TWI808313B - Low temperature curable resin composition and method of manufacturing device having color filter - Google Patents

Abstract

The present invention provides a resin composition for forming a cured film formed on a lower layer and an upper layer of a color filter.

The resin composition of the present invention contains a homopolymer having a structural unit represented by the following formula (1), a crosslinking compound having at least two alkoxyalkyl groups in one molecule, a photoacid generator, a surfactant, and an organic solvent. The content of the crosslinking compound is 40% to 60% by mass relative to the content of the homopolymer, and the content of the photoacid generator is at least 0.8% by mass relative to the sum of the contents of the homopolymer and the crosslinking compound.

(In the aforementioned formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms having at least one hydroxyl group as a substituent).

Description

Low-temperature curable resin composition, and method of manufacturing device with color filter

The present invention relates to a resin composition for forming a cured film formed on a lower layer and an upper layer of the color filter in a device including a color filter such as an image sensor or a display device. In particular, it relates to a low-temperature curable resin composition capable of forming a cured film at a baking temperature not exceeding 110°C.

In recent years, in devices such as CCD image sensors, CMOS image sensors, liquid crystal displays, and organic EL displays, color filters have become one of the indispensable components.

Generally, for the purpose of protecting the color filter and smoothing the unevenness of the surface of the color filter, a transparent resin film such as a protective film or a planarizing film is formed on the upper layer of the color filter. And based on improving the color filter and base The adhesiveness of the base substrate and the purpose of smoothing the unevenness caused by the existence of the circuit wiring part, light-shielding film, inner mirror, etc., also form a transparent resin film on the lower layer of the color filter. Compositions for forming such transparent resin films are disclosed in, for example, Patent Document 1 to Patent Document 4.

The formation of color filters generally uses, for example, three-color color resists containing red, green and blue pigments or dyes. The method of forming a color filter using three-color color resists first coats a color resist of the first color, then performs exposure, development and heat treatment to form a color resist pattern of the first color. Then, similarly to the color resist pattern of the first color, the color resist patterns of the second color and the third color are formed to form a color filter.

In these methods of forming color filters, in order to suppress deterioration of color reproducibility of color filters and decrease in yield of devices equipped with color filters, it is important to suppress the generation of color resist residues during the formation of color resist patterns.

Compared with other devices, the aforementioned organic EL display device is expected to be manufactured by a low-temperature process. For example, as disclosed in Patent Document 5, in order to maintain the characteristics of an organic EL element, it is required not to apply a temperature higher than 110°C. Therefore, the transparent resin film formed on the upper and lower layers of the color filter must be formed by curing the resin at a temperature of 110° C. or lower.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-344866

[Patent Document 2] Japanese Patent Laid-Open No. 2008-031370

[Patent Document 3] Japanese Patent No. 4222457

[Patent Document 4] International Publication No. 2013/005619

[Patent Document 5] International Publication No. 2017/203885

In the case of forming a color filter on the transparent resin film, the transparent resin film is required to have the property of suppressing the generation of residues of the color resist as described above. However, there is a problem that the transparent resin film formed from the conventional low-temperature curable material cannot achieve both the effect of sufficiently suppressing the residue of the color resist and the sufficient reliability as a permanent film.

The present invention was completed based on the foregoing, and its purpose is to provide a resin composition capable of forming a cured film with excellent solvent resistance and reliability at a temperature not exceeding 110°C, preferably below 100°C, and capable of suppressing color resist residues when forming a color filter on the cured film, and at the same time forming the cured film on the color filter. Another object of the present invention is to provide a method of manufacturing a color filter device having a color filter lower layer film and/or a color filter upper layer film having excellent solvent resistance and reliability.

The inventors of the present invention have completed the present invention as a result of diligent examinations to solve the aforementioned problems. That is to say, the present invention is composed of a resin A product comprising: a homopolymer having a structural unit represented by the following formula (1), a crosslinking compound having at least two alkoxyalkyl groups in one molecule, a photoacid generator, a surfactant, and an organic solvent, wherein the content of the crosslinking compound is 40% to 60% by mass relative to the content of the homopolymer, and the content of the photoacid generator is at least 0.8% by mass relative to the sum of the contents of the homopolymer and the crosslinking compound.

