1). The self-crosslinking copolymer has a weight average molecular weight of 6,000 to 25,000.

(式中，*表示與前述三嗪環之碳原子之鍵結鍵，A³ 及A⁴ 分別獨立表示氫原子或有機基)。The aforementioned triazine-based ultraviolet absorber is a compound comprising a triazine ring and three phenyl groups that are bonded to carbon atoms of the triazine ring and may have substituents, and at least one of the three phenyl groups is represented by the following formula: (4) the basis of representation,

(In the formula, * represents the bonding bond with the carbon atom of the aforementioned triazine ring, and A ³ and A ⁴ independently represent a hydrogen atom or an organic group).

The thermosetting resin composition of the present invention further contains a surfactant.

The thermosetting resin composition of the present invention is, for example, a resin composition for planarizing films or a resin composition for microlenses. [Invention effect]

The thermosetting resin composition of the present invention has thermosetting properties without adding a crosslinking agent because the copolymer contained in the composition is self-crosslinking. Furthermore, the thermosetting resin composition of the present invention has excellent storage stability because the carboxyl group in the structural unit represented by the formula (3) of the aforementioned copolymer is blocked (protected). Furthermore, the cured film formed from the thermosetting resin composition of the present invention has a high refractive index (above 1.65), excellent transparency, heat resistance, solvent resistance, flatness, and an etching rate equivalent to that of a resist pattern. Therefore, the thermosetting resin composition of the present invention can be preferably used as a material for forming microlenses and planarization films.

Each component of the thermosetting resin composition of the present invention will be described in detail below. In the thermosetting resin composition of the present invention, the content of the solid content defined as all components of the composition except the solvent is usually 1% by mass to 50% by mass. Moreover, in this invention, even if it is a liquid component, it can handle as a "solid content" for convenience.

＜Self-crosslinking copolymer＞ The self-crosslinking copolymer contained in the thermosetting resin composition of the present invention is a copolymer having structural units represented by the aforementioned formula (1), formula (2) and formula (3).

Specific examples of the compound (monomer) forming the structural unit represented by the aforementioned formula (1) include 1-vinylnaphthalene, 2-vinylnaphthalene, 6-methyl-2-vinylnaphthalene, 5,8-di Methyl-2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene, 5,8-dimethoxy-2-vinylnaphthalene, 6-hydroxy-2-vinylnaphthalene, 5,8- Dihydroxy-2-vinyl naphthalene, 6-bromo-2-vinyl naphthalene, 5,8-dibromo-2-vinyl naphthalene, 1-vinyl anthracene, 2-vinyl anthracene, 9-vinyl anthracene, N-vinylcarbazole. These compounds may be used alone or in combination of two or more.

Specific examples of the compound (monomer) forming the structural unit represented by the aforementioned formula (2) include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, (meth)acrylic acid 3,4-epoxycyclopentyl methyl ester, 3,4-epoxycyclohexyl methyl (meth)acrylate, 5,6-epoxy-2-bicyclo[2.2.1 (meth)acrylate ]heptyl methyl ester, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]dec-8-yl (meth)acrylate. These monomers may be used alone or in combination of two or more. In addition, in this specification, description of (meth)acrylate or (meth)acrylic acid means both methacrylate and acrylate, and methacrylic acid and acrylic acid.

As a specific example of the compound (monomer) forming the structural unit represented by the aforementioned formula (3), acrylate or methacrylate having a protected carboxyl group is obtained by reacting acrylic acid or methacrylic acid with an alkenyl ether compound. Instead of the above-mentioned method, the structural unit represented by the aforementioned formula (3) can also be formed by a method of reacting a structural unit shared by acrylic acid or methacrylic acid with an alkenyl ether compound.

(式中，R⁵ 表示氫原子或碳數1至10之烷基，R⁶ 表式碳原子數1至10之烷基或碳原子數6至10之環狀烴基)。The aforementioned alkenyl ether compound is represented by the following formula (5).

(wherein, R ⁵ represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and R ⁶ represents an alkyl group with 1 to 10 carbon atoms or a cyclic hydrocarbon group with 6 to 10 carbon atoms).

