TW202104289A - Low temperature curable resin composition - Google Patents

Abstract

(前述式中，R¹ 表示具有至少1個羥基作為取代基之碳原子數1至6之烷基)。The present invention provides a resin composition for forming a cured film formed on the lower layer and the 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 crosslinkable compound having at least two alkoxyalkyl groups in one molecule, a photoacid generator, a surfactant, and In the organic solvent, the content of the crosslinkable compound is 40% to 60% by mass relative to the content of the homopolymer, and the photoacid generator is relative to the sum of the content of the homopolymer and the crosslinkable compound. The content is at least 0.8% by mass.

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

Description

Low-temperature curable resin composition

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

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

Generally, for the purpose of protecting the color filter and smoothing the unevenness on the surface of the color filter, a transparent resin film of a protective film and a flattening film is formed on the color filter. And for the purpose of improving the adhesion between the color filter and the base substrate, and smoothing the unevenness due to the presence of the circuit wiring part, light-shielding film, endoscope, etc., a transparent resin film is also formed under the color filter. Compositions for forming these transparent resin films are disclosed in Patent Document 1 to Patent Document 4, for example.

The formation of color filters generally uses, for example, three color resists of red, green and blue containing pigments or dyes. To form a color filter using three-color color resists, first coat the color resist of the first color, and perform exposure, development and heating treatments to form a pattern of the color resist of the first color. Subsequently, similar to the color resist pattern of the first color, the color resist pattern of the second color and the third color are formed to form a color filter.

In these color filter forming methods, in order to suppress the deterioration of the color reproducibility of the color filter and the decrease in the yield of the device equipped with the color filter, it is important to suppress the color resist during the formation of the color resist pattern The residue occurred.

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 the organic EL device, 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 below 110°C. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2000-344866 A [Patent Document 2] JP 2008-031370 A [Patent Document 3] Japanese Patent No. 4222457 [Patent Document 4] International Publication No. 2013/005619 [Patent Document 5] International Publication No. 2017/203885

[The problem to be solved by the invention]

In the case of forming a color filter on the transparent resin film, the transparent resin film is required to suppress the generation of residues of the color resist as described above. However, the transparent resin film formed from the conventional low-temperature curable material cannot have both the effect of sufficiently suppressing the generation of residues 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 cured film that can be formed at a temperature not exceeding 110°C, preferably below 100°C, with excellent solvent resistance and reliability, and forming a color on the cured film When the filter is used, the generation of residues of the color resist can be suppressed, and at the same time, the resin composition of the hardened film can be formed on the color filter. In addition, another object of the present invention is to provide a method for manufacturing a color filter device having a color filter lower layer film and/or a color filter upper layer film with excellent solvent resistance and reliability. [Means to solve the problem]

(前述式中，R¹ 表示具有至少1個羥基作為取代基之碳原子數1至6之烷基)。The inventors of the present invention have completed the present invention as a result of active reviews in order to solve the aforementioned problems. That is, the present invention is a resin composition containing: a homopolymer having a structural unit represented by the following formula (1), a crosslinkable compound having at least two alkoxyalkyl groups in one molecule, and a photoacid generator Agent, surfactant and organic solvent, relative to the content of the aforementioned homopolymer, the content of the aforementioned crosslinkable compound is 40% to 60% by mass, relative to the sum of the content of the aforementioned homopolymer and the aforementioned crosslinkable compound , The content of the aforementioned photoacid generator is at least 0.8% by mass.

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

The acid generated from the aforementioned photoacid generator is a super strong acid, and its acid dissociation constant pKa is, for example, less than -7.

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

The aforementioned photoacid generator is, for example, N-(trifluoromethanesulfonyloxy)-1,8-naphthalenedimethimide or its derivatives or diphenyl[4-(phenylthio)phenyl]sulfonate Compound.

Another aspect of the present invention is a method for manufacturing a device with color filters, which has the following steps: The step of coating the resin composition of the present invention on the substrate, pre-baking the resin composition at 75°C to 110°C, and after exposure to near-ultraviolet rays, post-baking at 75°C to 110°C to form the lower layer of the color filter The step of filming, and the step of using a color resist to form a color filter on the lower layer film of the aforementioned color filter.