(In the aforementioned formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms having at least one hydroxyl group as a substituent).

The acid generated from the aforementioned photoacid generator is a superacid with an acid dissociation constant pKa of, for example, less than -7.

The acid generated from the aforementioned photoacid generator is, for example, Brunner's acid.

The aforementioned photoacid generator is, for example, N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide or a derivative thereof, or a diphenyl[4-(phenylthio)phenyl]conium salt compound.

Another aspect of the present invention is a method of manufacturing a device with a color filter, which has the following steps: a step of coating the resin composition of the present invention on a substrate, and the temperature is 75°C to Pre-baking the resin composition at 110°C, exposing to near-ultraviolet rays, and post-baking at 75°C to 110°C to form a color filter underlayer film, and using a color resist to form a color filter on the aforementioned color filter underlayer film.

The manufacturing method of the aforementioned device equipped with a color filter may further include the following steps: a step of coating the aforementioned resin composition on the aforementioned color filter, and a step of prebaking the resin composition at 75°C to 110°C, exposing it to near ultraviolet light, and post-baking at 75°C to 110°C to form the upper layer film of the color filter.

The aforementioned pre-baking and post-baking are preferably performed below 100°C.

The color filter lower layer film or the color filter upper layer film formed from the resin composition of the present invention has excellent chemical resistance, heat resistance and transparency. Thereby, when the color filter lower layer film or the color filter upper layer film formed from the resin composition of the present invention is exposed to a chemical solution such as an acid or alkaline solution, or a solvent treatment, or is exposed to sputtering and dry etching in the forming process or the forming process of peripheral devices such as wiring, the possibility of device deterioration or damage can be significantly reduced. In addition, when the color resist is formed from the resin composition of the present invention and the color resist is coated thereon, the problems of mixing with the color resist, residues of the color resist, and deformation and peeling of the color filter lower film caused by the above-mentioned chemical solution can also be significantly reduced. Furthermore, the resin composition of the present invention is formed After the color filter lower layer film or the color filter upper layer film is exposed, the desired pattern can be formed by developing with an alkaline developer. Therefore, the resin composition of the present invention is suitable as a material for forming a color filter lower layer film or a color filter upper layer film.

The present invention is a resin composition containing a specific homopolymer, a crosslinkable compound having at least two alkoxyalkyl groups in one molecule, a photoacid generator, a surfactant, and an organic solvent. The details of each component are described below. The solid content except the organic solvent from the resin composition of this invention is 0.01 mass % - 50 mass % normally.

<Homopolymer>

The homopolymer contained in the resin composition of the present invention is a polymer having a structural unit represented by the aforementioned formula (1). In the aforementioned formula (1), examples of the group represented by R ¹ include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, dihydroxypropyl and dihydroxybutyl.

Examples of the compound (monomer) forming the structural unit represented by the aforementioned formula (1) include, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 3,4-dihydroxybutyl methacrylate, diethylene glycol monomethacrylate, and dipropylene glycol monomethacrylate. In the resin composition of the present invention, by using the compound represented by the formula (1) The homopolymer of the structural unit can suppress the residue of the color resist that occurs on the color filter underlayer film after the color filter is formed on the color filter underlayer film formed from the resin composition.

The weight average molecular weight of the aforementioned homopolymer is usually 1,000 to 200,000, preferably 3,000 to 100,000. The weight average molecular weight is the value obtained by gel permeation chromatography (GPC).

Also, the homopolymer content in the resin composition of the present invention is usually 30% to 99% by mass, preferably 60% to 75% by mass, based on the solid content of the resin composition.

In the present invention, the method for obtaining the aforementioned homopolymer is not particularly limited, but it can generally be obtained by polymerizing the compound (monomer) forming the structural unit represented by the aforementioned formula (1) in a solvent in the presence of a polymerization initiator, usually at a temperature of 50°C to 120°C. The homopolymer thus obtained is usually in a solution state dissolved in a solvent, and can be used in the resin composition of the present invention without isolation in this state.