The reaction between the compound having a carboxyl group and the alkenyl ether compound can be carried out by stirring at 70°C using monooctyl phosphate, one of phosphoric acid esters, as a catalyst, as described in Japanese Patent No. 3042033, for example.

Examples of the alkenyl ether compound represented by the aforementioned formula (5) include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, third Butyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether.

(式中，R² 表示氫原子或甲基，R⁶ 表示碳原子數1至10之烷基或碳原子數6至10之環狀烴基)。The structural unit represented by the aforementioned formula (3) is represented by, for example, the following formula (3-1).

(In the ^formula , R2 represents a hydrogen atom or a methyl group, and R6 represents an alkyl group with 1 to 10 carbon atoms or a cyclic hydrocarbon group with ⁶ to 10 carbon atoms).

Specific examples of the compound (monomer) forming the structural unit represented by the aforementioned formula (3) include 1-methoxyethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, (methoxyethyl) Base) 1-propoxyethyl acrylate, 1-isopropoxyethyl (meth)acrylate, 1-n-butoxyethyl (meth)acrylate, 1-tert-butoxy (meth)acrylate ethyl ethyl ester, 1-n-hexyloxyethyl (meth)acrylate, 1-cyclohexyloxyethyl (meth)acrylate. These monomers may be used alone or in combination of two or more.

In the self-crosslinking copolymer having the structural units represented by the aforementioned formula (1), formula (2) and formula (3), the structural unit represented by the aforementioned formula (1) and the structural unit represented by the aforementioned formula (2) The sum of the structural unit and the structural unit represented by the aforementioned formula (3) is 100 mole%, and the content rate of the structural unit represented by the aforementioned formula (1) is 60 mole% to 95 mole%, preferably 70 mole% % to 90 mol%, the content rate of the structural unit represented by the aforementioned formula (2) is 2 mol% to 20 mol%, preferably 5 mol% to 15 mol%, and the content rate of the structural unit represented by the aforementioned formula (3) The content of the indicated structural unit is 2 mol % to 30 mol %, preferably 5 mol % to 15 mol %.

The weight average molecular weight of the aforementioned self-crosslinking copolymer is usually 1,000 to 100,000, preferably 6,000 to 25,000, more preferably 6,000 to 20,000. In addition, the weight average molecular weight is the value obtained by gel permeation chromatography (GPC) using the polystyrene which is a standard sample.

Also, the content of the aforementioned self-crosslinkable copolymer in the thermosetting resin composition of the present invention is usually 50% by mass to 99% by mass, preferably 70% by mass, based on the solid content of the thermosetting resin composition. % to 95% by mass.

In the present invention, the method for obtaining the above-mentioned self-crosslinking copolymer is not particularly limited. Generally, the compound (monomer) forming the structural unit represented by the above-mentioned formula (1), formula (2) and formula (3) and Compounds other than the desired compounds (hereinafter referred to as compound X in this specification) are obtained by polymerization in a solvent in the presence of a polymerization initiator, usually at a temperature of 50°C to 120°C. The copolymer thus obtained is usually in a solution state dissolved in a solvent, and may be used in the thermosetting resin composition of the present invention in this state without being isolated.

In addition, the solution of the self-crosslinking copolymer obtained as described above is put into a weak solvent such as diethyl ether, toluene, methanol, ethanol, isopropanol, acetonitrile, water, etc. under stirring, and the copolymer is reprecipitated to form The precipitate is decanted or filtered, washed as necessary, and then dried at normal temperature or heated under normal pressure or reduced pressure to make the copolymer an oil or powder. By these operations, the polymerization initiator or unreacted compound coexisting with the aforementioned copolymer can be removed. In the present invention, the oil or powder of the aforementioned copolymer may be used as it is, or may be used as a solution by redissolving the oil or powder in, for example, a solvent described later.

Specific examples of the aforementioned compound X include styrene, 4-vinylbiphenyl, 2-alkenylfluorene, acenaphthylene, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate , (meth) isopropyl acrylate, (meth) cyclohexyl acrylate, (meth) isobornyl acrylate, (meth) adamantyl acrylate, (meth) dicyclopentyl acrylate, (meth) Base) dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, γ-butyrolactone (meth)acrylate, indene, maleimide , N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide , N-(4-hydroxyphenyl)maleimide, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether ether, 6-hydroxyhexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, and dipropylene glycol monovinyl ether.

