TW202112833A - Resin composition - Google Patents

Abstract

This resin composition containing (A) an alkali-soluble copolymer, (B) a compound having two or more polymerizable groups which are one or more kinds of groups selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group and an allyl group, (C) a photoinitiator, (D) a black pigment, (E) a liquid repellent component and (F) a solvent exhibits good curability in a light exposure process even in a colored state, and is capable of forming a pattern, thereby enabling the achievement of a cured film having high visible light blocking properties after curing of this resin composition.

Description

Resin composition

The present invention relates to a resin composition having photosensitivity. More specifically, it relates to a resin composition suitable as a material for self-luminous displays such as quantum dot-organic electroluminescent (QD-OLED) displays or Micro LED displays.

Self-luminous displays such as QD-OLED displays or Micro LED displays are based on blue self-luminous elements as the base, and the red and green wavelength conversion layers are assembled by inkjet method based on the next-generation display technology. This technology is evaluated as a technology that has high color reproducibility and can express richer colors.

In the above-mentioned self-luminous display, in order to further improve the image quality, the use of light-shielding colored partitions (colored liquid-repellent partitions) for partitions formed of sub-pixels of the wavelength conversion layer of the display panel has been studied. However, in the conventional colored photosensitive resin composition, since the transmittance of incident light is low in the exposure process of forming the partition, it cannot be cured sufficiently to the deep part of the film, and pattern formation defects may occur. On the other hand, when the hardening of the film is the priority, it is difficult to ensure the necessary light-shielding properties due to insufficient addition of the colorant.

In addition, aspects of prior art documents related to the present invention can be cited as follows. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2015/060240

[The problem to be solved by the invention]

The present invention was developed in view of the above matters, and its purpose is to provide a product that has good curability in the exposure process even in a colored state, can form a pattern, and can bring high light-shielding properties to visible light after curing. The resin composition of the cured film. [Means to solve the problem]

The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object. As a result, they have found that as a photoinitiator, a photoinitiator, which has a specific absorption coefficient (in the present invention, means gram absorption coefficient. The same applies below) is used. The resin composition used in combination with a specific black pigment can form patterns, and the transmittance of ultraviolet rays in the exposure process is high, and it can be fully cured to the deep part of the film, and the composition can be cured by curing the composition. The present invention has been completed by forming a cured film with high light-shielding properties of visible light.

That is, the present invention provides the following resin composition. 1. A resin composition characterized by containing: (A) an alkali-soluble copolymer; (B) having two or more groups consisting of an acrylate group, a methacrylate group, a vinyl group, and an allyl group (C) Photoinitiator: (C-1) has an oxime ester group and has an absorption coefficient of 5,000 ml/g in methanol or acetonitrile at 365 nm・Photoinitiator above cm; (D) Black pigment: absorb light containing (A) component, (B) component, (C-1) component, (C-2) in methanol or acetonitrile at 365nm The photoinitiator with a coefficient of 100 ml/g·cm or less, (D) black pigment, (E) liquid-repellent component, (F) solvent, and (G) thiol compound, relative to 100 mass of (A) component The dispersion of the component (D) is 10 parts by mass in the component (F), which is coated on a glass substrate and dried to form a thin film with a thickness of 10μm, and make the light with a wavelength of 365nm A black pigment with a transmittance of T ₁ and a light transmittance of 550 nm with a wavelength of T ₂ , _{the value of T 1} /T ₂ is 0.3 or more; (E) liquid-repellent component; and (F) solvent. 2. The resin composition of item 1, wherein the content of component (D) is 1-50 parts by mass relative to 100 parts by mass of component (A). 3. The resin composition of 1 or 2, wherein the number average molecular weight of component (A) is 2,000-50,000 in terms of polystyrene. 4. The resin composition described in any one of Claims 1 to 3, wherein the component (A) contains a group consisting of acrylic acid, methacrylic acid, maleic anhydride, and maleimide A copolymer of at least one monomer mixture selected in. 5. The resin composition of any one of 1 to 4, wherein the content of the component (C-1) is 0.3 to 5 parts by mass relative to 100 parts by mass of the component (A). 6. The resin composition of any one of 1 to 5, wherein the content of the component (B) is 10 to 150 parts by mass relative to 100 parts by mass of the component (A). 7. The resin composition of any one of 1 to 6, wherein the component (C-1) is a photoinitiator having a carbazole structure. 8. A cured film obtained from any resin composition of 1-7. 9. A partition wall for self-luminous displays, which is formed of any resin composition from 1 to 7. 10. A wavelength conversion layer of a self-luminous display with 9 partitions. 11. An organic electroluminescence element with 10 wavelength conversion layers. 12. A Micro LED element with 10 wavelength conversion layers. [Effects of the invention]

The resin composition of the present invention has a high transmittance of ultraviolet rays in the exposure process, and can be fully cured to the deep part of the film, and by curing the composition, a curing with high light-shielding properties of visible light can be formed membrane. The resulting cured film can be suitably used as a material for self-luminous displays such as QD-OLED displays or Micro LED displays, especially for pattern formation, as sub-pixels of the wavelength conversion layer of self-luminous display panels. The structure of the partition (colored partition) can be used to further improve the image quality.

The resin composition of the present invention contains: (A) an alkali-soluble copolymer; (B) having two or more selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group, and an allyl group At least one type of polymerizable group compound; (C) Photoinitiator: (C-1) has an oxime ester group, and the absorption coefficient in methanol or acetonitrile at 365 nm is 5,000 ml/g·cm or more (D) Black pigment: The absorption coefficient of (A) component, (B) component, (C-1) component, (C-2) in methanol or acetonitrile at 365nm is 100 ml/g·cm or less of the photoinitiator, (D) black pigment, (E) liquid repellent component, (F) solvent, and (G) thiol compound, with respect to 100 parts by mass of (A) component ( D) component is 10 parts by mass dispersed in component (F). The dispersion is coated on a glass substrate and dried to form a thin film with a thickness of 10μm. The light transmittance at a wavelength of 365nm It is T _1, so that the light transmittance of the wavelength of 550nm is ₂ T, T ₁ / T is 0.3 or more of the black pigment _2; (E) repellent composition; and (F) a solvent a resin composition.

＜(A) Ingredient＞ (A) The alkali-soluble copolymer is a copolymer obtained by copolymerization of a monomer mixture containing a monomer having an alkali-soluble group and other monomers (hereinafter referred to as "copolymer of component (A)").

The copolymer of the component (A) only needs to have a structure having an alkali-soluble group in its repeating unit, and there are no particular restrictions on the type of the backbone and side chains of the main chain of the polymer constituting the copolymer.

(A) The number average molecular weight Mn of the copolymer of the component is 2,000 to 50,000, and more preferably 5,000 to 20,000, considering the developability of the unexposed part (solubility in alkaline solution). In addition, in the present invention, the number average molecular weight Mn and the weight average molecular weight Mw described later are all polystyrene conversion values by gel permeation chromatography (GPC).

Examples of the alkali-soluble group system contained in the monomer having an alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleimide group.

Examples of the single system having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy) )Ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide and 4-vinylbenzoin acid.

Examples of the single system having a phenolic hydroxyl group include: hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleic Imine.

Examples of the single system having an acid anhydride group include maleic anhydride and itaconic anhydride.

As a single system having a maleimide group, for example, maleimide, or the aforementioned N-(carboxyphenyl)maleimide and N-(hydroxyphenyl)maleimide .

In the present invention, among these monomers having alkali-soluble groups, at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride and maleimide The copolymer of the mixture is preferred.

Furthermore, in the present invention, when obtaining the above-mentioned copolymer, another monomer capable of copolymerizing with the above-mentioned alkali-soluble group-containing monomer may be used in combination. Examples of other single systems include: acrylate compounds, methacrylate compounds, N-substituted maleimide compounds, acrylonitrile compounds, acrylamide compounds, methacrylamide compounds, styrene compounds, and ethylene Base compound.

