阅读说明：本技术 低温固化性树脂组合物 (Low-temperature curable resin composition ) 是由 大竹阳介 安达勋 坂口崇洋 于 2020-03-09 设计创作，主要内容包括：本发明的课题是提供在滤色器的下层和上层形成的固化膜形成用树脂组合物。解决手段是一种树脂组合物,其含有具有下述式(1)所示的结构单元的均聚物、1分子中具有至少2个烷氧基烷基的交联性化合物、光产酸剂、表面活性剂、以及有机溶剂,上述交联性化合物的含量相对于上述均聚物的含量为40质量％～60质量％,上述光产酸剂的含量相对于上述均聚物和上述交联性化合物的含量之和至少为0.8质量％。(在上述式中,R～(1)表示具有至少1个羟基作为取代基的碳原子数1～6的烷基。)(The 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 comprises a homopolymer having a structural unit represented by the following formula (1), a crosslinkable compound having at least 2 alkoxyalkyl groups in 1 molecule, a photoacid generator, a surfactant, and an organic solvent, wherein the content of the crosslinkable compound is 40 to 60 mass% relative to the content of the homopolymer, and the content of the photoacid generator containsThe amount of the crosslinking agent is at least 0.8% by mass relative to the sum of the contents of the homopolymer and the crosslinkable compound. (in the above formula, R 1 Represents an alkyl group having 1 to 6 carbon atoms and having at least 1 hydroxyl group as a substituent. ))

1. A resin composition comprising a homopolymer having a structural unit represented by the following formula (1), a crosslinkable compound having at least 2 alkoxyalkyl groups in 1 molecule, a photoacid generator, a surfactant, and an organic solvent,

the content of the crosslinkable compound is 40 to 60 mass% based on the content of the homopolymer, the content of the photoacid generator is at least 0.8 mass% based on the sum of the contents of the homopolymer and the crosslinkable compound,

in the formula, R¹Represents an alkyl group having 1 to 6 carbon atoms and having at least 1 hydroxyl group as a substituent.

2. The resin composition according to claim 1, wherein the acid generated from the photoacid generator is a superacid having an acid dissociation constant pKa of less than-7.

3. The resin composition according to claim 1 or 2, wherein the acid generated from the photoacid generator is a Bronsted acid.

4. The resin composition according to any one of claims 1 to 3, wherein the photoacid generator is N- (trifluoromethanesulfonyloxy) -1, 8-naphthalimide or a derivative thereof.

5. The resin composition according to claim 1, wherein the photoacid generator is a diphenyl [4- (phenylthio) phenyl ] sulfonium salt compound.

6. A method for manufacturing a device having a color filter, comprising the steps of:

a step of coating the resin composition according to any one of claims 1 to 5 on a substrate;

pre-baking the resin composition at 75 to 110 ℃, exposing the resin composition to near ultraviolet rays, and post-baking the resin composition at 75 to 110 ℃ to form a color filter underlayer film; and

and forming a color filter on the color filter underlayer film by using a color resist.

7. The method for manufacturing a device having a color filter according to claim 6, further comprising the steps of: a step of coating the resin composition on the color filter; and a step for forming an upper film of a color filter by pre-baking the resin composition at 75 to 110 ℃, exposing the resin composition to near ultraviolet rays, and post-baking the resin composition at 75 to 110 ℃.

8. The method for manufacturing a device having a color filter according to claim 6 or 7, wherein the pre-baking and the post-baking are performed at 100 ℃ or lower.

Technical Field

The present invention relates to a resin composition used for forming a cured film formed on a lower layer and an upper layer of a color filter in a device having the 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 of not more than 110 ℃.

Background

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

In general, a transparent resin film such as a protective film or a planarizing film is formed on a color filter for the purpose of protecting the color filter and smoothing irregularities on the surface of the color filter. In addition, a transparent resin film is formed also under the color filter for the purpose of improving the adhesion between the color filter and the base substrate and smoothing irregularities due to the presence of circuit wiring portions, light-shielding films, internal lenses, and the like. Compositions for forming such transparent resin films are disclosed in, for example, patent documents 1 to 4.

In the formation of the color filter, for example, a color resist of 3 colors of red, green, and blue containing a pigment or a dye is generally used. A color filter using a 3-color resist is formed by first applying a 1 st color resist, and performing exposure, development, and heat treatment to form a 1 st color resist pattern. Then, color resist patterns of the 2 nd color and the 3 rd color are formed in the same manner as the color resist pattern of the 1 st color, thereby forming a color filter.