In addition, if the solution of the homopolymer obtained above is put into a stirred weak solvent such as hexane, diethyl ether, toluene, methanol, water, etc., the homopolymer is reprecipitated, and the resulting precipitate is decanted or filtered, washed if necessary, and dried at normal temperature or under reduced pressure, and the homopolymer can be made into an oil or powder. By these operations, the polymerization initiator or unreacted compound coexisting with the homopolymer can be removed. In the present invention, the oil or powder of the homopolymer may be used as it is, or may be used as a solution by redissolving the oil or powder in, for example, an organic solvent described below.

<Crosslinkable compound>

The crosslinkable compound contained in the resin composition of this invention has at least 2 alkoxyalkyl groups in 1 molecule. As such a crosslinkable compound, a compound having an alkoxyalkylated nitrogen atom is exemplified.

As the aforementioned compounds having alkoxyalkylated nitrogen atoms are, for example, (poly)methylolated melamine, (poly)methylolated glycoluril, (poly)methylolated benzoguanidine, (poly)methylolated urea, etc., a nitrogen-containing compound having a plurality of active methylol groups in one molecule, for example, a compound in which at least one hydrogen atom of a hydroxyl group in the methylol group is substituted by an alkyl group such as a methylol group or a butyl group.

The aforementioned compounds having alkoxyalkylated nitrogen atoms may be mixtures of plural substituted compounds, or mixtures containing a part of oligomer components formed by self-condensation, and such mixtures may also be used. More specifically, for example, hexamethoxymethyl melamine (manufactured by Japan CYTEC Industry Co., Ltd., CYMEL [registered trademark] 303), tetrabutoxymethyl glycoluril (manufactured by Japan CYTEC Industry Co., Ltd., CYMEL [registered trademark] 1170), tetramethoxymethylbenzoguanidine (manufactured by Japan CYTEC Industry Co., Ltd., CYMEL [registered trademark] 1123), tetramethoxymethyl glycoluril (Japan CYMEL [registered trademark] 1123), etc. YTEC Industry Co., Ltd., POWDERLINK [registered trademark] 1174) and other POWDERLINK series products, and methylated melamine resin (Sanwa Chemical Co., Ltd., NIKALAC [registered trademark] MW-30HM, same MW-390, same MW-100LM, same MW-750LM), methylated urea resin (Sanwa Chemical Co., Ltd., Nikalac [registered trademark] MX- 270, same as MX-280, same as MX-290) and other products of NIKALAC series. the A crosslinkable compound may be used individually by 1 type, and may use it in combination of 2 or more types.

The content of the crosslinking compound in the resin composition of the present invention is preferably 40% by mass to 60% by mass based on the content of the aforementioned homopolymer in the resin composition. When the content of the above-mentioned crosslinking compound in the resin composition of the present invention is too much or too small, after the color filter is formed on the color filter underlayer film formed from the resin composition, the residue of the color resist observed on the color filter underlayer film may increase.

<Photoacid Generator>

The photoacid generator contained in the resin composition of the present invention is a compound that generates a strong acid by exposure, preferably a superacid with an acid dissociation constant pKa less than -7. Specific examples of the compound include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

Specific examples of onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tertiary butylphenyl)iodonium camphorsulfonate, bis(4-tertiary butylphenyl)iodonium trifluoromethanesulfonate, etc. Phenylaccordance (pentafluoroethyl) trifluorophosphate, triphenylaccordium hexafluoroantimonate, triphenylaccordium (pentafluorophenyl) borate, triphenylaccordium nonafluoro-n-butane sulfonate, triphenylaccordance camphor sulfonate, triphenylacathane trifluoromethanesulfonate, diphenyl[4-(phenylthio)phenyl]accordium hexafluorophosphate, diphenyl[4-(phenylthio)phenyl]accordium (pentafluoroethyl) trifluorophosphate, Phenyl[4-(phenylthio)phenyl]percite hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl] Calcite salt compounds such as percite (pentafluorophenyl) borate, etc. Among the onium salt compounds, percite salt compounds are preferable, and diphenyl[4-(phenylthio)phenyl] percite salt compounds are more preferable as compounds that generate acid by i-line (365 nm) exposure.