<Triazine-based UV absorber> The triazine-based UV absorber contained in the thermosetting resin composition of the present invention is, for example, compounds represented by the following formulas (T-1) to (T-13).

Examples of commercially available triazine-based ultraviolet absorbers include Tinuvin [registered trademark] 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 1577ED, Tinuvin 1600 (manufactured by BASF Japan Co., Ltd.), Adeka Stab [registered trademark] LA-46, Adeka Stab LA-F70 (manufactured by ADEKA Co., Ltd.), KEMISORE [registered trademark] 102 (manufactured by Chemipro Chemicals Co., Ltd.). These triazine-type ultraviolet absorbers may be used alone or in combination of two or more.

The content of the triazine-based ultraviolet absorber contained in the thermosetting resin composition of the present invention is preferably from 3% by mass to 20% by mass, more preferably from 5% by mass to 20% by mass.

The preparation method of the thermosetting resin composition of the present invention is not particularly limited, but it can be, for example, a self-crosslinking copolymer having structural units represented by the aforementioned formula (1), formula (2) and formula (3) It is a method of dissolving in an organic solvent described below, and mixing the aforementioned triazine-based ultraviolet absorber in a specific ratio in the obtained solution to prepare a homogeneous solution. Another example is a method of adding and mixing other additives as necessary at an appropriate stage of the preparation method.

＜Organic solvent＞ The organic solvent contained in the thermosetting resin composition of the present invention is not particularly limited as long as it can dissolve the self-crosslinkable copolymer and the triazine-based ultraviolet absorber contained in the thermosetting resin composition. Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulose acetate, ethyl cellulose acetate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, toluene, Xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, Methyl 2-Hydroxy-3-Methylbutyrate, Methyl 3-Methoxypropionate, Ethyl 3-Methoxypropionate, Ethyl 3-Ethoxypropionate, 3-Ethoxypropionate Methyl ester, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, γ-butyrolactone, N,N-dimethylacetamide, N-methyl -2-pyrrolidone and N-ethyl-2-pyrrolidone. These organic solvents may be used alone or in combination of two or more.

From the viewpoint of improving the flatness of the coating film formed by coating the thermosetting resin composition of the present invention on a substrate, among the aforementioned organic solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, ethyl lactate, butyl lactate, methyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclopentanone, Cyclohexanone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and γ-butyrolactone.

＜Surfactant＞ In addition, the thermosetting resin composition of the present invention may contain a surfactant for the purpose of improving coatability. As the surfactant, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc., polyoxyethylene Polyoxyethylene alkyl aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene. Polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan Sorbitan fatty acid esters such as trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monopalmitate, etc. Polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Ionic surfactants, EF TOP [registered trademark] EF301, EF TOP EF303, EF TOP EF352 (manufactured by Mitsubishi Materials Denshi Co., Ltd.), MEGAFAC [registered trademark] F171, MEGAFAC F173, MEGAFAC R-30, MEGAFAC R-40, MEGAFAC R-40-LM (the above are manufactured by DIC), FLUORAD FC430, FLUORAD FC431 (the above are manufactured by Sumitomo 3M), ASHHI GUARD [registered trademark] AG710, SURFLON [registered trademark] S -382, SURFLON SC101, SURFLON SC102, SURFLON SC103, SURFLON SC104, SURFLON SC105, SURFLON SC106 (manufactured by AGC), DFX-18, FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX- 230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G and other Ftergent series (NEOS Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd. (share) system). These surfactants may be used alone or in combination of two or more.

Also, when the aforementioned surfactant is used, the content in the thermosetting resin composition of the present invention is usually 0.0001 to 3% by mass, preferably 0.001% by mass, based on the solid content of the resin composition. to 1% by mass, more preferably 0.01% to 0.5% by mass.

In addition, the thermosetting resin composition of the present invention may add curing agents, curing aids, sensitizers, plasticizers, antioxidants, light stabilizers (HALS), adhesion Additives such as additives.