Examples of acrylate compound systems include: methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, and phenyl acrylate Ester, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate , Methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate , 2-Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate Ester, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloxy) ethyl ester, poly(ethylene glycol) ethyl ether acrylate, 5- Acryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, acryloylethyl isocyanate, 8-ethyl-8-tricyclodecyl acrylate and glycidyl acrylate.

Examples of the methacrylate compound system include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and anthracenyl methacrylate. Ester, anthracenyl methyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate Ester, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate Base ester, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, methyl methacrylate 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloxy) ethyl ester, Poly(ethylene glycol) ethyl ether methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, methacryloyl ethyl isocyanate, 8 -Ethyl-8-tricyclodecyl methacrylate and glycidyl methacrylate.

Examples of the vinyl compound system include: methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl Vinyl ether and propyl vinyl ether.

Examples of the styrene compound system include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the N-substituted maleimide compound system include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

As an acrylonitrile compound system, acrylonitrile is mentioned, for example.

Examples of the acrylamide compound system include: hydroxyacrylamide, N-methacrylamide, N-ethacrylamide, N-isopropylacrylamide, N-butylacrylamide, and diacetone Acrylic amide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N,N-dipropyl acrylamide, acryl morpholine, Nn-butoxymethyl Allylamide, N-isobutoxymethacrylamide and N-methoxymethacrylamide.

Examples of the methacrylamide compound system include: hydroxymethacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-butylmethacrylamide, diacetone methacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N,N-dipropylmethacrylamide Methacrylamide, 4-methacrylomorpholine, Nn-butoxymethylmethacrylamide, N-isobutoxymethylmethacrylamide and N-methoxymethylmethacrylate Allyl amide.

In the present invention, among the above-mentioned other monomers, it contains acrylate compounds, methacrylate compounds, N-substituted maleimide compounds, acrylonitrile compounds, acrylamide compounds, and methacrylamide compounds. At least one selected from the group consisting of an amine compound, a styrene compound, and a vinyl compound is preferable, and it is preferable to contain a methacrylate compound.

In addition, among the above-mentioned monomers having alkali-soluble groups and other monomers, the combination of a monomer having a carboxyl group and a methacrylate compound is preferred, and a combination of methacrylic acid and methyl methacrylate is more preferred. good.

The method for obtaining the copolymer of component (A) is not particularly limited, but it can be achieved by, for example, making a monomer mixture containing the above-mentioned alkali-soluble group-containing monomer and other monomers in a solvent at 50 to 110°C Under the method of polymerization. As said solvent, if it can dissolve the monomer and other monomers which have an alkali-soluble group, and the copolymer of (A) component, it can use without a restriction|limiting in particular. As a specific example, the solvent illustrated in (F) component mentioned later can be mentioned. In addition, at the time of polymerization, a known polymerization initiator such as azobisisobutyronitrile is preferably used.

The solution of the copolymer of component (A) obtained as described above is poured into diethyl ether or water with stirring to re-precipitate, and the resulting precipitate is filtered and washed, and then under normal pressure or reduced pressure, Drying at room temperature or by heating can obtain the above-mentioned copolymer powder. By doing this, the polymerization initiator or unreacted monomer coexisting with the copolymer can be removed. As a result, a purified copolymer powder can be obtained. If it is not possible to purify sufficiently by one operation, only need to re-dissolve the obtained powder in the solvent and repeat the above operation.

In the present invention, the polymerization solution of the above-mentioned (A) alkali-soluble copolymer can be used as it is, or a solution obtained by re-dissolving the powder of the isolated polymer in a suitable solvent can also be used. As said solvent system, the solvent exemplified in (F) component mentioned later can be mentioned, for example.

The mass ratio of alkali-soluble monomer to other monomers ([alkali-soluble monomer]/[other monomer]) is preferably 5/95-50/50, preferably 10/90-30/70. By setting the above mass ratio to the above range, good curability can be obtained in the exposed portion, and good developability can be obtained in the unexposed portion.

＜(B) Ingredient＞ (B) The component is a compound having at least one polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group, and an allyl group. In the present invention, the "compound having two or more polymerizable groups" refers to a compound having two or more polymerizable groups in one molecule, and these polymerizable groups are located at the end of the molecule. The (B) component is a compound having a Mw of 1,000 or less from the viewpoint that the compatibility with each component is good and does not affect the developability.

Specific examples of the component (B) include: dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethyl Acrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane Methane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-tripropenyl hexahydro- S-triazine, 1,3,5-trimethacryloyl hexahydro-S-triazine, ginseng (hydroxyethyl acrylate) isocyanurate, ginseng (hydroxyethyl methacrylate) Base) isocyanurate, triacryloyl methylal, trimethacryloyl methylal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, new Pentylene glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethyl Acrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethyl Acrylate, N,N'-bis(acryloyl)cysteine, N,N'-bis(methacryloyl)cysteine, thiodiglycol diacrylate, thiodiglycol two Methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethyl Acrylic esters, bisphenoxyethanol diacrylate, bisphenoxyethanol dimethacrylate, diallyl ether bisphenol A, o-diallyl bisphenol A, diallyl maleate Base ester and triallyl trimellitate. Compounds having two or more of these polymerizable groups can be used singly or in combination of two or more.

The above-mentioned compounds can also be obtained as commercially available products. Examples of such commercially available products include: KAYARAD (registered trademark) T-1420, the same as DPHA, the same as DPHA-2C, the same as D-310, and the same as D -330, same DPCA-20, same DPCA-30, same DPCA-60, same DPCA-120, same DN-0075, same DN-2475, same R-526, same NPGDA, same PEG400DA, same MANDA, same R- 167, same HX-220, same HX620, same R-551, same R-712, same R-604, same R-684, same GPO-303, same TMPTA, same THE-330, same TPA-320, same TPA -330, same as PET-30, same as RP-1040 (the above are all manufactured by Nippon Kayaku Co., Ltd.); ARONIX (registered trademark) M-210, same as M-208, same as M-211B, same as M-215, same M-220, same M-225, same M-270, same M-240, same M-6100, same M-6250, same M-6500, same M-6200, same M-309, same M-310, same M-321, same M-350, same M-360, same M-313, same M-315, same M-306, same M-303, same M-452, same M-408, same M-403, same M-400, same M-402, same M-405, same M-406, same M-450, same M-460, same M-510, same M-520, same M-1100, same M-1200, same M-6100, same M-6200, same M-6250, same M-6500, same M-7100, same M8030, same M8060, same M8100, same M8530, same M-8560, same M9050 (all above are East Asia Synthetic ( VISCOAT 295, the same 300, the same 360, the same GPT, the same 3PA, the same 400, the same 260, the same 312, the same 335HP, the same 700 (the above are the Osaka Organic Chemical Industry (stock) system); A- 200, A-400, A-600, A-1000, A-B1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9 PG, 701A, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (all of the above are manufactured by Shinnakamura Chemical Industry Co., Ltd.); light ester EG, the same 2EG, the same 3EG, the same 4EG, the same 9EG, the same 14EG, the same 1.4BG, the same NP, the same 1.6HX, the same 1.9ND, same G-101P, same G-201P, same DCP-M, same BP-2EMK, same BP-4EM, same BP-6EM, same TMP, light acrylate 3EG-A, same 4EG-A, same 9EG -A, same 14EG-A, same PTMGA-250, same NP-A, same MPD-A, same 1.6HX-A, same 1.9ND-A, same MOD-A, same DCP-A, same BP-4PA, Same as BA-134, same BP-10EA, same HPP-A, same G-201P, same TMP-A, same TMP-3EO-A, same TMP-6EO-3A, same PE-3A, same PE-4A, same DPE-6A, epoxy ester 40EM, same 70PA, same 200PA, same 80MFA, same 3002M, same 3002A, same 3000MK, same 3000A, same EX-0205, AH-600, AT-600, UA-306H, UA- 306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.); EBECRYL (registered trademark) TPGDA, the same as 145, the same as 150, the same as PEG400DA, the same as 11, the same as HPNDA, Same PETIA, Same PETRA, Same TMPTA, Same TMPEOTA, Same OTA480, Same DPHA, Same 180, Same 40, Same 140, Same 204, Same 205, Same 210, Same 215, Same 220, Same 6202, Same 230, Same 244 , Same 245, same 264, same 265, same 270, same 280/15IB, same 284, same 285, same 294/25HD, same 1259, same KRM8200, same 4820, same 4858, same 5129, same 8210, same 8301 Same 8307, same 8402, same 8405, same 8411, same 8804, same 8807, same 9260, same 9270, same KRM7735, same KRM8296, same KRM8452, same 8311, same 8701, same 9227EA, same 80, same 436, same 438 , Same 446, same 450, same 505, same 524, same 525, same 770, same 800, same 810, same 811, same 812, same 1830, same 846, same 851, same 852, same 853, same 1870, same 884、The same 885、The same 600, same 605, same 645, same 648, same 860, same 1606, same 3500, same 3608, same 3700, same 3701, same 3702, same 3703, same 3708, same 6040 (DAICEL-ALLNEX (share) system); SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, CD9043, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036, SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, CD9021, SR9035, SR350, SR295, SR355, SR399, SR494, SR9041 (manufactured by Sartomer).