In such a color filter forming method, it is important to suppress the generation of residues of a color resist when forming a color resist pattern in order to suppress the deterioration of color reproducibility of a color filter and the reduction of yield of a device including a color filter.

The above organic EL display device is expected to be manufactured by a process at a low temperature compared to other devices. For example, as disclosed in patent document 5, it is required not to apply a temperature higher than 110 ℃. Therefore, the transparent resin film formed on the upper and lower layers of the color filter needs to be formed by curing a resin composition at a temperature of 110 ℃.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication 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

Disclosure of Invention

Problems 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 have the above-described property of suppressing the generation of residues of the color resist. However, the transparent resin film formed of a conventional low-temperature curable material has a problem that it does not have a sufficient effect of suppressing the generation of color resist residues and has sufficient reliability as a permanent film.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition which can form a cured film having excellent solvent resistance and reliability at a temperature of not more than 110 ℃, preferably not more than 100 ℃, can suppress the generation of residues of a color resist when forming a color filter on the cured film, and can form the cured film on the color filter. Further, another object of the present invention is to provide a method for manufacturing a device having a color filter underlayer film and/or a color filter overlayer film having excellent solvent resistance and reliability.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, the present invention has been completed. 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 2 alkoxyalkyl groups in 1 molecule, a photoacid generator, a surfactant, and an organic solvent, wherein the content of the crosslinkable compound is 40 to 60 mass% with respect to the content of the homopolymer, and the content of the photoacid generator is at least 0.8 mass% with respect to the sum of the contents of the homopolymer and the crosslinkable compound.

(in the above formula, R¹Represents an alkyl group having 1 to 6 carbon atoms and having at least 1 hydroxyl group as a substituent. )

The acid generated from the above-mentioned photoacid generator is, for example, a superacid whose acid dissociation constant pKa is, for example, less than-7.

The acid generated by the photoacid generator is, for example, a bronsted acid.

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

Another aspect of the present invention is a method for manufacturing a device having a color filter, including the steps of: a step of coating the resin composition of the present invention on a substrate; pre-baking the resin composition at 75 to 110 ℃, exposing the resin composition to near ultraviolet rays, and post-baking the resin composition at 75 to 110 ℃ to form a color filter underlayer film; and forming a color filter on the color filter underlayer film by using a color resist.

The method for manufacturing a device having a color filter may further include: a step of applying the resin composition to the color filter; and a step for forming an upper film of a color filter by pre-baking the resin composition at 75 to 110 ℃, exposing the resin composition to near ultraviolet rays, and post-baking the resin composition at 75 to 110 ℃.

The above pre-baking and post-baking are preferably performed at 100 ℃ or lower.

ADVANTAGEOUS EFFECTS OF INVENTION

The color filter underlayer film or color filter overlayer film formed from the resin composition of the present invention has excellent chemical resistance, heat resistance and transparency. Thus, in the color filter underlayer film or color filter overlayer film formed from the resin composition of the present invention, the possibility of element deterioration or damage can be significantly reduced when the film is subjected to a treatment of exposure to a chemical solution such as an acid or alkali solution, a solvent, or a treatment of exposure to sputtering or dry etching in the formation step of the film or the formation step of peripheral devices such as wiring. In addition, when a color filter underlayer film is formed from the resin composition of the present invention and a color resist is applied thereon, the problem of mixing with the color resist, the problem of the generation of residues of the color resist, and the problems of deformation and peeling of the color filter underlayer film due to the chemical solution can be significantly reduced. Further, the color filter underlayer film or color filter overlayer film formed from the resin composition of the present invention can be developed using an alkaline developer after exposure to light to form a desired pattern. Therefore, the resin composition of the present invention is suitable as a material for forming a color filter underlayer film or a color filter overlayer film.

Detailed Description

The present invention is a resin composition containing a specific homopolymer, a crosslinkable compound having at least 2 alkoxyalkyl groups in 1 molecule, a photoacid generator, a surfactant, and an organic solvent. The details of each component are described below. The solid content after removing the organic solvent from the resin composition of the present invention is usually 0.01 to 50% by mass.