Specific examples of the aforementioned sulfonyl imide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide, N-(trifluoromethanesulfonyloxy)-2-alkyl-1 , 8-naphthalimide, N-(trifluoromethanesulfonyloxy)-3-alkyl-1,8-naphthalimide and N-(trifluoromethanesulfonyloxy)-4-alkyl-1,8-naphthalimide. Among the sulfonimide compounds, N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide and its derivatives are preferred.

A specific example of the aforementioned disulfonyldiazomethane compound is bis(trifluoromethylsulfonyl)diazomethane.

Specific examples of the aforementioned photoacid generators include ADEKA ARKLS (registered trademark) SP-056, same SP-066, same SP-140, same SP-141, same SP-082, same SP-601, same SP-606, same SP-701, same SP-150, same SP-170, same SP-171 (the above are manufactured by ADEKA Co., Ltd.), CPI (registered trademark)-110P , DONG-110B, DONG-310B, DONG-210S, DONG-100P, DONG-101A, DONG-200K (the above are made by SAN APRO), DPI-105, DPI-106, DPI-109, DPI-201, BI-105, MPI-105, MPI-106, MPI-109, BBI-102, BBI-103 , BBI-105, BBI-106, BBI-109, BBI-110, BBI-200, BBI-201, BBI-300, BBI-301, TPS-102, TPS-103, TPS-105, TPS-106, TPS-109, TPS- 200, TPS-300, TPS-1000, HDS-109, MDS-103, MDS-105, MDS-205, MDS-209, BDS-109, MNPS-109, DTS-102, DTS-103, DTS-105, DTS-200, NDS-103, NDS-105, NDS-155, NDS- 165, SI-105, NDI-105, NDI-109, NAI-105, NAI-109 (all of which are manufactured by Midori Chemical Co., Ltd.). These photoacid generators can be used individually by 1 type or in combination of 2 or more types.

Also, the content of the photoacid generator in the resin composition of the present invention is usually 0.8 to 20% by mass, preferably 1.0 to 15% by mass, based on the sum of the contents of the homopolymer and the crosslinkable compound in the resin composition. When the content of the photoacid generator in the resin composition of the present invention is too small, the solvent resistance or reliability of the film formed from the resin composition may become insufficient.

<Surfactant>

The resin composition of the present invention contains 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 octylphenyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene. Polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc., sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan Anionic surfactants such as anhydride monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan fatty acid esters, etc., EF TOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Corporation), MEGAFAC [registered trademark] F-171, F-173, R-30, R-4 0. Same as R-40-LM (the above is DIC (stock) system), FLUORAD FC430, same FC431 (the above is Sumitomo 3M (stock) system), ASAHI GUARD (registered trademark) AG710, SURFLON (registered trademark) S-382, same SC101, same SC102, same SC103, same SC104, same SC105, same SC106 (AGC (stock) system), FTERGENT series (manufactured by NEOS Co., Ltd.) of FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, DFX-18 and other fluorine-based surfactants, and organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd. (share) system), etc. These surfactants may be used alone or in combination of two or more.

The surfactant content in the resin composition of the present invention is based on the aforementioned homopolymer content in the resin composition, usually 0.001% by mass to 3% by mass, preferably 0.01% by mass to 2% by mass, more preferably 0.1% by mass to 1% by mass.

<Organic solvent>

The organic solvent contained in the resin composition of the present invention is not particularly limited as long as it can dissolve the solid content contained in the resin composition. Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl Cellolytic acetate, ethyl cellolytic acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl 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, 2-hydroxy -Ethyl 2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, γ-butyrolactone, N-methylpyrrolidone and N-ethylpyrrolidone . These organic solvents may be used alone or in combination of two or more.