The content of the (B) component is preferably 10 to 150 parts by mass relative to 100 parts by mass of the (A) component, preferably 20 to 120 parts by mass, and more preferably 30 to 110 parts by mass. By setting the content of the component (B) to be equal to or greater than the lower limit of the above-mentioned range, the exposed portion can be sufficiently hardened, and pattern formation can be performed reliably. In addition, by setting the content of the (B) component to be equal to or less than the upper limit of the above-mentioned range, it is possible to prevent adhesion in the coating film after prebaking, and to ensure good developability in the unexposed area.

＜(C) Ingredient＞ The component (C) is a photoinitiator, and the following (C-1) photoinitiator having a specific absorption coefficient is used in the present invention.

＜(C-1) Ingredients＞ (C-1) The component is a photoinitiator having an oxime ester group and having an absorption coefficient of 5,000 ml/g·cm or more in methanol or acetonitrile at 365 nm. Specifically, the compound has an oxime ester group and a light absorption site, and has an absorption coefficient of 5,000 ml/g·cm or more in methanol or acetonitrile at 365 nm.

As said oxime ester group, the group represented by following formula (1) is mentioned, for example.

(式中，R¹ 係表示苯基、碳數1～10之烷基或苄基，R² 係表示氫原子、碳數1～10之烷基或苯基，虛線係表示鍵結處。)

(In the formula, R ¹ represents a phenyl group, an alkyl group having 1 to 10 carbons or a benzyl group, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbons or a phenyl group, and the dashed line represents a bonding site.)

The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and examples include methyl, ethyl, n-propyl, isopropyl, and cyclopropyl. , N-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl and 1-adamantyl.

As the above-mentioned light-absorbing part system, for example, it is selected from phenyl, thiophenylphenyl, N-alkylcarbazolyl, naphthyl, coumarin, alkoxyphenyl, phenylalkoxyphenyl, and benzene. The group selected for the oxyalkoxyphenyl group is preferably substituted with a group having a benzyl group such as a benzyl group and a naphthylcarbonyl group. Furthermore, the structure can also be substituted with phenyl, thiophenyl, diphenylamino, etc.

The component (C-1) is, for example, the oxime ester group represented by the formula (1) via a single bond or a carbonyl group, and a light absorption site from a phenyl group, a phenylthiophenyl group, and N-alkylcarba Compounds formed by bonding selected groups of azole group, naphthyl group, coumarin group, alkoxy phenyl group, phenyl alkoxy phenyl group, and phenoxy alkoxy phenyl group are preferred. In the present invention, among these, those having a carbazole structure are preferred.

Specific examples of the component (C-1) include: 1-(4-phenylthiophenyl)-1,2-octanedione-2-(O-benzyloxime), ethyl ketone, 1 -[9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), (E)-4-(4(4 -(Diphenylamino)benzyl)benzyloxy)benzaldehyde-O-acetyloxime, (E)-4-(4,8-dimethoxy-1-naphthyloxy) Benzaldehyde-O-acetyloxime, 1-(9-propyl-9H-carbazol-3-yl)butan-1,3-dione-1-(O-acetyloxime), and 1- [9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]butan-1,3-dione-1-(O-acetyloxime).

(C-1) Ingredients are readily available as commercially available products. Examples of such commercially available products include: IRGACURE (registered trademark) OXE01, IRGACURE (registered trademark) OXE02, IRGACURE (registered trademark) OXE03 (above It is made by BASF Corporation), ADEKA OPTOMER N-1919, ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930 (the above are ADEKA (shares) system). These (C-1) components may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the component (C-1) is preferably 0.3 to 5 parts by mass, and more preferably 0.5 to 4 parts by mass relative to 100 parts by mass of the component (A). By setting the content of the component (C-1) within the above range, good curability can be obtained.

＜(C-2) Ingredients＞ In the present invention, it is also possible to use (C-2) a photoinitiator having an absorption coefficient of 100 ml/g·cm or less in methanol or acetonitrile at 365 nm together with the component (C-1). As the component (C), two photoinitiators with different absorption coefficients can be used in combination to further improve the curability and developability. As the (C-2) component, for example, those having a hydroxyl group are preferable.

Specific examples of the component (C-2) include 1-hydroxy-cyclohexyl-phenyl-ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2 -Methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, methyl benzoate, and 2-oxy-2-phenylacetic acid 2-[2-Hydroxy-ethoxy] ethyl ester.

(C-2) Ingredients are readily available as commercially available products. Examples of such commercially available products include: IRGACURE (registered trademark) 2959, IRGACURE (registered trademark) 754, IRGACURE (registered trademark) 184, DAROCURE MBF, DAROCURE 1173 (all of the above are made by BASF). These (C-2) components may be used individually by 1 type, and may be used in combination of 2 or more types.

When using (C-2) component, its content is 0.5-10 mass parts with respect to 100 mass parts of (A) components, Preferably it is 0.5-10 mass parts, Preferably it is 1-7 mass parts. By setting the content of the component (C-2) to be at least the lower limit of the above-mentioned range, good curability can be obtained. By setting the content of the component (C-2) to be equal to or less than the upper limit of the above-mentioned range, good developability can be ensured in the unexposed part.

<(D) component> (D) component is to contain (A) component, (B) component, (C-1) component, (C-2) component, (D) black pigment, (E) liquid repellent Component, (F) solvent and (G) thiol compound, and dispersed in (F) component at a ratio of (A) component 100 mass parts and (D) component 10 mass parts ratio to (F) component In a thin film with a thickness of 10 μm formed by drying on a glass substrate, let the light transmittance at a wavelength of 365 nm be T ₁ , and when the light transmittance at a wavelength of 550 nm is T ₂ , the _{ratio of} T 1 /T ₂ A black pigment with a value of 0.3 or more. In the above dispersion, the types of (A) and (D) components, and the types and contents of components other than (A) and (D) are compatible with the above (A) to (C) components And the same as those described in the description of the components (D) to (G) described later. Moreover, as a solvent used for the said dispersion liquid, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are suitable. These solvents may be used alone or in combination of two types.

For the component (D), in consideration of the penetration of ultraviolet rays and the shielding properties of visible light, _{the value of T 1} /T ₂ is preferably 1.0 or more, and more preferably 1.5. The upper limit of the value of T ₁ /T ₂ is not particularly limited, but in general, 5.0 or less is preferable, and 3.0 or less is more preferable. By using the _{component (D) whose value of T 1} /T ₂ is included in the above range, it is possible to balance the penetration of ultraviolet rays in the exposure process and the shielding properties of visible light in the cured product obtained.