< homopolymer >

The homopolymer contained in the resin composition of the present invention is represented by the above formula (1)Polymers of the structural units shown. In the above formula (1), R is¹Examples of the group include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, dihydroxypropyl, and dihydroxybutyl.

Examples of the compound (monomer) forming the structural unit represented by the above formula (1) include 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. By using a homopolymer having a structural unit represented by the formula (1) in the resin composition of the present invention, it is possible to suppress the formation of a color resist residue on a color filter underlayer film formed from the resin composition after the color filter is formed thereon.

The weight average molecular weight of the homopolymer is usually 1,000 to 200,000, preferably 3,000 to 100,000. In addition, the weight average molecular weight is a value obtained by Gel Permeation Chromatography (GPC).

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

In the present invention, the method for obtaining the homopolymer is not particularly limited, and in general, the homopolymer is obtained by polymerizing a compound (monomer) forming the structural unit represented by the formula (1) in a solvent in the presence of a polymerization initiator, usually at a temperature of 50 to 120 ℃. The homopolymer obtained in this way 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.

The homopolymer obtained in the above-described manner may be put into a stirred poor solvent such as hexane, ether, toluene, methanol, or water to reprecipitate the homopolymer, and the precipitate may be decanted or filtered, and if necessary, washed, and then dried at normal temperature or under reduced pressure or heated to dry the homopolymer into oil or powder. By such an operation, the polymerization initiator and the 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 may be used in a state of being dissolved in an organic solvent described later.

< crosslinkable Compound >

The crosslinkable compound contained in the resin composition of the present invention has at least 2 alkoxyalkyl groups in 1 molecule. Examples of the crosslinkable compound include compounds having a nitrogen atom alkoxylated with an alkoxy group.

Examples of the compound having an alkoxy-alkylated nitrogen atom include nitrogen-containing compounds having a plurality of active methylol groups in one molecule, such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea, and compounds in which at least one of hydrogen atoms of a hydroxyl group in the methylol group is substituted with an alkyl group such as a methyl group or a butyl group.

The compound having a nitrogen atom alkoxylated with an alkoxy group may be a mixture obtained by mixing a plurality of substituted compounds, or a mixture containing an oligomer component partially self-condensed may be present, and such a mixture may be used. More specifically, examples thereof include CYMEL series commercial products such as hexamethoxymethylmelamine (manufactured by Nippon Kogyo サイテックインダストリーズ, CYMEL [ registered trademark ] 303), tetrabutoxymethylmelamine (manufactured by Nippon サイテックインダストリーズ, CYMEL [ registered trademark ] 1170), tetramethoxymethylbenzoguanamine (manufactured by Nippon Kogyo サイテックインダストリーズ, CYMEL [ registered trademark ] 1123), POERLINK series commercial products such as tetramethoxymethylmelamine (manufactured by Nippon Kogyo サイテックインダストリーズ, POERWDLINK [ registered trademark ] 1174), and methylated melamine resins (manufactured by Nippon Kogyo ケミカル, ニカラック [ registered trademark ] MW-30HM ニカラック MW-390, ニカラック MW-100LM ニカラック MX-750LM), ニカラック series products such as methylated urea resins (available from Sangan Kabushiki Kaisha, ケミカル, ニカラック (registered trademark) MX-270, ニカラック MX-280, ニカラック MX-290). These crosslinkable compounds may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the crosslinkable compound in the resin composition of the present invention is preferably 40 to 60% by mass based on the content of the homopolymer in the resin composition. When the content of the crosslinkable compound in the resin composition of the present invention is too large or too small, a color filter may be formed on a color filter underlayer film formed from the resin composition, and then a large amount of color resist residues may be observed on the color filter underlayer film.

< photoacid generators >

The photoacid generator included in the resin composition of the present invention is a compound that generates a strong acid upon exposure, and preferably a compound that generates a superacid having an acid dissociation constant pKa of less than-7. Specific examples of the compound includeSalt compounds, sulfonimide compounds, and disulfonyl diazomethane compounds.