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, cyclopentanone, cyclohexanone, and γ-butyrolactone are preferred from the viewpoint of improving the leveling property of the coating film formed by coating the resin composition of the present invention on a substrate.

<Other additives>

The resin composition of the present invention may contain additives such as light stabilizers, ultraviolet absorbers, sensitizers, plasticizers, antioxidants, adhesion aids, defoamers, etc. as required, as long as the effects of the present invention are not impaired.

<Preparation method of resin composition>

The preparation method of the resin composition of the present invention is not particularly limited, but An example is, for example, a method of dissolving a solution of a homopolymer having a structural unit represented by the aforementioned formula (1), a crosslinking compound, a photoacid generator, and a surfactant in an organic solvent at a specific ratio 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.

<Manufacturing method of color filter lower layer film or color filter upper layer film>

A method for producing a color filter lower layer film or a color filter upper layer film using the resin composition of the present invention will be described. The resin composition of the present invention is coated on substrates (such as semiconductor substrates, glass substrates, quartz substrates, silicon wafers, and substrates on which various metal films, planarizing films, color filters, organic EL elements, etc. are formed) by appropriate coating methods such as spin coaters and coaters, and then pre-baked with heating means such as heating plates and ovens to form coating films. Next, the coating film is exposed using an exposure machine. Furthermore, it is baked and hardened using heating means such as a hot plate and an oven to produce a color filter lower layer film or a color filter upper layer film. After the aforementioned resin composition is coated or pre-baked, an image development process may also be included. The aforementioned pre-baking and post-baking conditions are properly selected from a baking temperature of 75° C. to 110° C. and a baking time of 0.3 minutes to 60 minutes. This post-baking may be processed in two or more stages. For the aforementioned exposure, for example, near ultraviolet light (eg, i-ray) can be used. Also, the film thickness of the color filter lower layer film formed from the resin composition of the present invention is, for example, 0.06 μm to 0.5 μm, and the film thickness of the color filter upper layer film formed from the resin composition of the present invention is, for example, 0.3 μm to 1.0 μm.

[Example]

Hereinafter, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to these examples.

[Measurement of the weight average molecular weight of the homopolymer obtained in the following synthesis example]

The molecular weight of the homopolymer was measured with a GPC device, and the weight average molecular weight (Mw) was calculated as a value in terms of polyethylene glycol and polyethylene oxide.

GPC device: Showa Denko Co., Ltd. GPC system (Shodex [registered trademark] GPC-101)

Column: Shodex[registered trademark] KD-800RH, KD-800RL, KD-803 and KD-805

Column temperature: 50°C

Eluent: N,N-Dimethylformamide [As an additive, lithium bromide-hydrate (LiBr‧H ₂ O) 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) 30mmol/L, and tetrahydrofuran (THF) 10ml/L]

Flow rate: 1.0mL/min

Standard samples for calibration line preparation: TSK standard polyethylene oxide manufactured by TOSOH Co., Ltd. [weight average molecular weight (Mw) 900,000, 150,000, 100,000, 30,000] and polyethylene glycol manufactured by Polymer Laboratory Co., Ltd. [peak molecular weight (Mp) 12,000, 4,000, 1,000]

In order to avoid overlapping peaks, two samples were measured respectively, that is, the samples made by mixing four kinds of standard polyethylene oxide with Mw of 900,000 and 100,000 and polyethylene glycol with Mp of 12,000 and 1,000, and three kinds of mixed samples of standard polyethylene oxide with Mw of 150,000 and 30,000 and polyethylene glycol with Mp of 4,000. Synthetic samples.

[Synthesis of Polymer] <Synthesis Example 1>

After dissolving 40.0 g of 2-hydroxyethyl methacrylate and 3.0 g of 2,2'-azobisisobutyronitrile in 80.0 g of propylene glycol monomethyl ether, the solution was added dropwise over 4 hours to a flask holding 49.0 g of propylene glycol monomethyl ether at 70°C. After completion of the dropwise addition, the reaction was further performed for 18 hours to obtain a homopolymer solution (solid content concentration: 25% by mass). The weight average molecular weight Mw of the obtained homopolymer was 24,200.