Specific examples of the component (D) include zirconium nitride, titanium nitride and titanium oxynitride, and mixed powders containing zirconium nitride and titanium nitride as a mixture of these, and zirconium nitride and titanium oxynitride Zirconium nitride can be suitably used in the present invention.

The purity of the above-mentioned zirconium nitride, titanium nitride and titanium oxynitride is not particularly limited unless the effect of the present invention is impaired, but it is preferably 90% by mass or more, preferably 95% by mass or more, 98% by mass The above is even better.

Zirconium nitride is the above specific surface area by the BET method, measured at 20 ~ 90m ² / g preferably, 30 ~ 60m ² / g is preferred. In addition, the specific surface area of the above-mentioned titanium nitride and titanium oxynitride measured by the BET method is ^{preferably 10 to 90 m 2} /g. If the specific surface area is in the above range, sedimentation is unlikely to occur when the composition is stored for a long time, and the obtained cured film will have good visible light shielding properties.

As such a black pigment system, a commercially available product can be used, and for example, NITRBLACK UB-1 (manufactured by Mitsubishi Materials Co., Ltd.) can be used. In addition, as a mixed powder containing zirconium nitride and titanium nitride, and a mixed powder containing zirconium nitride and titanium oxynitride, a mixed powder for black film formation disclosed in Japanese Patent Application Laid-Open No. 2018-83730 can be mentioned.

The content of the component (D) is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass relative to 100 parts by mass of the component (A). By setting the content of the component (D) in the above-mentioned range, the penetration of ultraviolet rays in the exposure process and the shielding properties of visible light in the obtained cured film can be balanced.

In addition, component (D) can be directly mixed as a powder when preparing the composition. However, if it is considered to obtain a more uniform composition, it is better to disperse it in a suitable solvent in advance to prepare a dispersion. . As a specific example of the said solvent, the solvent described in (F) solvent mentioned later can be mentioned. Moreover, when preparing the dispersion liquid of (D)component, you may use a well-known dispersing agent as needed. As the above-mentioned dispersant, a commercially available product can be used, and for example, SOLSPERSE 34750 (manufactured by Japan Lubrizol Co., Ltd.) can be used.

＜(E) component: liquid repellent component＞ The component (E) is a polymer having a liquid repellent group (e1), or a predetermined surfactant described later.

＜(e1) Liquid repellent base＞ (E1) The liquid-repellent group system includes, for example, at least one group selected from a fluoroalkyl group, a polyfluoroether group, a silyl ether group, and a polysiloxyalkyl group.

As the fluoroalkyl group, a fluoroalkyl group having 3 to 10 carbon atoms is preferred, and a fluoroalkyl group having 4 to 10 carbon atoms is preferred. Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl, 2,2,3,3,3-heptafluoropropyl, 2-(perfluorobutyl)ethyl, 3- Perfluorobutyl-2-hydroxypropyl, 2-(perfluorohexyl) ethyl, 3-perfluorohexyl-2-hydroxypropyl, 2-(perfluorooctyl) ethyl, 3-perfluorooctyl -2-Hydroxypropyl, 2-(perfluorodecyl)ethyl, 2-(perfluoro-3-methylbutyl)ethyl, 3-(perfluoro-3-methylbutyl)-2- Hydroxypropyl, 2-(perfluoro-5-methylhexyl) ethyl, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl, 2-(perfluoro-7-methyloctyl) ) Ethyl, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl.

(式(i)中，X係表示亦可具有氟原子的碳數1～10之2價飽和烴基，且以n所括號的每單位為相同的基或不同的基；Y係表示氫原子(但是只限與Y相鄰之氧原子所相鄰的碳原子上無鍵結氟原子的情況)，或亦可具有氟原子的碳數1～20之1價飽和烴基；n係表示2～50之整數。其中，式(i)中的氟原子之總數係為2以上。)As a polyfluoroether group system, the Rf group which consists of a polyfluoroether structure represented by following formula (i) is mentioned.

(In formula (i), X represents a divalent saturated hydrocarbon group with 1 to 10 carbon atoms which may also have a fluorine atom, and each unit parenthesized by n represents the same group or a different group; Y represents a hydrogen atom ( However, it is limited to the case where there is no fluorine atom bonded to the carbon atom adjacent to the oxygen atom adjacent to Y), or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms with a fluorine atom; n represents 2 to 50 Integer. Wherein, the total number of fluorine atoms in formula (i) is 2 or more.)

Examples of preferred aspects of X and Y in formula (i) include: X represents an alkylene group having 1 to 10 carbon atoms substituted with a fluorine atom, or a carbon number of 1 to 10 Perfluoroalkylene of 10, and each unit in parenthesis of n is the same group or different group; Y means that one hydrogen atom of an alkyl group with 1 to 20 carbon atoms is substituted with a fluorine atom Alkyl group or perfluoroalkyl group with 1 to 20 carbon atoms.

As a more preferable aspect of X and Y in the formula (i), X is a perfluoroalkylene group having 1 to 10 carbon atoms, and each unit in the parentheses of n is the same group or different groups. ; Y is a perfluoroalkyl group with 1 to 20 carbon atoms.

In the Rf group represented by the formula (i), n is preferably an integer of 2-50, preferably an integer of 2-30, and more preferably an integer of 2-15. If n is 2 or more, good liquid repellency can be obtained. If n is 50 or less, the polymer of component (E) is combined with a monomer having an Rf group with a hydroxyl group, a carboxyl group, an amide group, an amino group, an N-alkoxymethyl amide group, and a sealing When a monomer of a terminal isocyanate group, a trialkoxysilyl group, or other monomers are copolymerized and synthesized, the compatibility of the monomers becomes good.

In addition, in the Rf group represented by the formula (i), the total number of carbon atoms is preferably 2-50, more preferably 2-30. Within this range, the polymer system of the (E) component can exhibit good liquid repellency. In addition, the polymer of component (E) is combined with a monomer having an Rf group with a hydroxyl group, a carboxyl group, an amide group, an amine group, an N-alkoxymethyl amide group, a blocked isocyanate group, and three When the alkoxysilyl monomers or other monomers are copolymerized and synthesized, the compatibility of the monomers is good.

Specific examples of X include: -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF ₂ CF(CF ₃ )-, -CF ₂ CF ₂ CF ₂ CF ₂ -, -CF ₂ CF ₂ CF(CF ₃ )-, and CF ₂ CF(CF ₃ )CF ₂ -.

Specific examples of Y include, for example, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -(CF ₂ ) ₂ CF ₃ , -(CF ₂ ) ₃ CF ₃ , -(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ , -(CF ₂ ) ₆ CF ₃ , -(CF ₂ ) ₇ CF ₃ , -(CF ₂ ) ₈ CF ₃ , -(CF ₂ ) ₉ CF ₃ , and ( CF ₂ ) ₁₁ CF ₃ , -(CF ₂ ) ₁₅ CF ₃ .

(式(ii)中，p係為2或3，n所括號的每單位為相同的基，q係表示1～20之整數，n係表示2～50之整數。)A preferable aspect of the Rf group represented in the formula (i) includes the Rf group represented in the formula (ii).

(In formula (ii), p is 2 or 3, each unit in the parentheses of n is the same base, q is an integer from 1 to 20, and n is an integer from 2 to 50.)

As a preferable specific example of the Rf group represented by the formula (ii), the following groups can be cited from the viewpoint of ease of synthesis.

The Rf groups in the polymer of the component (E) may all be the same or different.

(式中，X¹ 、X² 及X³ 係各自獨立而表示碳數1～3之烷基，X⁴ 係表示碳數1～6之伸烷基。)The above-mentioned silyl ether group refers to a group in which the hydroxyl group of an alcohol is protected by a trialkylsilyl group, and is preferably a group represented by the following formula.

(In the formula, X ¹ , X ² and X ³ each independently represent an alkyl group having 1 to 3 carbon atoms, and X ⁴ represents an alkylene group having 1 to 6 carbon atoms.)