As mentioned aboveSpecific examples of the salt compound include diphenyliodineHexafluorophosphate and diphenyl iodideTrifluoromethanesulfonate, diphenyliodideNonafluoro-n-butane sulfonate, diphenyl iodidePerfluoro-n-octane sulfonate, diphenyl iodideCamphorsulfonate, bis (4-t-butylphenyl) iodideCamphorsulfonate, bis (4-t-butylphenyl) iodideIodine such as trifluoromethanesulfonateSalt compound, and triphenylsulfonium hexafluorophosphate, triphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl ] sulfonate]Sulfonium hexafluorophosphate, diphenyl [4- (phenylthio) phenyl]Sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl]Sulfonium hexafluoroantimonate, diphenyl [4- (phenylthio) phenyl]Sulfonium salt compounds such as sulfonium tetrakis (pentafluorophenyl) borate. TheAmong the salt compounds, a sulfonium salt compound is preferable, and a compound which generates an acid by exposure to i-ray (365nm) is more preferable as a diphenyl [4- (phenylthio) phenyl group]Sulfonium salt compounds.

Specific examples of the above-mentioned sulfonimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-N-butanesulfonyloxy) 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 these sulfonimide compounds, N- (trifluoromethanesulfonyloxy) -1, 8-naphthalimide and its derivatives are preferable.

Specific examples of the disulfonyl diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane.

Specific examples of the photoacid generator include アデカアークルズ (registered trademark) SP-056, アデカアークルズ SP-066, アデカアークルズ SP-140, アデカアークルズ SP-141, アデカアークルズ SP-082, アデカアークルズ SP-601, アデカアークルズ SP-606, アデカアークルズ SP-701, アデカアークルズ SP-150, アデカアークルズ SP-170, アデカアークルズ SP-171 (available from ADEKA Co., Ltd.), CPI (registered trademark) -110P, CPI-110B, CPI-310B, CPI-210S, CPI-100P, CPI-101A, CPI-200K (available from サンアプロ (available from Japan Co., Ltd.), DPI-105, DPI-101, and, DPI-106, DPI-109, DPI-201, BI-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-109, BBI-105, BBI-106, TPS-200, TPS-103, NDS-105, TPS-205, TPS-200, TPS-103, TPS-105, and NDS-205, NAI-105 and NAI-109 (manufactured by みどり K.K., supra). These photoacid generators may be used alone in 1 kind or in combination in 2 or more kinds.

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 a 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. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate and sorbitan tristearate, nonionic sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, and the like A surfactant, エフトップ (registered trademark), EF301, エフトップ EF303, エフトップ EF352 (see above, Mitsubishi マテリアル electronic conversion Co., Ltd.), メガファック (registered trademark) F-171, メガファック F-173, メガファック R-30, メガファック R-40, メガファック R-40-LM (see above, DIC Co., Ltd.), フロラード FC430, フロラード FC431 (see above, Sumito スリーエム Co., Ltd.), アサヒガード (registered trademark) AG710, サーフロン (registered trademark) S-382, サーフロン SC101, サーフロン SC102, サーフロン SC103, サーフロン SC104, サーフロン SC105, サーフロン SC106 (see AGC Co., Ltd.), FTX-206D, FTX-212D, Fluorine-based surfactants such as フタージェント series (manufactured by ネオス, Inc.) including FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, DFX-18, and organosiloxane polymer KP341 (manufactured by shin-Etsu chemical Co., Ltd.). These surfactants may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

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

< organic solvent >

The organic solvent contained in the resin composition of the present invention is not particularly limited as long as it dissolves solid components contained in the resin composition. Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl cellosolve acetate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol, methylene glycol, and methylene glycol, and methylene glycol, and methylene glycol, and methylene glycol, and, Methyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, gamma-butyrolactone, N-methylpyrrolidone, and N-ethylpyrrolidone. These organic solvents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among the above organic solvents, 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 preferable from the viewpoint of improving the leveling property of a coating film formed by applying the resin composition of the present invention to a substrate.

< other additives >

The resin composition of the present invention may contain additives such as a light stabilizer, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, an adhesion promoter, and a defoaming agent, as necessary, as long as the effects of the present invention are not impaired.

< method for preparing resin composition >

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a solution of a homopolymer having a structural unit represented by the above formula (1), a crosslinkable compound, a photoacid generator and a surfactant are dissolved in an organic solvent at a predetermined ratio to prepare a uniform solution. Further, there may be mentioned a method of further adding and mixing other additives as necessary at an appropriate stage of the preparation method.