The manufacturing method of the aforementioned color filter-equipped device may further have the following steps: the step of coating the aforementioned resin composition on the aforementioned color filter, and pre-baking the aforementioned resin composition at 75°C to 110°C, After exposure to near-ultraviolet rays, post-baking at 75°C to 110°C to form the upper layer of the color filter.

The aforementioned pre-baking and post-baking are preferably performed below 100°C. [Effects of the invention]

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, 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 alkali solution during its formation step or the formation step of peripheral devices such as wiring. , Or solvent treatment, or exposure to sputtering and dry etching, can significantly reduce the possibility of component deterioration or damage. In addition, when the color filter underlayer film is formed from the resin composition of the present invention, and the color resist is coated on it, the problem of mixing with the color resist, the problem of the residue of the color resist, and the above-mentioned chemical solution The problem of deformation and peeling of the underlying film of the color filter can also be significantly reduced. Furthermore, the color filter lower layer film or the color filter upper layer film formed of the resin composition of the present invention can be developed with an alkaline developer to form a desired pattern after exposure. Therefore, the resin composition of the present invention is suitable as a material for forming a lower layer film of a color filter or an upper layer film of a color filter.

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 explained below. The solid content of the organic solvent removed from the resin composition of the present invention is usually 0.01% by mass to 50% by mass.

<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) are, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxymethyl methacrylate, and 3-hydroxyethyl methacrylate. Hydroxypropyl, 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 a homopolymer having a structural unit represented by the formula (1), after forming a color filter on the color filter underlayer film formed from the resin composition, it is possible to suppress Residues of the color resist generated on the underlayer film of the color filter.

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).

Furthermore, the content of the aforementioned homopolymer in the resin composition of the present invention is generally 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 achieved by putting the compound (monomer) forming the structural unit represented by the aforementioned formula (1) in a solvent in the presence of a polymerization initiator, It is usually obtained by polymerization reaction at a temperature of 50°C to 120°C. The homopolymer thus obtained is usually in the state of a solution dissolved in a solvent, and can also be used in the resin composition of the present invention without undergoing isolation in this state.

In addition, the homopolymer solution obtained as described above is poured into a stirred weak solvent such as hexane, diethyl ether, toluene, methanol, water, etc., to re-precipitate the homopolymer, and the resulting precipitate is decanted or filtered After washing as needed, drying at room temperature or heating under normal pressure or reduced pressure can make the homopolymer into oil or powder. By this operation, the polymerization initiator or unreacted compound coexisting with the homopolymer can be removed. In the present invention, the oily substance or powder of the homopolymer may be used as it is, or the oily substance or powder may be re-dissolved in, for example, an organic solvent described later, and used as a solution state.

＜Crosslinkable compound＞ The crosslinkable compound contained in the resin composition of the present invention has at least two alkoxyalkyl groups in one molecule. As the crosslinkable compound, a compound having a nitrogen atom alkylated with an alkoxy group can be exemplified.

As the aforementioned compound having an alkoxy-alkylated nitrogen atom, for example (poly)methylolated melamine, (poly)methylolated glycoluril, (poly)methylolated benzoguanidine, (poly)hydroxy A nitrogen-containing compound having multiple active methylol groups in one molecule such as methylated urea can be exemplified as a compound in which at least one of the hydrogen atoms of the hydroxyl group in the methylol group is substituted by an alkyl group such as a methyl group, a butyl group, etc. .