The use of the thermosetting resin composition of the present invention will be described below. ＜How to make hardened film＞ A method for producing a cured film using the thermosetting resin composition of the present invention will be described. On substrates (such as PET films, TAC films, semiconductor substrates, glass substrates, quartz substrates, silicon wafers, and substrates with various metal films or color filters formed on these surfaces), by a spin coater Appropriate coating methods such as an applicator, etc. After coating the thermosetting resin composition of the present invention, it is baked using a heating means such as a hot plate or an oven to prepare a cured film. Baking conditions are appropriately selected from a baking temperature of 50° C. to 300° C. and a baking time of 0.1 minutes to 360 minutes. Baking when making the above-mentioned cured film can also be processed in two or more steps. Furthermore, the film thickness of the cured film formed from the thermosetting resin composition of the present invention is, for example, 0.001 μm to 1000 μm, preferably 0.01 μm to 100 μm, more preferably 0.1 μm to 10 μm.

＜How to make microlens＞ A method for producing a microlens using the thermosetting resin composition of the present invention will be described. Apply a resist on the cured film produced by the above method of producing the cured film, expose the resist through a specific mask, perform post-exposure heating (PEB) if necessary, and then develop with alkali and wash and drying to form a specific resist pattern on the cured film. For exposure, g-line, i-line, KrF excimer laser, ArF excimer laser can be used, for example. Secondly, by heat treatment, the aforementioned resist pattern is reflowed to form a lens pattern. The lens pattern is used as an etching mask, the aforementioned cured film under the lens pattern is etched back, and the shape of the lens pattern is transferred to the aforementioned cured film to produce a microlens. [Example]

The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to these examples. [Measurement of the weight average molecular weight of the copolymer obtained in the following synthesis example] Device: GPC system manufactured by Nippon Spectroscopic Co., Ltd. Column: Shodex [registered trademark] GPC KF-804L and GPC KF-803L Column oven: 40°C Flow rate: 1mL/min Eluent: Tetrahydrofuran

[Synthesis of self-crosslinked copolymer] <Synthesis Example 1> Dissolve 15.0g of 2-vinylnaphthalene, 3.9g of 1-n-butoxyethyl methacrylate, 3.0g of glycidyl methacrylate and 1.5g of 2,2'-azobisisobutyronitrile in propylene glycol monomethyl Ether acetate 23.3g. The obtained solution was dripped at 70 degreeC in the flask which preserve|saved 31.1 g of propylene glycol monomethyl ether acetates over 4 hours. After completion of the dropwise addition, the reaction was carried out for 18 hours to obtain a copolymer solution (solid content concentration: 30% by mass). The weight average molecular weight Mw of the obtained copolymer was 6,000 (polystyrene conversion).

<Synthesis Example 2> Dissolve 18.0g of 2-vinylnaphthalene, 2.7g of 1-n-butoxyethyl methacrylate, 2.1g of glycidyl methacrylate and 0.7g of 2,2'-azobisisobutyronitrile in propylene glycol monomethyl Ether acetate 23.5g. The obtained solution was dripped at 70 degreeC in the flask which preserve|saved 31.4 g of propylene glycol monomethyl ether acetates over 4 hours. After completion of the dropwise addition, the reaction was carried out for 18 hours to obtain a copolymer solution (solid content concentration: 30% by mass). The weight average molecular weight Mw of the obtained copolymer was 16,000 (in terms of polystyrene).

＜Synthesis Example 3＞ Dissolve 20.0g of 2-vinylnaphthalene, 1.4g of 1-n-butoxyethyl methacrylate, 1.1g of glycidyl methacrylate and 0.5g of 2,2'-azobisisobutyronitrile in propylene glycol monomethyl After 23.5 g of ether acetate, the resulting solution was dropped into a flask storing 31.4 g of propylene glycol monomethyl ether acetate at 70° C. over 4 hours. After completion of the dropwise addition, the reaction was carried out for 18 hours to obtain a copolymer solution (solid content concentration: 30% by mass). The weight average molecular weight Mw of the obtained copolymer was 20,000 (polystyrene conversion).