< method for producing lower layer film or upper layer film of color filter >

A method for producing a color filter underlayer film or a color filter overlayer film using the resin composition of the present invention will be described. The resin composition of the present invention is applied to a base material (for example, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer, or a substrate having various metal films, a planarization film, a color filter, an organic EL element, or the like formed on the surface thereof) by an appropriate application method such as a spin coater or a coater, and then pre-baked using a heating device such as a hot plate or an oven to form a coating film. The coating film is then exposed using an exposure machine. Further, post baking is performed by using a heating device such as a hot plate or an oven to cure the film, thereby producing a color filter lower layer film or a color filter upper layer film. The above resin composition may contain a developing treatment after coating or after pre-baking. The pre-baking and post-baking conditions are properly selected from the baking temperature of 75-110 ℃ and the baking time of 0.3-60 minutes. The post-baking may be performed in more than 2 steps. In the above exposure, for example, near ultraviolet rays (e.g., i-rays) may be used. The film thickness of the color filter underlayer film formed from the resin composition of the present invention is, for example, 0.06 to 0.5. mu.m, and the film thickness of the color filter overlayer film formed from the resin composition of the present invention is, for example, 0.3 to 1.0. mu.m.

Examples

The present invention will be described in more detail below 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 apparatus, and the weight average molecular weight (Mw) was calculated as a value converted from polyethylene glycol or polyethylene oxide.

GPC apparatus: GPC System (Shodex (registered trademark) GPC-101) column manufactured by Showa Denko K.K.: shodex (registered trademark) KD-800RH, KD-800RL, KD-803 and KD-805 column temperatures: 50 deg.C

Eluent: n, N-dimethylformamide [ as an additive, lithium bromide-hydrate (LiBr. H) was contained₂O)30mmol/L, phosphoric acid-anhydrous crystals (O-phosphoric acid) 30mmol/L, and Tetrahydrofuran (THF)10 ml/L.]

Flow rate: 1.0 mL/min

Standard sample for standard curve preparation: TSK-Standard polyethylene oxide (weight-average molecular weight (Mw)900,000, 150,000, 100,000, 30,000, manufactured by DONG ソー Ltd.), and polyethylene glycol (peak Top molecular weight (Mp)12,000, 4,000, 1,000, manufactured by ポリマーラボラトリー Ltd.)

In order to avoid the peak overlapping, samples obtained by mixing 4 types of polyethylene glycol having Mw of 900,000, 100,000 and Mp of 12,000, 1,000, and 3 types of polyethylene glycol having Mw of 150,000, 30,000 and Mp of 4,000, i.e., 2 types, were measured, respectively.

[ Synthesis of Polymer ]

< Synthesis example 1 >

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

< Synthesis example 2 >

After 30.2g of 2-hydroxypropyl acrylate, 10.0g of benzyl acrylate and 3.4g of 2, 2' -azobisisobutyronitrile were dissolved in 80.9g of propylene glycol monomethyl ether, the solution was added dropwise over 4 hours to a flask containing 49.8g of propylene glycol monomethyl ether maintained at 70 ℃. After completion of the dropwise addition, the reaction was further allowed to proceed for 18 hours to obtain a solution of a copolymer (solid content concentration: 25.0 mass%). The weight average molecular weight Mw of the resulting copolymer was 13,500.

[ preparation of resin composition ]

< example 1 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 0.8g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, and 0.028g of SP-606 (manufactured by ADEKA [ trademark ]) and 0.002g of メガファック (manufactured by DIC [ trademark ]) R-40 (manufactured by DIC [ trademark ]) as a photoacid generator were dissolved in 13.9g of propylene glycol monoethyl ether and 26.3g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition.

< example 2 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 0.8g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co.)) as a crosslinkable compound, and 0.14g of CPI-210S (manufactured by サンアプロ Co.)) and 0.002g of メガファック [ registered trademark ] R-40 (manufactured by DIC [ trademark ]) were dissolved in 13.9g of propylene glycol monoethyl ether and 26.3g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition.

< example 3 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 0.8g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, 0.14g of CPI-110B (manufactured by サンアプロ Co., Ltd.) and 0.002g of メガファック [ registered trademark ] R-40 (manufactured by DIC [ Co., Ltd.)) as a photoacid generator were dissolved in 13.9g of propylene glycol monoethyl ether and 26.3g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition.

< example 4 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 1.2g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, and 0.032g of SP-606 (manufactured by ADEKA [ trademark ]) and 0.002g of メガファック (manufactured by DIC [ trademark ]) R-40 (manufactured by DIC [ trademark ]) as a photoacid generator were dissolved in 15.8g of propylene glycol monoethyl ether and 30.9g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition.