The aforementioned compounds with alkoxy-alkylated nitrogen atoms may be mixtures of plural substituted compounds, or mixtures containing a part of self-condensed oligomer components, and these may also be used. mixture. More specifically, for example, hexamethoxymethyl melamine (manufactured by CYTEC Industry Co., Ltd., CYMEL [registered trademark] 303), tetrabutoxymethyl glycoluril (manufactured by CYTEC Industry Co., Ltd., CYMEL [registered trademark) ] 1170), tetramethoxymethyl phenylguanidine (CYTEC Industry Co., Ltd. of Japan, CYMEL [registered trademark] 1123) and other CYMEL products, tetramethoxymethyl glycoluril (CYTEC Industry Co., Ltd., Japan) POWDERLINK [registered trademark] 1174) and other POWDERLINK series products, and methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., NIKALAC [registered trademark] MW-30HM, same as MW-390, same as MW-100LM, Same as MW-750LM), methylated urea resin (manufactured by Sanwa Chemical Co., Ltd., NIKALAC [registered trademark] MX-270, same as MX-280, same as MX-290) and other products of the NIKALAC series. These crosslinkable compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the crosslinkable 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 aforementioned cross-linking compound in the resin composition of the present invention is excessive or insufficient, after forming a color filter on the color filter underlayer film formed by the resin composition, apply the color filter underlayer film The residue of the color resist observed above may increase.

＜Photoacid generator＞ The photoacid generator contained in the resin composition of the present invention generates a strong acid by exposure, preferably a compound that generates a super acid with an acid dissociation constant pKa of less than -7. As specific examples of the compound, an onium salt compound, a sulfonylimide compound, and a disulfonylimide compound are exemplified.

Specific examples of onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butane sulfonate, diphenyliodonium perfluoro-n-octane Alkyl sulfonate, diphenyl iodophor camphor sulfonate, bis (4-tertiary butyl phenyl) iodonium camphor sulfonate, bis (4- tertiary butyl phenyl) iodonium trifluoromethane sulfonate, etc. The phosphonium salt compound, and triphenyl sulfonium hexafluorophosphate, triphenyl fen ginseng (pentafluoroethyl) trifluorophosphate, triphenyl sulfonium hexafluoroantimonate, triphenyl sulfonium (pentafluorobenzene) Base) borate, triphenyl sulfonium nonafluoro n-butane sulfonate, triphenyl sulfonium camphor sulfonate, triphenyl sulfonium trifluoromethane sulfonate, diphenyl [4-(phenylsulfanyl) benzene Phosphate, diphenyl[4-(phenylthio)phenyl] ginseng (pentafluoroethyl) trifluorophosphate, diphenyl[4-(phenylthio)phenyl] sulfonium Hexafluoroantimonate, diphenyl [4-(phenylthio) phenyl] sulfonate (pentafluorophenyl) borate and other sulphonate compounds. Among the onium salt compounds, a sulfonium salt compound is preferred, and a diphenyl[4-(phenylthio)phenyl] sulfonate compound is more preferred as a compound that generates an acid by exposure using i-line (365 nm).

As specific examples of the aforementioned sulfonimide compound, N-(trifluoromethanesulfonyloxy) succinimide, N-(nonafluoron-butanesulfonyloxy) succinimide, N-(camphor) Sulfonyloxy) succinimidyl, N-(trifluoromethanesulfonyloxy)-1,8-naphthalenedimethimide, N-(trifluoromethanesulfonyloxy)-2-alkyl- 1,8-Naphthalenedimethimide, N-(trifluoromethanesulfonyloxy)-3-alkyl-1,8-naphthalenedimide and N-(trifluoromethanesulfonyloxy) -4-Alkyl-1,8-naphthalenedimethimide. Among the sulfonimide compounds, N-(trifluoromethanesulfonyloxy)-1,8-naphthalenedimide and its derivatives are preferred.

As a specific example of the aforementioned disulfonyl diazomethane compound, bis(trifluoromethylsulfonyl) diazomethane is exemplified.

As a specific example of the aforementioned photoacid generator, ADEKA ARKLS (registered trademark) SP-056, the same SP-066, the same SP-140, the same SP-141, the same SP-082, the same SP-601, the same SP-606 , Same SP-701, same SP-150, same SP-170, same SP-171 (above are ADEKA (share) system), CPI (registered trademark) -110P, same -110B, same -310B, same -210S, Same-100P, same-101A, same-200K (the above is SAN APRO (share) system), 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 the above 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.

In addition, the content of the photoacid generator in the resin composition of the present invention is usually 0.8 to 20% by mass based on the sum of the content of the homopolymer and the crosslinkable compound in the resin composition. It is preferably 1.0% by mass to 15% by mass. 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.