[Preparation of Thermosetting Resin Composition] <Example 1> 20.0 g of the copolymer solution obtained in Synthesis Example 1, 0.3 g of the compound represented by the aforementioned formula (T-9) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 2> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of the compound represented by the aforementioned formula (T-9) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 3> 20.0 g of the copolymer solution obtained in Synthesis Example 3, 0.3 g of the compound represented by the aforementioned formula (T-9) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 4> 20.0 g of the copolymer solution obtained in Synthesis Example 1, 0.18 g of the compound represented by the aforementioned formula (T-9) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.0 g of propylene glycol monomethyl ether acetate and 14.0 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 5> 20.0 g of the copolymer solution obtained in Synthesis Example 1, 0.6 g of the compound represented by the aforementioned formula (T-9) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 5.3 g of propylene glycol monomethyl ether acetate and 12.9 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 6> 20.0 g of the copolymer solution obtained in Synthesis Example 1, 1.2 g of the compound represented by the aforementioned formula (T-9) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 3.3 g of propylene glycol monomethyl ether acetate and 11.5 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 7> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of the compound represented by the aforementioned formula (T-7) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 8> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of the compound represented by the aforementioned formula (T-6) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 9> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of the compound represented by the aforementioned formula (T-11) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 10> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of the compound represented by the aforementioned formula (T-13) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 11> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of the compound represented by the aforementioned formula (T-5) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Example 12> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of the compound represented by the aforementioned formula (T-4) as a triazine-based ultraviolet absorber, and MEGAFAC [registered trademark] R-40 (DIC Co., Ltd.) ) 0.003 g was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

＜Comparative example 1＞ Dissolve 20.0 g of the copolymer solution obtained in Synthesis Example 2 and 0.003 g of MEGAFAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) as a surfactant in 6.4 g of propylene glycol monomethyl ether acetate and 13.6 g of cyclohexanone. g, a solution was obtained. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition. The thermosetting resin composition prepared in this comparative example does not contain an ultraviolet absorber.

<Comparative Example 2> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of a compound represented by the following formula (BT-1) as a benzotriazole-based ultraviolet absorber, and MEGAFAC [registered trademark] as a surfactant 0.003 g of R-40 (manufactured by DIC Co., Ltd.) was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Comparative Example 3> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of a compound represented by the following formula (BT-2) as a benzotriazole-based ultraviolet absorber, and MEGAFAC [registered trademark] as a surfactant were prepared. 0.003 g of R-40 (manufactured by DIC Co., Ltd.) was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Comparative Example 4> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of a compound represented by the following formula (BT-3) as a benzotriazole-based ultraviolet absorber, and MEGAFAC [registered trademark] as a surfactant 0.003 g of R-40 (manufactured by DIC Co., Ltd.) was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Comparative Example 5> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of a compound represented by the following formula (BT-4) as a benzotriazole-based ultraviolet absorber, and MEGAFAC [registered trademark] as a surfactant 0.003 g of R-40 (manufactured by DIC Co., Ltd.) was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Comparative Example 6> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of a compound represented by the following formula (BP-1) as a benzophenone-based ultraviolet absorber, and MEGAFAC [registered trademark] as a surfactant 0.003 g of R-40 (manufactured by DIC Co., Ltd.) was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Comparative Example 7> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of a compound represented by the following formula (BP-2) as a benzophenone-based ultraviolet absorber, and MEGAFAC [registered trademark] as a surfactant 0.003 g of R-40 (manufactured by DIC Co., Ltd.) was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Comparative Example 8> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of a compound represented by the following formula (BP-3) as a benzophenone-based ultraviolet absorber, and MEGAFAC [registered trademark] as a surfactant 0.003 g of R-40 (manufactured by DIC Co., Ltd.) was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

<Comparative Example 9> 20.0 g of the copolymer solution obtained in Synthesis Example 2, 0.3 g of a compound represented by the following formula (BP-4) as a benzophenone-based ultraviolet absorber, and MEGAFAC [registered trademark] as a surfactant 0.003 g of R-40 (manufactured by DIC Co., Ltd.) was dissolved in 7.4 g of propylene glycol monomethyl ether acetate and 14.3 g of cyclohexanone to obtain a solution. Then, the resulting solution was filtered using a microfilter made of polyethylene with a pore size of 0.10 μm to prepare a thermosetting resin composition.