< comparative example 1 >

8.0g of a solution of the homopolymer obtained in Synthesis example 1, 0.8g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, 0.028g of TAG2689 (manufactured by King InDUSTRIES Co., Ltd.) and 0.002g of メガファック [ registered trademark ] R-40 (manufactured by DIC [ Co., Ltd.)) as a thermal acid generator were dissolved in 13.9g of propylene glycol monoethyl ether and 26.3g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition.

< comparative example 2 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 0.8g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, 0.028g of p-toluenesulfonic acid (manufactured by Tokyo chemical industry Co., Ltd.) and 0.002g of メガファック [ registered trademark ] R-40 (manufactured by DIC [ Co., Ltd.)) as an acid compound were dissolved in 13.9g of propylene glycol monoethyl ether and 26.3g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition.

< comparative example 3 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 0.8g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japanese サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, and pyridine as an acid compound were added0.028g of p-toluenesulfonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.002g of メガファック [ registered trademark ] R-40 (manufactured by DIC Co., Ltd.) were dissolved in 13.9g of propylene glycol monoethyl ether and 26.3g of propylene glycol monomethyl ether to prepare solutions. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition.

< comparative example 4 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 0.8g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japanese サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, and pyridine as an acid compound were added0.14g of p-toluenesulfonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.002g of メガファック [ registered trademark ] R-40 (manufactured by DIC Co., Ltd.) were dissolved in 14.4g of propylene glycol monoethyl ether and 27.6g of propylene glycol monomethyl ether to prepare solutions. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition.

< comparative example 5 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 0.2g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, and 0.022g of SP-606 (manufactured by ADEKA [ trademark ]) and 0.002g of メガファック (manufactured by DIC [ trademark ]) R-40 (manufactured by DIC [ trademark ]) as a photoacid generator were dissolved in 10.9g of propylene glycol monoethyl ether and 19.4g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition. The present comparative example shows an example in which the content of the crosslinkable compound is too small.

< comparative example 6 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 1.6g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, and 0.036g of SP-606 (manufactured by ADEKA [ trademark ]) and 0.002g of メガファック (manufactured by DIC [ trademark ]) R-40 (manufactured by DIC [ trademark ]) as a photoacid generator were dissolved in 17.8g of propylene glycol monoethyl ether and 35.6g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition. The present comparative example shows an excessive content of the crosslinkable compound.

< comparative example 7 >

8.0g of the homopolymer solution obtained in Synthesis example 1, 0.4g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, and 0.024g of SP-606 (manufactured by ADEKA [ trademark ]) and 0.002g of メガファック (manufactured by DIC [ trademark ]) R-40 (manufactured by DIC [ trademark ]) as a photoacid generator were dissolved in 11.9g of propylene glycol monoethyl ether and 21.7g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size of 1.0 μm to prepare a resin composition. The present comparative example shows an example in which the content of the crosslinkable compound is too small.

< comparative example 8 >

8.0g of a solution of the copolymer obtained in Synthesis example 2, 0.8g of tetramethoxymethyl glycoluril (POWDERLINK [ registered trademark ] 1174 (manufactured by Japan サイテックインダストリーズ Co., Ltd.)) as a crosslinkable compound, 0.028g of SP-606 (manufactured by ADEKA [ trademark ]) and 0.002g of メガファック (manufactured by DIC [ trademark ]) R-40 (manufactured by DIC [ trademark ]) as a photoacid generator were dissolved in 13.9g of ethyl lactate and 26.3g of propylene glycol monomethyl ether to prepare a solution. Then, the solution was filtered through a microfilter made of PTFE and having a pore size 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 applied to a silicon wafer using a spin coater, baked at 100 ℃ for 1 minute on a hot plate, and exposed to 500mJ/cm using an i-ray stepper NSR-2205i12D (NA 0.63) (manufactured by Ltd.) (ニコン)²After exposure, the film was further baked at 100 ℃ for 9 minutes to form a film having a thickness of 0.2. mu.m. For these films, they were immersed in propylene glycol at a temperature of 23 ℃ respectivelyAlcohol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, cyclohexanone, and a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter, abbreviated as TMAH.) were added to the solution for 5 minutes, and then dried and baked at 100 ℃ for 1 minute. The film thickness of the film before immersion and the film after drying and baking were measured, and the film thickness change rate was calculated from the following equation.