＜Surface active agent＞ The resin composition of the present invention contains a surfactant for the purpose of improving coatability. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, and polyoxyethylene octyl ether. Polyoxyethylene alkyl aryl ethers such as phenyl ether, polyoxyethylene nonylphenyl ether, etc., polyoxyethylene. Polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan Sorbitan fatty acid esters such as trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene Anions such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. It is a surfactant, EF TOP (registered trademark) EF301, the same as EF303, the same as EF352 (the above are manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFAC [registered trademark] F-171, the same as F-173, the same as R-30, Same as R-40, same as R-40-LM (the above is DIC (share) system), FLUORAD FC430, the same as FC431 (the above is Sumitomo 3M (share) system), ASAHI GUARD (registered trademark) AG710, SURFLON (registered trademark) S-382, same SC101, same SC102, same SC103, same SC104, same SC105, same SC106 (AGC (share) system), FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX -240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, DFX-18, etc. FTERGENT series (made by NEOS) and other fluorine-based surfactants, and organosiloxane polymer KP341( Shin-Etsu Chemical Industry Co., Ltd.), etc. These surfactants may be used individually by 1 type, or may be used in combination of 2 or more types.

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

＜Organic solvents＞ 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, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, and diethylene two Alcohol 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, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl glycolate Ester, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Methyl propionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, γ-butyrolactone, N-methylpyrrolidone and N-ethylpyrrole Pyridone. These organic solvents may be used individually by 1 type, or may be used in combination of 2 or more types.

Among the aforementioned organic solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether are preferred from the viewpoint of improving the leveling properties of the coating film formed by applying the resin composition of the present invention on a substrate. Ethyl ether, propylene glycol monopropyl ether, 2-heptanone, ethyl lactate, butyl lactate, cyclopentanone, cyclohexanone and gamma-butyrolactone.

＜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 needed, 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 examples include, for example, a solution of a homopolymer having a structural unit represented by the aforementioned formula (1), a crosslinkable compound, a photoacid generator, and a surfactant A method of dissolving in an organic solvent in a specific ratio to make a uniform solution. An example is a method of adding and mixing other additives as needed at an appropriate stage of the preparation method.

＜Making method of color filter lower layer film or color filter upper layer film＞ The manufacturing method of the color filter lower layer film or the color filter upper layer film using the resin composition of the present invention will be described. By appropriate coating methods such as spin coaters, coaters, etc., on substrates (such as semiconductor substrates, glass substrates, quartz substrates, silicon wafers, and various metal films, planarization films, and color filters are formed on these surfaces). The resin composition of the present invention is coated on a substrate (such as a light sheet, an organic EL element, etc.), and then pre-baked using heating means such as a hot plate, an oven, etc., to form a coating film. Next, an exposure machine is used to expose the coating film. Further, use heating means such as a heating plate, an oven, etc., to bake and harden it 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, a development process may also be included. The aforementioned pre-baking and post-baking conditions are appropriately selected from the baking temperature of 75°C to 110°C and the baking time of 0.3 minutes to 60 minutes. This post-baking can also be processed in two or more stages. The aforementioned exposure may use, for example, near ultraviolet rays (for example, i-line). In addition, the 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 by a GPC device, and the weight average molecular weight (Mw) was calculated as a polyethylene glycol and polyethylene oxide conversion value. GPC device: Showa Denko Corporation 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 additives include lithium bromide-hydrate (LiBr·H ₂ O) 30mmol/L, phosphoric acid anhydrous crystals (o-phosphoric acid) 30mmol/L, and tetrahydrofuran (THF) 10ml /L] Flow rate: 1.0mL/min. Standard sample for calibration line preparation: TOSOH (stock) TSK standard polyethylene oxide [weight average molecular weight (Mw) 900,000, 150,000, 100,000, 30,000] and Polymer Laboratory company’s polyethylene Diol [Peak Top Molecular Weight (Mp) 12,000, 4,000, 1,000] In order to avoid overlapping of peaks, two samples were measured separately, that is, standard polyethylene oxide with Mw of 900,000 and 100,000 and polyethylene oxide with Mp of 12,000 and 1,000 A sample of 4 types of alcohols, and a sample of 3 types of standard polyethylene oxide with Mw of 150,000 and 30,000, and polyethylene glycol with Mp of 4,000.