(但是，R^a 及R^b 係各自獨立而表示氫原子、烷基、環烷基或芳基，R^c 係表示氫原子或碳數1～10之有機基，m係表示1～200之整數。)。Examples of the polysiloxane group include a group having a polysiloxane structure represented by formula (iii). Hereinafter, the group having the polysiloxane structure represented by the formula (iii) is referred to as a pSi group.

(However, R ^a and R ^b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R ^c represents a hydrogen atom or an organic group with 1 to 10 carbon atoms, and m represents an integer of 1 to 200 .).

R ^a and R ^b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and may be the same or different for each silanoxy unit. Since the polymer of component (E) needs to exhibit good liquid repellency, it ^{is preferable that Ra} and R ^b are independently hydrogen atoms, methyl groups or phenyl groups. Furthermore, all silanoxy units It is ^{preferable that both Ra} and R ^b are methyl groups. In addition, R ^c may contain nitrogen atoms, oxygen atoms, and the like.

<(e2) At least one group selected from the group consisting of N-alkoxymethylamino group, blocked isocyanate group, and trialkoxysilyl group> In the present invention, from the viewpoint of the wettability of the ink at the opening of the sub-pixel, in addition to the group (e1), it also contains an N-alkoxymethyl amide group, a blocked isocyanate group, and a trioxane group. At least one group selected from the group consisting of oxysilyl groups is preferred.

Examples of the N-alkoxymethyl amide group include: N-methoxymethyl (meth) acrylamide group, N-ethoxymethyl (meth) acrylamide group, and N -Butoxymethyl (meth)acrylamido.

Blocked isocyanate groups are those that deprotect the blocked groups by heating and become isocyanate groups. Specifically, they include alcohols, phenols, thiols, imines, ketimines, amines, lactams, and pyrazoles. , Oxime, β-diketone and other substituted isocyanate groups.

Examples of the trialkoxysilyl group include those shown below.

<(e3) At least one group selected from the group consisting of hydroxyl group, carboxyl group, amide group and amino group> (E) Component, in addition to the groups (e1) and (e2), from the viewpoint of the wettability of the ink in the openings of the sub-pixels, it also contains (e3) from the hydroxyl group, carboxyl group, amide group and At least one group selected from the group consisting of amine groups is preferred.

＜(e4) Acrylate group＞ (E) The component system can also be introduced, and the acrylate group bonded to the polymer having the group (e1) described above via a urethane bond. Examples of the acrylate group include (meth)acrylic acid groups and the like, which can be introduced by reacting an acrylate having an isocyanate group into a polymer having a group (e1). Examples of the acrylate system having an isocyanate group include 2-(meth)acryloxyethyl isocyanate and 1,1-bis((meth)acryloxymethyl)ethyl isocyanate.

Examples of the polymer system of the component (E) include those containing the group (e1), the group (e2), or even the group (e3) as needed, acrylic polymer, polyamide acid, and polyacrylic acid. Amine, polyamide, polyurea, polyurethane, phenol resin, epoxy resin, polysiloxane and polyester; in the present invention, acrylic polymer is preferred.

[Acrylic Polymer] Acrylic polymer is made by polymerizing the monomer containing the group (e1), preferably by copolymerizing the monomer containing the group (e2), and adding the monomer containing the group (e3) It is better to do copolymerization, which can be obtained.

(e1) Monomers containing liquid repellent groups Examples of monomers having a fluoroalkyl group include monomers having a fluoroalkyl group with a carbon number of 3-10, such as 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethane Methyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl) Ethyl acrylate, 2-(perfluorobutyl) ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate Ester, 2-(perfluorohexyl) ethyl acrylate, 2-(perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2- Hydroxypropyl methacrylate, 2-(perfluorooctyl) ethyl acrylate, 2-(perfluorooctyl) ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate , 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-(perfluorodecyl) ethyl acrylate, 2-(perfluorodecyl) ethyl methacrylate, 2-(all Fluoro-3-methylbutyl)ethyl acrylate, 2-(perfluoro-3-methylbutyl)ethyl methacrylate, 3-(perfluoro-3-methylbutyl)-2- Hydroxypropyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-5-methylhexyl) ethyl acrylate, 2-( Perfluoro-5-methylhexyl) ethyl methacrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-methylhexyl)- 2-Hydroxypropyl methacrylate, 2-(perfluoro-7-methyloctyl) ethyl acrylate, 2-(perfluoro-7-methyloctyl) ethyl methacrylate, 2- (Perfluoro-7-methyloctyl)-2-hydroxypropyl acrylate, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate.

Examples of the single system having a silyl ether group include methacryloxypropyl ginseng (trimethylsilyloxy) silane and acryloxypropyl ginseng (trimethylsilyloxy) silane.

As a single system having a polysiloxane group, for example, CH ₂ =CHCOO(pSi), and CH ₂ =C(CH ₃ )COO(pSi). Here, the pSi system represents a pSi group. The monomer having a pSi group may be used singly, or two or more of them may be used in combination.

In addition, in the case of introducing pSi groups into the polymer of component (E), in addition to the above-mentioned method of copolymerizing monomers having pSi groups, it is also possible to use a reaction site-containing polymer with a pSi group-containing compound Various modification methods, or methods using a pSi-based polymerization initiator, etc.

In terms of various modification methods for reacting a polymer having a reaction site with a compound having a pSi group, the following methods can be mentioned, for example.

A method of pre-copolymerizing a monomer having an epoxy group and then reacting it with a compound having a carboxyl group at one end and a pSi group at the other end. A method of pre-copolymerizing a monomer having an epoxy group and then reacting it with a compound having an amino group at one end and a pSi group at the other end. A method of pre-copolymerizing a monomer having an epoxy group and then reacting it with a compound having a mercapto group at one end and a pSi group at the other end. A method of pre-copolymerizing a monomer having an amine group and then reacting it with a compound having a carboxyl group at one end and a pSi group at the other end.

A method of pre-copolymerizing a monomer having an amine group and then reacting it with a compound having an epoxy group at one end and a pSi group at the other end. A method of pre-copolymerizing a monomer having a carboxyl group and then reacting it with a compound having an epoxy group at one end and a pSi group at the other end. A method of pre-copolymerizing a monomer having a carboxyl group and then reacting it with a compound having an amino group at one end and a pSi group at the other end. A method of pre-copolymerizing a monomer having a carboxyl group and then reacting it with a compound having a chlorosilyl group at one end and a pSi group at the other end. A method of pre-copolymerizing a monomer having a hydroxyl group and then reacting it with a compound having a chlorosilyl group at one end and a PSi group at the other end.

As a polymerization initiator having a pSi group, it may be a group having a divalent polysiloxane structure in the main chain of the molecule, or it may include a monovalent group in the terminal part or side chain of the initiator molecule. The base of the polysiloxane structure. Examples of the initiator system containing a group having a divalent polysiloxane structure in the molecular main chain include a compound having a group having a divalent polysiloxane structure and an azo group alternately. Such polymerization initiators are easily available as commercially available products, and examples include VPS-1001 and VPS-0501 (all of which are manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

(e2) A monomer containing a group selected from the group consisting of N-alkoxymethyl amide group, blocked isocyanate group and trialkoxysilyl group Examples of the single system having an N-alkoxymethyl amide group include: N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N- Ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide and other (meth)acrylamide compounds substituted with hydroxymethyl or alkoxymethyl .

As a single system having a blocked isocyanate group, for example, 2-(0-(1'-methyl propylene amino) carboxyamino) ethyl methacrylate and 2-((3) methacrylic acid ,5-Dimethylpyrazolyl)carbonylamino)ethyl ester.

As a single system of trialkoxysilyl groups, for example, 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxy methacrylate Silyl propyl ester, and 3-triethoxy silyl propyl methacrylate.