[Solvent resistance test] Each of the thermosetting resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 9 was coated on a silicon wafer using a spin coater, and baked on a heating plate at 100°C for 1 minute , and further baked at 220° C. for 5 minutes to form a cured film with a film thickness of 1 μm. For these cured films, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, 2-propanol, and 2.38% by mass concentration of tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution Among them, after dipping at 23°C for 5 minutes, bake at 100°C for 1 minute to dry. The film thickness of each of the aforementioned cured films was measured before and after immersion and after drying, and the change in film thickness was calculated. Even if one of the solvents used in the aforementioned dipping, the film thickness after drying is evaluated as "×" when the film thickness after drying is more than 5% relative to the film thickness before dipping, for all the solvents used in the aforementioned dipping, the film thickness after drying is relative to When the increase in film thickness before immersion was less than 5%, it was evaluated as "◯", and solvent resistance was evaluated. The evaluation results are shown in Table 1.

[Measurement of Refractive Index] Each of the thermosetting resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 9 was coated on a silicon wafer using a spin coater, and baked on a heating plate at 100°C for 1 minute , and further baked at 220° C. for 5 minutes to form a cured film with a film thickness of 1 μm. About these cured films, the refractive index of wavelength 550nm was measured using spectroscopic ellipsometer M-2000 (J.A. Woollam Japan Co., Ltd.). The evaluation results are shown in Table 1.

[Heat resistance test] Each of the thermosetting resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 9 was coated on a quartz substrate using a spin coater, and baked on a heating plate at 100° C. for 1 minute. Further, it was baked at 220° C. for 5 minutes to form a cured film with a film thickness of 1 μm. About these cured films, the transmittance in the range of wavelength 400nm - 800nm was measured using the ultraviolet visible light spectrophotometer UV-2600 (made by Shimadzu Corporation). Furthermore, after these cured films were baked at 260° C. for 5 minutes, the transmittance in the wavelength range from 400 nm to 800 nm was measured again. After baking at 220°C for 5 minutes and after baking at 260°C for 5 minutes, when the minimum transmittance measured in the wavelength range of 400nm to 800nm is 90% or more, it is evaluated as "○", and when it is less than 90%, it is evaluated As "x", the heat resistance was evaluated. The evaluation results are shown in Table 1.

[Light resistance test] Each of the thermosetting resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 9 was coated on a quartz substrate using a spin coater, and baked on a heating plate at 100° C. for 1 minute. Further, it was baked at 220° C. for 5 minutes to form a cured film with a film thickness of 1 μm. About these cured films, the transmittance in the range of wavelength 400nm - 800nm was measured using the ultraviolet visible light spectrophotometer UV-2600 (made by Shimadzu Corporation). Furthermore, after performing a light resistance test on these cured films on the following conditions, the transmittance in the range of wavelength 400nm - 800nm was measured again. For each of the light resistance test before and after the light resistance test, when the minimum transmittance measured in the wavelength range of 400nm to 800nm is 90% or more, it is evaluated as "○", and when it is less than 90%, it is evaluated as "X", and light resistance is evaluated. sex. The evaluation results are shown in Table 1.

[Light fastness test conditions] Device: Xenon accelerated weathering tester Q-Sun Xe-1-B (manufactured by Q-Lab Corporation) Light source: Xenon arc lamp Optical filter: Window-B/SL Illuminance: 60W/m ² (wavelength 300nm to 400nm) Black panel temperature: 63°C Test time: 20 hours

[Gap flatness] Each of the thermosetting resin compositions prepared in Examples 1 to 12 was coated on a step substrate (refer to FIG. 1 ) with a height of 0.3 μm, a line width of 10 μm, and a space between lines of 10 μm using a spin coater. Bake at 100°C for 1 minute on a hot plate, and then bake at 220°C for 5 minutes to form a cured film with a film thickness of 1 μm. From the values of h1 (step difference of the step substrate) and h2 (step difference of the cured film, that is, the difference between the height of the cured film on the line and the height of the cured film on the interval) shown in the step substrate 1 in Figure 1, use "Formula: (1-(h2/h1)) x 100" calculated|required the planarization rate. When the flattening rate was 80% or more, it was evaluated as "◯", when it was 50% or more and less than 80%, it was evaluated as "△", and when it was less than 50%, it was evaluated as "×", and the step flattening property was evaluated. The evaluation results are shown in Table 1.