[Synthesis of Polymers] ＜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 to the propylene glycol monomethyl ether 49.0. g Keep in a flask at 70°C. After the dropwise addition, the reaction was continued 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 30.2 g of 2-hydroxypropyl acrylate, 10.0 g of benzyl acrylate and 3.4 g of 2,2'-azobisisobutyronitrile were dissolved in 80.9 g of propylene glycol monomethyl ether, the solution was added dropwise to the propylene glycol over 4 hours. 49.8 g of monomethyl ether was kept in a flask at 70°C. After completion of the dropping, the reaction was continued for 18 hours to obtain a copolymer solution (solid content concentration of 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, and 0.8 g of tetramethoxymethyl glycoluril as a crosslinkable compound (POWDERLINK [registered trademark] 1174 (manufactured by CYTEC Industry Co., Ltd.)) as a photoacid SP-606 (manufactured by ADEKA (stock)) 0.028g and MEGA FAC [registered trademark] R-40 (manufactured by DIC (stock)) 0.002g, dissolved in 13.9g of propylene glycol monoethyl ether and 26.3g of propylene glycol monomethyl ether Make a solution. Subsequently, the 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, and 0.8 g of tetramethoxymethyl glycoluril as a crosslinkable compound (POWDERLINK [registered trademark] 1174 (manufactured by CYTEC Industry Co., Ltd.)) as a photoacid CPI-210S (manufactured by SAN APRO (stock)) 0.14g and MEGA FAC [registered trademark] R-40 (manufactured by DIC (stock)) 0.002g, dissolved in 13.9g of propylene glycol monoethyl ether and 26.3g of propylene glycol monomethyl ether In the solution. Subsequently, the 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, and 0.8 g of tetramethoxymethyl glycoluril as a crosslinkable compound (POWDERLINK [registered trademark] 1174 (manufactured by CYTEC Industry Co., Ltd.)) as a photoacid CPI-110B (manufactured by SAN APRO (stock)) 0.14g and MEGA FAC [registered trademark] R-40 (manufactured by DIC (stock)) 0.002g, dissolved in 13.9g of propylene glycol monoethyl ether and 26.3g of propylene glycol monomethyl ether In the solution. Subsequently, the 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, and 1.2 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by CYTEC Industry Co., Ltd.)) as a crosslinking compound, as a photoacid SP-606 (manufactured by ADEKA (stock)) 0.032g and MEGA FAC [registered trademark] R-40 (manufactured by DIC (stock)) 0.002g, dissolved in 15.8g of propylene glycol monoethyl ether and 30.9g of propylene glycol monomethyl ether Make a solution. Subsequently, the 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 CYTEC Industry Co., Ltd.)) as a cross-linking compound, as a thermal acid 0.028 g of TAG2689 (manufactured by KING INDUSTRIES) and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC (stock)) as a generator were dissolved in 13.9 g of propylene glycol monoethyl ether and 26.3 g of propylene glycol monomethyl ether to make a solution. Subsequently, the 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, and 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Japan CYTEC Industry Co., Ltd.)) as a cross-linking compound, as an acid compound 0.028 g of p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.002 g of MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.), dissolved in 13.9 g of propylene glycol monoethyl ether and 26.3 of propylene glycol monomethyl ether Make a solution in g. Subsequently, the 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, and 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Japan CYTEC Industry Co., Ltd.)) as a cross-linking compound, as an acid compound Pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.028g and MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002g, dissolved in 13.9g of propylene glycol monoethyl ether and propylene glycol mono A solution was made in 26.3 g of methyl ether. Subsequently, the 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, and 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by Japan CYTEC Industry Co., Ltd.)) as a cross-linking compound, as an acid compound Pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.14g and MEGA FAC [registered trademark] R-40 (manufactured by DIC Co., Ltd.) 0.002g, dissolved in 14.4g of propylene glycol monoethyl ether and propylene glycol mono A solution was made in 27.6 g of methyl ether. Subsequently, the 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, and 0.2 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by CYTEC Industry Co., Ltd.)) as a cross-linking compound, as a photoacid SP-606 (made by ADEKA (stock)) 0.022g and MEGA FAC [registered trademark] R-40 (made by DIC (stock)) 0.002g of the generator, dissolved in 10.9g of propylene glycol monoethyl ether and 19.4g of propylene glycol monomethyl ether Make a solution. Subsequently, the 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 cross-linkable 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 CYTEC Industry Co., Ltd.)) as a cross-linking compound, as a photoacid SP-606 (manufactured by ADEKA (stock)) 0.036g and MEGA FAC [registered trademark] R-40 (manufactured by DIC (stock)) 0.002g, dissolved in 17.8g of propylene glycol monoethyl ether and 35.6g of propylene glycol monomethyl ether Make a solution. Subsequently, the 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 where the content of the cross-linking 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 CYTEC Industry Co., Ltd.)) as a cross-linking compound, as a photoacid SP-606 (manufactured by ADEKA (stock)) 0.024g and MEGA FAC [registered trademark] R-40 (manufactured by DIC (stock)) 0.002g, dissolved in 11.9g of propylene glycol monoethyl ether and 21.7g of propylene glycol monomethyl ether Make a solution. Subsequently, the 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 cross-linkable compound is too small.