(e3) A monomer containing at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amine group Examples of the single system having a hydroxyl group include: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol Monomethacrylate, 2-(acryloxy) ethyl caprolactone, 2-(methacryloxy) ethyl caprolactone, poly(ethylene glycol) acrylate, poly(propylene glycol) acrylic acid Ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-propenoxy-6-hydroxynorbornene-2-carboxylic acid-6-in Esters, and 5-methacryloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxybenzene Maleimide, N-hydroxybenzal acrylamide, N-hydroxybenzyl methacrylamide, p-hydroxybenzyl acrylate, and p-hydroxybenzyl methacrylate. In the present invention, among these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

Examples of the single system having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy) ) Ethyl) phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

Examples of the single system having an amide group include: acrylamide, methacrylamide, N-methacrylamide, N,N-dimethylacrylamide, and N,N-diethyl propylene Amide. In the present invention, among these, methacrylamide is preferred.

Examples of the single system having an amino group include: aminomethyl acrylate, aminomethyl methacrylate, 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 3-aminopropyl acrylate, and methacrylic acid 3-aminopropyl ester.

[Polyamide acid, polyimide] Examples of the polyamide acid system include polyamide acid obtained by reacting a diamine having a fluoroalkyl group with a dianhydride. As the polyimide system, for example, a polyimide obtained by imidizing the aforementioned polyimide acid can be mentioned.

[Polyamide] As a polyamide system, the polyamide obtained by polymerizing the diamine which has a fluoroalkyl group, and dicarboxylic anhydride is mentioned, for example.

[Polyurea] Examples of the polyurea system include polyureas obtained by polymerizing a diamine having a fluoroalkyl group and a diisocyanate.

[Polyurethane] As the polyurethane system, for example, a polyurethane obtained by polymerizing a diol having a fluoroalkyl group or a fluoroalkoxy group, a diol having an amino group, and a diisocyanate.

[Phenolic resin] Examples of the phenol resin system include Novolak resin obtained by polymerizing phenol having a fluoroalkyl group or a fluoroalkoxy group with formaldehyde.

[Epoxy resin] Examples of the epoxy resin system include dicondensation of either or both of bisphenol A and bisphenol F having a fluoroalkyl group or a fluoroalkoxy group, and the diglycidyl ether of bisphenol A and bisphenol F Epoxy resin obtained by the reaction of either or both of glycerol ethers.

[Polysiloxane] Examples of the polysiloxane series include trialkoxysilanes having fluoroalkyl groups or dialkoxysilanes having fluoroalkyl groups, and trialkoxysilanes having amine groups or those having amine groups. Polysiloxane obtained by polymerization of a mixture of silane monomers of dialkoxysilane.

[Polyester] Examples of the polyester system include polyesters obtained by reacting dicarboxylic acid or tetracarboxylic dianhydride with a diol having a fluoroalkyl group or a fluoroalkoxy group.

(E) In addition to the monomer having the groups of (e1) to (e3), other monomers (hereinafter referred to as other monomer E) may be added to the polymer of the component (E).

Specific examples of other monomers E include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, onion methacrylate, Anthracene methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-methacrylate Ethoxyethyl, tetrahydrofuran methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, methacrylic acid 8-methyl-8-tricyclodecyl ester, 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate Ester, methyl anthracene acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofuran acrylate, acrylic acid 3 -Methoxybutyl ester, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclic acrylate Decyl ester, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, vinyl naphthalene, Vinyl anthracene and vinyl biphenyl.

In the polymer of the component (E), the introduction amount of the group (e1) is preferably 5-60 mol%, and more preferably 5-40 mol% relative to the total repeat unit. By setting the introduction amount of the base (e1) to be equal to or greater than the lower limit of the above-mentioned range, good liquid repellency can be obtained. By setting the introduction amount of the base (e1) to be equal to or less than the upper limit of the above-mentioned range, problems such as aggregation hardly occur.

In the polymer of component (E), (e2) the introduction amount of a group selected from the group consisting of N-alkoxymethyl amide group, blocked isocyanate group and trialkoxysilyl group , Relative to the total repeat unit, it is preferably 5 to 70 mol%, more preferably 5 to 50 mol%. By setting the introduction amount of the group (e2) to be at least the lower limit of the above-mentioned range, the obtained cured film will have good heat resistance or solvent resistance. By setting the introduction amount of the base (e2) to be equal to or less than the upper limit of the above-mentioned range, good developability can be obtained.

In the case of introducing (e3) at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group into the polymer of the component (E), the amount of introduction is relative to the total The repeating unit is preferably 5-60 mol%, more preferably 5-40 mol%. By setting the introduction amount of the group (e3) to be at least the lower limit of the above-mentioned range, the cured film obtained will have good heat resistance or solvent resistance. By setting the introduction amount of the base (e3) to be equal to or less than the upper limit of the above-mentioned range, good liquid repellency can be obtained.

(E) The number average molecular weight Mn of the polymer of the component is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and more preferably 4,000 to 10,000. (E) When the Mn of the polymer of the component is less than the upper limit of the above-mentioned range, it is difficult to generate a residue. In addition, the number average molecular weight Mn of the polymer of the component (E) is a polystyrene conversion value measured by a gel permeation chromatography (GPC).

In addition, in the present invention, the polymer of the component (E) may be a mixture of a plurality of copolymers.

(E) The polymer of component is made by making (e1) a monomer having a liquid repellent group, for example, a monomer having a fluoroalkyl group with 3 to 10 carbon atoms, a monomer having a polyfluoroether group, (e1) e2) A monomer having at least one group selected from the group consisting of N-alkoxymethyl amide group, blocked isocyanate group, and trialkoxysilyl group, and if necessary (e3) A monomer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amine group, and other monomers E, carried out in a solvent in the presence of a polymerization initiator Obtained by polymerization reaction. In addition, the reaction temperature during polymerization can be appropriately set according to the type of polymer to be produced, etc. However, in the case of producing an acrylic polymer, it is preferably set to 50 to 110°C. In addition, the solvent used in the polymerization reaction is not particularly limited as long as it can dissolve the monomers used and the resulting polymer. As a specific example of the said solvent, the solvent described in (F) solvent mentioned later can be mentioned.

The above-mentioned (E) component may usually be a solution, but if necessary, it may be isolated, purified, etc. by the same method as described in the description of the (A) component. In addition, the polymerization solution of the copolymer of the above-mentioned component (E) can also be used as it is, or a solution obtained by re-dissolving the powder of the isolated polymer in a suitable solvent can be used. As said solvent system, the solvent exemplified in (F) component mentioned later can be mentioned, for example.

The surfactant system as the (E) component includes, for example, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. These surfactants can also be obtained as commercial products. Examples of such commercial products include PolyFox PF-136A, 151, 156A, 154N, 159, 636, 6320, 656, 6520 (manufactured by Omnova) , MEGAFAC (registered trademark) R30, R08, R40, R41, R43, F251, F477, F552, F553, F554, F555, F556, F557, F558, F559, F560, F561, F562, F563, F565, F567, F570 ( DIC (stock) system), FC4430, FC4432 (Sumitomo 3M (stock) system), AsahiGuard (registered trademark) AG710, SURFLON (registered trademark) S-386, S-611, S-651 (AGC Kiyomi Chemical Co., Ltd.) ), FTERGENT (registered trademark) FTX-218, DFX-18, 220P, 251, 212M, 215M (made by Neos (stock)) and other fluorine-based surfactants; BYK-300, 302, 306, 307, 310, 313 , 315, 320, 322, 323, 325, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455 (manufactured by BYK-Chemie Japan), SH3746, SH3749 , SH3771, SH8400, SH8410, SH8700, SF8428 (manufactured by Toray Dow Corning Silicone Co., Ltd.), KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011, KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.) and other silicone-based surfactants. These surfactants can be used individually by 1 type or in combination of 2 or more types.

The content of the (E) component is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass relative to 100 parts by mass of the (A) component. (E) If the content of the component is within the above range, good liquid repellency can be obtained, and it is also preferable from an economic point of view.

＜(F)Component: Solvent＞ The solvent for component (F) is if it can dissolve component (A), component (B), and component (C), and can dissolve component (G) described later, etc. added as needed, then its type and The structure and the like are not particularly limited.