<Synthesis Example 2>

After dissolving 30.2 g of 2-hydroxypropyl acrylate, 10.0 g of benzyl acrylate, and 3.4 g of 2,2'-azobisisobutyronitrile in 80.9 g of propylene glycol monomethyl ether, the solution was added dropwise over 4 hours to a flask holding 49.8 g of propylene glycol monomethyl ether at 70°C. After completion of the dropwise addition, the reaction was further carried out for 18 hours to obtain a copolymer solution (solid content concentration: 25.0% by mass). The weight average molecular weight Mw of the obtained copolymer was 13,500.

[Preparation of resin composition] <Example 1>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)) as a crosslinking compound, 0.028 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator, and MEGA FAC [registered trademark] R-40 (DIC (Co., Ltd.)) 0.002 g was dissolved in 13.9 g of propylene glycol monoethyl ether and 26.3 g of propylene glycol monomethyl ether to prepare a solution. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition.

<Example 2>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)) as a crosslinking compound, 0.14 g of CPI-210S (manufactured by SAN APRO Co., Ltd.) as a photoacid generator, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) were dissolved in propanediol. A solution was prepared in 13.9 g of alcohol monoethyl ether and 26.3 g of propylene glycol monomethyl ether. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition.

<Example 3>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)) as a crosslinking compound, 0.14 g of CPI-110B (manufactured by SAN APRO Co., Ltd.) as a photoacid generator, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) were dissolved in propanediol. A solution was prepared in 13.9 g of alcohol monoethyl ether and 26.3 g of propylene glycol monomethyl ether. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition.

<Example 4>

8.0 g of the homopolymer solution obtained in Synthesis Example 1 was used as a cross-linking compound 1.2 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)), 0.032 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.), were dissolved in 15.8 g of propylene glycol monoethyl ether and 30.9 g of propylene glycol monomethyl ether. g to make a solution. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition.

<Comparative example 1>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)) as a crosslinking compound, 0.028 g of TAG2689 (manufactured by King Industries Co., Ltd.) as a thermal acid generator, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) were dissolved in A solution was prepared in 13.9 g of propylene glycol monoethyl ether and 26.3 g of propylene glycol monomethyl ether. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition.

<Comparative example 2>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)) as a crosslinking compound, 0.028 g of p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acid compound, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) were dissolved in propylene glycol mono A solution was prepared in 13.9 g of diethyl ether and 26.3 g of propylene glycol monomethyl ether. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition.

<Comparative example 3>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)) as a crosslinking compound, 0.028 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acid compound, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) were dissolved in acrylic acid A solution was prepared in 13.9 g of glycol monoethyl ether and 26.3 g of propylene glycol monomethyl ether. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition.

<Comparative example 4>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)) as a crosslinking compound, 0.14 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acid compound, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) were dissolved in propane A solution was prepared in 14.4 g of alcohol monoethyl ether and 27.6 g of propylene glycol monomethyl ether. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition.

<Comparative example 5>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.2 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)) as a crosslinking compound, 0.022 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator, and MEGA FAC [registered trademark] R-40 (DIC (Co., Ltd.)) 0.002 g was dissolved in 10.9 g of propylene glycol monoethyl ether and 19.4 g of propylene glycol monomethyl ether to prepare a solution. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition. This comparative example is an example in which the content of the crosslinking compound is too small.

<Comparative example 6>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 1.6 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinking compound, 0.036 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) were dissolved in propylene glycol A solution was prepared in 17.8 g of monoethyl ether and 35.6 g of propylene glycol monomethyl ether. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition. This comparative example is an example in which the content of the crosslinking compound is excessive.

<Comparative example 7>

8.0 g of the homopolymer solution obtained in Synthesis Example 1, 0.4 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon Cytec Industries Co., Ltd.)) as a crosslinking compound, 0.024 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) were dissolved in propylene glycol A solution was prepared in 11.9 g of monoethyl ether and 21.7 g of propylene glycol monomethyl ether. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition. This comparative example is an example in which the content of the crosslinking compound is too small.