<Comparative Example 8> 8.0 g of the copolymer solution obtained in Synthesis Example 2 and 0.8 g of tetramethoxymethyl glycoluril (POWDERLINK [registered trademark] 1174 (manufactured by CYTEC Industry Co., Ltd.)) as a cross-linking compound were produced as photoacid SP-606 (made by ADEKA (stock)) 0.028g and MEGA FAC[registered trademark] R-40 (made by DIC (stock)) 0.002g, dissolved in 13.9g of ethyl lactate and 26.3g of propylene glycol monomethyl ether Solution. Subsequently, the 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 Example 1 to Example 4 and Comparative Example 1 to Comparative Example 8 were respectively coated on a silicon wafer using a spin coater, and baked at 100°C on a hot plate bake for 1 minute, using an i-line exposure device NSR-2205i12D (NA = 0.63) (NIKON ( shares), Ltd.), to 500mJ / cm ² exposure, and further baked at 100 ℃ 9 minutes to form a film of a thickness of 0.2μm. For these films, use propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-ethoxy ethyl propionate, cyclohexanone, and 2.38 mass% tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution In each, they were immersed 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 equation. [1-(Film thickness after drying and baking/Film thickness before immersion)]×100(%) Even if the film thickness change rate of one type of immersion solvent is 10% or more, the solvent resistance is evaluated as "×" , For the case where the film thickness change rate of all solvents is less than 10%, the solvent resistance is evaluated as "○". 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 respectively coated on a quartz substrate using a spin coater, and baked at 100°C on a hot plate 1 minutes, using an i-line exposure device NSR-2205i12D (NA = 0.63) (NIKON ( shares), Ltd.), to 500mJ / cm ² exposure, and further baked at 100 ℃ 9 minutes to form a film having a thickness of 0.2μm. For these films, an ultraviolet-visible light spectrophotometer UV-2550 (manufactured by Shimadzu Corporation) was used to measure the transmittance at a wavelength of 400nm to 800nm with successive changes of 2nm. The lowest transmittance values measured in the wavelength range of 400nm~800nm are shown in Table 1.