As the solvent for component (F), solvents commonly used in photoresist materials can be used, such as: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl Cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, Xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate Ester, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate Ester, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. In the present invention, among these, considering the coating properties and safety of the composition, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate , Butyl lactate is better. These solvents may be used alone or in combination of two or more kinds.

＜(G) Ingredient＞ (G) The component system is a thiol compound. The purpose of this component is to increase the curing speed of the above-mentioned resin composition, and it can be blended within a range that does not impair the effect of the present invention.

The thiol compound as the component (G) is not particularly limited, but examples include 1-hexyl mercaptan, 1-heptane mercaptan, 1-octyl mercaptan, 1-nonane mercaptan, 1-decane mercaptan, 1 -Undecyl mercaptan, 1-dodecyl mercaptan, 1-octadecyl mercaptan, 2-mercaptobenzothiazole, 6-methyl-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 2-naphthyl mercaptan, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, β-mercaptopropionic acid, methyl-3-mercapto Propionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercapto Propionate, trimethylolpropane (3-mercaptopropionate), ginseng-[(3-mercaptopropionoxy)-ethyl]isocyanurate, pentaerythritol 4 (3-mercaptopropionic acid Ester), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol (3-mercaptopropionate), pentaerythritol 4 (3-mercaptobutyrate), pentaerythritol 4 (3-mercaptobutyrate) , 1,4-bis(3-mercaptobutanoyloxy)butane, and 1,3,5-gin[2-(3-sulfonylbutanoyloxy)ethyl]-1,3,5- Triazine-2,4,6-trione. In the present invention, among these, pentaerythritol 4 (3-mercaptobutyrate) and pentaerythritol 4 (3-mercaptobutyrate) are used from the viewpoint of high storage stability of the resin composition and sufficient curability. Mercaptobutyrate), 1,4-bis(3-mercaptobutanoyloxy)butane, and 1,3,5-gin[2-(3-sulfonylbutanoyloxy)ethyl]-1 ,3,5-triazine-2,4,6-trione is preferred. These thiol compounds can be used individually by 1 type or in combination of 2 or more types.

When the component (G) is used, its content is preferably 0.01-10 parts by mass, and more preferably 0.03-5 parts by mass relative to 100 parts by mass of the component (A). If the content of the component (G) is greater than or equal to the lower limit of the above range, the curability will be relatively good. If the content of the component (G) is equal to or less than the upper limit of the above range, the pattern resolution will be relatively good.

＜(H)component＞ The component (H) is an adhesion promoter. For the resin composition of the present invention, for the purpose of improving the adhesion to the substrate after development, an adhesion promoter may be added. Specific examples of such adhesion promoters include: chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; Trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane Silane, vinyl trichlorosilane, gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-(N-piperidyl)propyltriethoxysilane, 3-ureapropyltriethoxysilane and 3-ureapropyltrimethoxysilane Alkoxysilanes such as silanes; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine and trimethylsilimidazole Class; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, ureaazole, thiouracil, mercaptoimidazole and mercapto Heterocyclic compounds such as pyrimidine; urea compounds such as 1,1-dimethylurea; and thiourea compounds such as 1.3-dimethylurea. In the present invention, among these, alkoxysilanes (that is, silane coupling agents) are preferred in terms of obtaining good adhesion. Moreover, these adhesion promoter systems can be used individually by 1 type or in combination of 2 or more types.

The above-mentioned adhesion promoters can be used, for example, compounds from commercial products manufactured by Shin-Etsu Chemical Co., Ltd., Momentive Performance Materials Worldwide Inc., or Toray Dow Corning Silicone Co., Ltd., etc. These commercial products can be used easy to get.

When blending (H) component, its content is usually 0.1-20 parts by mass, preferably 0.5-10 parts by mass relative to 100 parts by mass of (A) component. By setting the content of the component (H) to be equal to or less than the upper limit of the above-mentioned range, good sensitivity can be obtained. By setting the content of the component (H) to be at least the lower limit of the above-mentioned range, a sufficient effect of the adhesion promoter can be obtained.

＜Other additives＞ Furthermore, the resin composition of the present invention may also contain sensitizers, chain transfer agents, crosslinking agents, rheology modifiers, pigments, dyes, and storage stability as needed within the range that does not impair the effects of the present invention. Agents, defoamers, or dissolution accelerators for polyvalent phenols, polyvalent carboxylic acids, etc.

＜Resin composition＞ The resin composition of the present invention is an alkali-soluble polymer of the component (A), a compound having two or more polymerizable groups of the component (B), and an oxime ester group of the component (C-1), and at 365 nm A photoinitiator with an absorption coefficient of 5,000 ml/g·cm or more in methanol or acetonitrile, a black pigment of component (D), and a liquid-repellent component of component (E), which are dissolved or dispersed in component (F) It is made in solvent; if necessary, it can still contain: (C-2) component photoinitiator, (G) component thiol compound, (H) component adhesion promoter, and other additives 1 More than one kind of composition.

As a preferable aspect of the resin composition of this invention, as shown below can be illustrated, but it is not limited to this. [1]: With respect to 100 parts by mass of (A) component, 10 to 150 parts by mass of (B) component, 0.3 to 5 parts by mass of (C-1) component, 1 to 50 parts by mass of (D) component, and (E) A resin composition in which the components are dissolved or dispersed in the solvent of the (F) component. [2]: In the composition of the above-mentioned [1], a resin composition containing 0.5 to 10 parts by mass of the (E) component with respect to 100 parts by mass of the (A) component. [3]: In the composition of the above-mentioned [1] or [2], the (G) component further contains 0.01 to 10 parts by mass of the resin composition with respect to 100 parts by mass of the (A) component. [4]: In the composition of [1], [2], or [3] above, the component (H) is further contained in a resin composition of 0.1-20 parts by mass relative to 100 parts by mass of the component (A) . [5]: In any of the above-mentioned compositions [1] to [4], the component (C-2) further contains 0.5-10 parts by mass of the resin composition relative to 100 parts by mass of the component (A) .

The solids concentration in the resin composition of the present invention is not particularly limited if the components are uniformly dissolved or dispersed in the solvent, but it is preferably 1 to 80% by mass, and more preferably 5 to 70% by mass , More preferably 10-60% by mass. The solid content here refers to the total amount of components other than the solvent constituting the resin composition.

The preparation method of the resin composition of the present invention is not particularly limited, but the preparation method may include, for example, dissolving the copolymer of the component (A) in the solvent of the component (F), and applying the solution of the component (B) to the solution. A method in which a compound having two or more polymerizable groups, the photoinitiator of component (C-1), the black pigment of component (D), and the liquid-repellent component of component (E) are mixed in a predetermined ratio, or, In the appropriate stage of the preparation method, a method of adding the photoinitiator of the component (C-2), the thiol compound of the component (G), the adhesion promoter of the component (H), and other additives as needed.

When preparing the resin composition of the present invention, the polymerization solution of the copolymer of the component (A) obtained by the polymerization reaction in the solvent of the component (F) can be used as it is. In this case, when adding (B) component, (C-1) component, (D) component, etc., to the polymerization solution of (A) component in the same manner as above, and mixing, it can also be used for the purpose of adjusting the concentration. And add the solvent of component (F). At this time, the solvent of component (F) used in the formation of the copolymer of component (A) may be the same as the solvent of component (F) used to adjust the concentration during the preparation of the resin composition, or Can be different.

Although the resin composition obtained above can be used as it is for pattern formation, it is preferable to use it after filtering it with a filter with a pore size of about 1.0 μm or the like.