[Measurement of Dry Etching Rate] Each of the thermosetting resin compositions prepared in Examples 1 to 12 was coated on a silicon wafer using a spin coater, and baked on a heating plate at 100° C. for 1 minute. Further, it was baked at 220° C. for 5 minutes to form a cured film with a film thickness of 1 μm. These cured films were dry-etched using a dry etching apparatus RIE-10NR (manufactured by SAMOCO Co., Ltd.) (etching gas: CF ₄ ), and the dry etching rate was measured. Similarly, the resist solution (THMR-iP1800 (manufactured by Tokyo Ohka Industry Co., Ltd.)) is coated on the silicon wafer using a spin coater, baked on a heating plate at 90°C for 1.5 minutes, and then baked at 110°C Bake for 1.5 minutes, then bake at 180°C for 1 minute to form a resist film with a thickness of 1 μm, and measure the dry etching rate. Next, the dry etching rate of the cured film obtained from the thermosetting resin composition prepared in Examples 1 to 12 with respect to the resist film was determined. The evaluation results are shown in Table 1.

From the results in Table 1, it can be seen that the cured film formed by the thermosetting resin composition of the present invention has high solvent resistance, high refractive index, and high transparency. The minimum transmittance within the range is above 90%, which means it has high heat resistance and high light resistance. Furthermore, all the cured films formed from the thermosetting resin composition of the present invention have excellent level difference planarization properties with a planarization rate of 80% or more. Moreover, in the etch-back method, when the shape of the resist pattern is faithfully transferred to the underlying resin layer for microlenses, the dry etching rate X of the resist is required to be equal to the dry etching rate Y of the resin layer for microlenses. (X:Y=1:0.8~1.2), but the cured film formed from the thermosetting resin composition of the present invention has the result of satisfying these.

On the other hand, although the cured films formed from the thermosetting resin compositions prepared in Comparative Examples 1 to 9 have high solvent resistance, high refractive index, and high heat resistance, when the light resistance test is performed, at a wavelength of 400 nm, The minimum transmittance in the range to 800nm is as low as less than 90%, as a result of the lack of light resistance.

From the above, the thermosetting resin composition of the present invention can be used as a protective film, a planarization film, an insulating film, an antireflection film, a refractive index control film, a microlens, an intralayer lens, an optical waveguide, and a film base material. Resin composition of optical components, etc.

1: Step difference substrate 2: hardened film 3: line width 4: Space between lines h1: Step difference of substrate h2: step difference of hardened film

FIG. 1 is a schematic diagram showing a cured film formed by coating the resin composition of the present invention on a step substrate and baking.

1: Step difference substrate

2: hardened film

3: line width

4: Space between lines

h1: Step difference of substrate

h2: step difference of hardened film

Claims (7)

A thermosetting resin composition comprising a self-crosslinking copolymer having a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3) . A triazine-based ultraviolet absorber and an organic solvent, wherein the triazine-based ultraviolet absorber is contained in a ratio of 3% by mass to 20% by mass relative to the content of the self-crosslinkable copolymer,

(In the formula, Ar represents naphthyl, R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ represents a single bond or an alkylene group, A ¹ represents an epoxy group, R ⁴ represents an alkyl group, and A ² represents an alkane oxygen). The thermosetting resin composition according to claim 1, wherein the aforementioned self-crosslinking copolymer contains at least 70 mol % of the structural unit represented by the aforementioned formula (1). The thermosetting resin composition according to claim 1 or 2, wherein the self-crosslinking copolymer has a weight average molecular weight of 6,000 to 25,000. The thermosetting resin composition according to claim 1 or 2, wherein the triazine-based ultraviolet absorber is a compound comprising a triazine ring and three phenyl groups that are bonded to carbon atoms of the triazine ring and may have substituents , at least one of the three phenyl groups is a group represented by the following formula (4),

(In the formula, * represents the bonding bond with the carbon atom of the aforementioned triazine ring, and A ³ and A ⁴ independently represent a hydrogen atom or an organic group). The thermosetting resin composition according to claim 1 or 2, further comprising a surfactant. The thermosetting resin composition according to Claim 1 or 2, which is used for a planarization film. The thermosetting resin composition according to claim 1 or 2, which is used for microlenses.

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