[Reliability Test] The resin compositions prepared in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 6 were respectively coated on a silicon wafer using a spin coater, and baked at 100°C on a hot plate For 1 minute, the i-line exposure machine NSR-2205i12D (NA= 0.63) (manufactured by NIKON) was used to ^{expose at 500 mJ/cm 2} 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 to the air at 90°C for 240 hours, and the reliability test was carried out. Use an interference film thickness meter to measure the film thickness of the film before and after the test. The film thickness change rate was calculated from the following formula, and when the film thickness change rate 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 respectively coated on a silicon wafer using a spin coater, and baked on a hot plate at 100°C for 1 minute, using i Line exposure machine NSR-2205i12D (NA= 0.63) (manufactured by NIKON (stock)) was exposed, and then baked on a hot plate at 100°C for 9 minutes to form a color filter underlayer film with a thickness of 0.2μm. On the lower film of the color filter, apply a photoradical polymerizable pigment dispersion type red color resist solution containing CI Pigment Red 254 and CI Pigment Red 177 as pigments, and bake it on a hot plate at 100°C for 1 minute Bake to form a red color resist film with a thickness of 0.5μm. Next, using an i-line exposure machine NSR-2205i12D (NA= 0.63) (manufactured by NIKON), the red color resist film was exposed through a mask, and the image was developed with a 2.38% by mass TMAH aqueous solution for 60 seconds. After washing with pure water for 20 seconds, it was 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.), observe the residue of the red color resist on the underlayer film of the color filter around the rectangular pattern. Table 1 shows the evaluation result of the residue level when comparing with Comparative Example 6 as a reference. The red color resist residues observed on the lower layer film of the color filter were evaluated in three levels of "less", "more", and "equal" compared with Comparative Example 6. The residue level was evaluated.

From the results of Table 1, the film formed from the resin composition of the present invention has high solvent resistance and high transparency. In addition, the film formed from the resin composition of the present invention has less color resist residues, and the film formed from the resin composition of the present invention has an excellent effect of suppressing the generation of color resist residues. On the other hand, although the film formed from the resin composition prepared in Comparative Example 1 has high transparency, the solvent resistance is insufficient. Regarding the film formed from the resin composition prepared in Comparative Example 2 to Comparative Example 4, although it has high solvent resistance and high transparency, the reliability is insufficient. Regarding the film formed from the resin composition prepared in Comparative Example 5 and Comparative Example 6, although the film has high solvent resistance, high transparency, and high reliability, the residue level is the standard or more than the standard. Although the film formed from the resin composition prepared in Comparative Example 7 has high solvent resistance and high transparency, the residue level is equal to the standard. Regarding the film formed from the resin composition prepared in Comparative Example 8, although it has high solubility and high transparency, the residue level is higher than the reference. [Industrial availability]

The resin composition of the present invention is suitable for forming a color filter lower layer film, a color filter upper layer film, and a filler dispersion resist in devices such as CCD image sensors, CMOS image sensors, liquid crystal displays, organic EL displays, etc. Materials such as underlayer film. In addition, the formation of color resist patterns on the color filter underlayer film formed by the resin composition of the present invention can suppress the generation of color resist residues, which is useful for 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 crosslinkable compound having at least two alkoxyalkyl groups in one molecule, a photoacid generator, and a surfactant And the organic solvent, the content of the crosslinkable compound is 40% to 60% by mass relative to the content of the homopolymer, and the photoacid is generated relative to the sum of the content of the homopolymer and the crosslinkable compound The content of the agent is at least 0.8% by mass,

In the foregoing 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 of claim 1, wherein the acid generated from the aforementioned photoacid generator is a super acid, and its acid dissociation constant pKa is less than -7. The resin composition of claim 1 or 2, wherein the acid generated from the aforementioned photoacid generator is Brucella acid. The resin composition of any one of claims 1 to 3, wherein the aforementioned photoacid generator is N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide or its derivative. The resin composition of claim 1, wherein the aforementioned photoacid generator is a diphenyl[4-(phenylthio)phenyl]sulfonate compound. A method for manufacturing a device with color filters, which has the following steps: The step of coating the resin composition of any one of claims 1 to 5 on the substrate, The step of pre-baking the resin composition at 75°C to 110°C, exposure to near-ultraviolet rays, and post-baking at 75°C to 110°C to form the color filter underlayer film, and The step of forming a color filter using a color resist on the lower layer film of the color filter. For example, the method for manufacturing a device with a color filter of claim 6, which further has the following steps: The step of coating the aforementioned resin composition on the aforementioned color filter, and pre-baking the resin composition at 75°C to 110°C, and after exposure to near-ultraviolet rays, post-baking at 75°C to 110°C to form a color filter The step of the film on the chip. According to claim 6 or 7, the method for manufacturing a device with a color filter, wherein the aforementioned pre-baking and post-baking are performed at 100°C or lower.