<Comparative example 8>

8.0 g of the copolymer solution obtained in Synthesis Example 2, 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Nippon CYTEC Industries Co., Ltd.)) as a crosslinking compound, 0.028 g of SP-606 (manufactured by ADEKA Co., Ltd.) as a photoacid generator, and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) were dissolved in ethyl lactate 1 3.9 g and 26.3 g of propylene glycol monomethyl ether to make a solution. Then, this solution was filtered using a PTFE microfilter with a pore diameter of 1.0 μm to prepare a resin composition.

[Solvent resistance test]

The resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 were coated on a silicon wafer using a spin coater, baked on a heating plate at 100°C for 1 minute, and exposed at 500mJ/ ^cm2 using an i-line exposure machine NSR-2205i12D (NA=0.63) (manufactured by NIKON Co., Ltd.), and then baked at 100°C for 9 minutes to form a film with a thickness of 0.2 μm. These films were immersed in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, cyclohexanone, and 2.38% by mass tetramethylammonium hydroxide (hereinafter abbreviated as TMAH) aqueous solution at a temperature of 23°C for 5 minutes, and then dried and baked at 100°C for 1 minute. The film thickness of the film before immersion and the film after drying and baking was measured, and the film thickness change rate was calculated from the following formula.

[1-(film thickness after drying/baking/film thickness before dipping)]×100(%)

Even if one of the aforementioned immersion solvents had a film thickness change rate of 10% or more, the solvent resistance evaluation was "×", and the film thickness change rate for all solvents did not reach In 10% of the cases, the solvent resistance evaluation was "○". The evaluation results are shown in Table 1.

[Transmittance measurement]

The resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 were coated on a quartz substrate using a spin coater, baked on a hot plate at 100°C for 1 minute, and exposed at 500mJ/ ^cm2 using an i-line exposure machine NSR-2205i12D (NA=0.63) (manufactured by NIKON Co., Ltd.), and baked at 100°C for 9 minutes to form a film with a thickness of 0.2 μm. For these films, the transmittance was measured in steps of 2 nm in the wavelength range of 400 nm to 800 nm using an ultraviolet visible light spectrophotometer UV-2550 (manufactured by Shimadzu Corporation). Table 1 shows the minimum transmittance measured in the wavelength range of 400nm~800nm.

[Reliability Test]

The resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were coated on a silicon wafer using a spin coater, baked on a heating plate at 100°C for 1 minute, and exposed at 500mJ/ ^cm2 using an i-line exposure machine NSR-2205i12D (NA=0.63) (manufactured by NIKON Co., Ltd.), and then baked at 100°C for 9 minutes to form a film with a thickness of 0.2 μm. The obtained film was exposed in air at 90° C. for 240 hours, and a reliability test was carried out. The film thickness of the film before and after the test was measured using an interference film thickness meter. The rate of change in film thickness was calculated from the following formula, and when the rate of change in film thickness exceeded 5%, it was evaluated as "×", and when it was 5% or less, it was evaluated as "○". The evaluation results are shown in Table 1.

[1-(film thickness after test/film thickness before test)]×100(%)

[Color resist residue]

The resin compositions prepared in Example 1, Example 4, and Comparative Example 5 to Comparative Example 8 were coated on a silicon wafer using a spin coater, baked on a heating plate at 100°C for 1 minute, exposed using an i-line exposure machine NSR-2205i12D (NA=0.63) (manufactured by NIKON Co., Ltd.), and baked on a heating plate at 100°C for 9 minutes to form a color filter lower layer film with a film thickness of 0.2 μm. On the lower film of the color filter, apply a photoradically polymerizable pigment-dispersed red color resist liquid containing C.I. Pigment Red 254 and C.I. Pigment Red 177 as pigments, and bake it on a heating plate at 100°C for 1 minute to form a red color resist film with a film thickness of 0.5 μm. Next, using an i-line exposure machine NSR-2205i12D (NA=0.63) (manufactured by NIKON Co., Ltd.), the red color resist film was exposed through a mask, developed with 2.38% by mass TMAH aqueous solution for 60 seconds, washed with ultrapure water for 20 seconds, and dried to form a rectangular pattern of 100 μm×100 μm. Using a scanning electron microscope S-9260 (manufactured by Hitachi High-Tech Co., Ltd.), the residue of the red color resist on the lower layer film of the color filter around the rectangular pattern was observed. Table 1 shows the evaluation results of the residue level when comparing with Comparative Example 6 as a reference. The red color resist residue observed on the lower layer film of the aforementioned color filter was compared with Comparative Example 6 in three grades of "less", "more" and "equal" to evaluate the residue level.