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

Solvent resistance was evaluated as "x" when the film thickness change rate was 10% or more in 1 of the above immersion solvents, and as "o" when the film thickness change rate was less than 10% in all the solvents. The evaluation results are shown in table 1.

[ measurement of transmittance ]

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, respectively, baked on a hot plate at 100 ℃ for 1 minute, and exposed to 500mJ/cm using an i-ray stepper NSR-2205i12D (NA 0.63) (manufactured by strain ニコン)²After exposure, the film was further baked at 100 ℃ for 9 minutes to form a film having a thickness of 0.2. mu.m. The transmittance of these films was measured by changing the wavelength of the films in a range of 400nm to 800nm in a little by little manner at 2nm using an ultraviolet-visible spectrophotometer UV-2550 (manufactured by Shimadzu corporation). The values of the minimum transmittance measured at a wavelength of 400nm to 800nm are shown in Table 1.

[ reliability test ]

The resin compositions prepared in examples 1 to 4 and comparative examples 2 to 6 were applied to a silicon wafer using a spin coater, baked at 100 ℃ for 1 minute on a hot plate, and exposed to 500mJ/cm using an i-ray stepper NSR-2205i12D (NA 0.63) (manufactured by Ltd.) (ニコン)²After exposure, the film was further baked at 100 ℃ for 9 minutes to form a film having a thickness of 0.2. mu.m. The resulting film was exposed to air at 90 ℃ for 240 hours, and a reliability test was performed. The film thickness of the film before and after the test was measured using an interference film thickness meter. The film thickness change rate was calculated from the following formula, and when the film thickness change rate exceeded 5%, the film was evaluated as "x", and the film was formedWhen the thickness change rate was 5% or less, the evaluation was "o". The evaluation results are shown in table 1.

[1- (post-test film thickness/pre-test film thickness) ]. times.100 (%)

[ color resist residue ]

The resin compositions prepared in examples 1 and 4 and comparative examples 5 to 8 were applied to a silicon wafer using a spin coater, exposed to light at 100 ℃ for 1 minute on a hot plate using an i-ray stepper NSR-2205i12D (NA 0.63) (manufactured by strain ニコン) and further baked at 100 ℃ for 9 minutes on a hot plate, to form a color filter underlayer film having a thickness of 0.2 μm. A photo radical polymerizable pigment dispersion type red color resist solution containing c.i. pigment red 254 and c.i. pigment red 177 as pigments was applied on the color filter underlayer film, and baked on a hot plate at 100 ℃ for 1 minute to form a red color resist film with a film thickness of 0.5 μm. Next, the red color resist film was exposed through a mask using an i-ray stepper NSR-2205i12D (NA 0.63) (manufactured by strain ニコン), developed with a 2.38 mass% aqueous TMAH solution for 60 seconds, rinsed with ultrapure water for 20 seconds, and then dried to form a rectangular pattern of 100 μm × 100 μm. The residue of the red color resist on the lower film of the color filter around the rectangular pattern was observed by using a scanning electron microscope S-9260 (manufactured by hitachi ハイテクノロジーズ, ltd.). The evaluation results of the residue levels when compared with comparative example 6 are shown in table 1. The red color resist residue observed on the color filter underlayer film was evaluated at 3 levels of "less", "more", and "equivalent" as compared with comparative example 6.

TABLE 1

According to the results of table 1, the film formed from the resin composition of the present invention is high in solvent resistance and high in transparency. In addition, the film formed from the resin composition of the present invention has less residue of a color resist, and the film formed from the resin composition of the present invention has an excellent effect of suppressing the generation of residue of a color resist. On the other hand, the film formed from the resin composition prepared in comparative example 1 had high transparency but 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 the reliability was insufficient. The films formed from the resin compositions prepared in comparative examples 5 and 6 had high solvent resistance, high transparency and high reliability, but the residue level was the standard level or more. The film formed from the resin composition prepared in comparative example 7 had high solvent resistance and high transparency, but the residue level was the same as 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 reference level.

Industrial applicability

The resin composition of the present invention is suitable as a material for forming a color filter underlayer film, a color filter overlayer film, a filler dispersed resist underlayer film, and the like 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 a color filter underlayer film formed from the resin composition of the present invention, the generation of residues of the color resist can be suppressed, and it is useful for improving the quality and yield of a device provided with a color filter.