From the results in Table 1, the film formed from the resin composition of the present invention has high solvent resistance and high transparency. Furthermore, the film formed from the resin composition of the present invention has less color resist residue, and the film formed from the resin composition of the present invention is excellent in suppressing the generation of color resist residue. On the other hand, the film formed from the resin composition prepared in Comparative Example 1 was highly transparent, but had insufficient solvent resistance. The films formed from the resin compositions prepared in Comparative Examples 2 to 4 had high solvent resistance and high transparency, but their reliability was not sufficient. The films formed from the resin compositions prepared in Comparative Example 5 and Comparative Example 6 had high solvent resistance, high transparency, and high reliability, but the residue level was at or above the standard. The film formed from the resin composition prepared in Comparative Example 7 had high solvent resistance and high transparency, but the residue level was equal to the standard. The film formed from the resin composition prepared in Comparative Example 8 had high solubility and high transparency, but the residue level was higher than the standard.

[Industrial availability]

The resin composition of the present invention is suitable as a material for forming a color filter lower layer film, a color filter upper layer film, a filler-dispersed resist lower layer film, etc. in devices such as CCD image sensors, CMOS image sensors, liquid crystal displays, and organic EL displays. In addition, when a color resist pattern is formed on the color filter underlayer film formed of the resin composition of the present invention, the generation of color resist residue can be suppressed, which is useful in improving the quality and yield of devices equipped with color filters.

Claims (8)

A resin composition comprising: a homopolymer having a structural unit represented by the following formula (1), a cross-linking compound, a photoacid generator, a surfactant, and an organic solvent. The cross-linking compound is a cross-linking compound having at least two alkoxyalkyl groups in one molecule, and is a compound having an alkoxyalkylated nitrogen atom. The content of the cross-linking compound is 40% to 60% by mass relative to the content of the homopolymer. The content of photoacid generator is at least 0.8% by mass,

In the aforementioned formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms having at least one hydroxyl group as a substituent. The resin composition as claimed in claim 1, wherein the acid generated from the photoacid generator is a superacid, and its acid dissociation constant pKa is less than -7. The resin composition as claimed in claim 1 or 2, wherein the acid generated from the aforementioned photoacid generator is Brookfield's acid. The resin composition as claimed in item 1 or 2, wherein the aforementioned The photoacid generator is N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide or a derivative thereof. The resin composition according to claim 1, wherein the aforementioned photoacid generator is a diphenyl[4-(phenylthio)phenyl]conium salt compound. A method for manufacturing a device with a color filter, comprising the following steps: coating a substrate with the resin composition according to any one of Claims 1 to 5, pre-baking the resin composition at 75°C to 110°C, exposing to near ultraviolet light, and post-baking at 75°C to 110°C to form a color filter underlayer film, and using a color resist to form a color filter on the aforementioned color filter underlayer film. The manufacturing method of a device equipped with a color filter as claimed in claim 6, which further has the following steps: a step of coating the aforementioned resin composition on the aforementioned color filter, and a step of prebaking the resin composition at 75°C to 110°C, exposing it to near ultraviolet rays, and post-baking at 75°C to 110°C to form the upper layer of the color filter. The method of manufacturing a device with a color filter according to Claim 6 or 7, wherein the aforementioned pre-baking and post-baking are carried out at a temperature below 100°C.