＜Coating film and hardened film＞ The resin composition of the present invention is applied to a suitable substrate (e.g., silicon/silicon dioxide coated substrate, silicon nitride substrate, metal such as aluminum, molybdenum, chromium, etc.) coated substrate, glass substrate, quartz substrate, ITO Substrate, etc.) or film (e.g. triacetyl cellulose film, cycloolefin polymer film, cycloolefin copolymer film, polyethylene terephthalate film, polyester film, acrylic film, polyimide, etc. Resin film) and other substrates are coated by spin coating, cast coating, roll coating, slit coating, slit coating followed by spin coating, inkjet method, etc. After that, it is preliminarily dried by a hot plate, oven, etc., to form a coating film. After that, the coating film is heated (pre-baked) to form a negative photosensitive resin film having photosensitivity.

The above-mentioned preliminary drying is not particularly limited as long as the solvent contained in the composition can be removed without adversely affecting the coating film. Natural drying, or heat drying using a hot plate or oven, etc. can be used. In addition, this preliminary drying can also be performed integrally with the pre-baking.

The pre-baking conditions are generally used, preferably 60-150℃, preferably 80-120℃, 0.5-30 minutes in the case of using a hot plate, or 0.5-30 minutes in the case of using an oven Method of heating for 0.5 to 90 minutes.

The film thickness of the negative photosensitive resin film formed from the above resin composition is preferably 0.1-50 μm, preferably 0.5-40 μm, more preferably 1-30 μm, and most preferably 5-20 μm.

The negative photosensitive resin film formed from the resin composition of the present invention is exposed to light such _{as ultraviolet rays, ArF, KrF, F 2 laser light, etc. using a mask with a predetermined pattern.} The function of the radicals generated by the photopolymerization initiator of the component (C-1) and the component (C-2) contained in the resin film will cause the exposed part of the film to become insoluble in the alkaline developer.

In the present invention, in consideration of sufficient curing to the deep part of the film, it is preferable to use ultraviolet rays as the irradiation light, and it is preferable to use ultraviolet rays with a wavelength of 365 nm.

After that, development was performed using an alkaline developer. Thereby, in the negative photosensitive resin film, the unexposed part is removed, and pattern-like relief is formed.

Examples of alkaline developer systems that can be used in the present invention include aqueous solutions of alkali metal hydroxides such as sodium carbonate, potassium carbonate, potassium hydroxide, and sodium hydroxide; tetramethylammonium hydroxide, tetramethylammonium hydroxide, etc. Aqueous solutions of quaternary ammonium hydroxide such as ethyl ammonium and choline; and alkaline aqueous solutions of amine aqueous solutions such as ethanolamine, propylamine and ethylenediamine. Furthermore, surfactants and the like may be added to these developing solutions.

The systems generally used as photoresist developers include, for example, 0.5 to 3% by mass sodium carbonate aqueous solution, 0.01 to 0.5% by mass potassium hydroxide aqueous solution, and 0.1 to 2.38% by mass tetraethylammonium hydroxide aqueous solution. In the resin composition of the present invention, such an alkaline developer can also be used without problems such as swelling, and good development can be carried out.

In addition, as the development method, any method such as a spray method, a liquid filling method, a dipping method, or a shaking dipping method may be used. The development time at this time is usually 15 to 200 seconds.

After development, the negative photosensitive resin film was washed with running water. At this time, the washing time is not particularly limited as long as the developer can be sufficiently removed, but it is usually 20 to 90 seconds. In addition, after washing, compressed air or compressed nitrogen can also be used, or it can be air-dried by rotating. The moisture on the substrate is removed, and a patterned film is obtained.

Next, the resulting patterned film is subjected to thermal curing followed by baking or photocuring followed by exposure. Specifically, it can be heated with a hot plate, oven, etc., or exposed with an ultraviolet irradiation device. A film (cured film) with improved heat resistance, planarization, low water absorption, and chemical resistance is obtained, and has a good undulating pattern.

As the conditions for post-baking, generally speaking, 150-300°C is preferred, 200-250°C is better, in the case of using a hot plate, it is 1-30 minutes, in the case of an oven, It is a method of heating for 1 to 90 minutes. In the present invention, by performing such post-baking, a cured film with a good pattern shape can be obtained.

As described above, the resin composition of the present invention has a high transmittance of ultraviolet rays in the exposure process, and can be fully cured to the deep part of the film, and by curing the composition, the visible light shielding property can be formed. High hardened film. The obtained cured film can be suitably used as a material for self-luminous displays such as QD-OLED displays or Micro LED displays, especially as partition walls (coloring) that constitute the sub-pixels of the wavelength conversion layer of self-luminous display panels. Next door) to use, which can contribute to the further improvement of its image quality. [Example]

The following examples illustrate the present invention in more detail, but the present invention is not limited to these examples.

[The abbreviations used in the examples] The meanings of the abbreviations used in the following examples are as follows. MAA: methacrylic acid MMA: methyl methacrylate AIBN: azobisisobutyronitrile PRG1: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole- 3-yl]-1-(O-acetyloxime) (365nm absorbance coefficient: 7,749 ml/g‧cm in CH ₃ CN) PRG2: 1-hydroxy-cyclohexyl-phenyl-ketone (365nm absorbance coefficient: 88.64 ml/g‧cm in MeOH) PRG3: manufactured by BASF, IRGACURE (registered trademark) OXE03 DPHA: manufactured by Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) DPHA (product name), a mixture of dipentaerythritol penta and hexaacrylate A-DPH-12E: manufactured by Shin Nakamura Chemical Industry Co., Ltd., NK ESTER (registered trademark) A-DPH-12E (product name), ethoxylated dipentaerythritol hexaacrylate CTA: manufactured by Showa Denko Co., Ltd., Karenz -MT (registered trademark) PE1 (product name), pentaerythritol 4 (3-mercaptobutyrate) PFHMA: 2-(perfluorohexyl) ethyl methacrylate KBM-503: 3-methacryloxy propyl Trimethoxysilane (alias: 3-triethoxysilyl propyl acrylate) HEMA: 2-hydroxyethyl methacrylate PFPE1: Both ends do not have a poly(oxyalkylene) group but two hydroxyl groups Perfluoropolyether [Fomblin (registered trademark) T4 manufactured by Solvay Specialty Polymers] BEI: 1,1-bis(acryloxymethyl) ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko Corporation] DOTDD: Dioctyltin dineodecanoate [Nitto Kasei Co., Ltd. Neostan (registered trademark) U-830] PGME: Propylene glycol monomethyl ether MEK: Methyl ethyl ketone

[Black Pigment and Dispersant] Black pigment 1: manufactured by Mitsubishi Materials Co., Ltd., NITRBLACK UB-1 Black pigment 2: manufactured by Mitsubishi Materials Co., Ltd., 13M-T Dispersant: made by Japan Lubrizol (stock), SOLSPERSE 34750

＜The light transmittance of black pigment containing film＞ (1) Black pigment 1 contains the formation of a thin film P1 (8.11g), DPHA (1.99g), PRG1 (0.03g), PRG2 (0.09g), CTA (0.01g) obtained in Synthesis Example 1 described below, and the pigment dispersion liquid 1 (0.63g) described below P2 (0.50g) and PGME (0.65g) obtained in Synthesis Example 2 described later were mixed, and prepared to be dispersed in (F) at a ratio of 100 parts by mass of (A) component and 10 parts by mass of (D) component A dispersion liquid (the black pigment 1 contains a resin composition) in the components. After coating the obtained dispersion liquid on an alkali-free glass (substrate) using a spin coater, it was prebaked on a hot plate at 100° C. for 120 seconds to form a black pigment 1 containing thin film with a film thickness of 10 μm.

(2) The formation of black pigment 2 containing thin film Instead of the pigment dispersion liquid 1 used in (1), the pigment dispersion liquid 2 described later is used. The rest is the same method as (1) to prepare the component (D) relative to 100 parts by mass of the component (A) It is a dispersion liquid in which the component (F) is dispersed in a ratio of 10 parts by mass (the black pigment 2 contains a resin composition). Using the obtained dispersion liquid, a black pigment 2 containing thin film having a thickness of 10 μm was formed on an alkali-free glass (substrate) in the same manner as in (1).

(3) Measurement of light transmittance For the film formed above, use an ultraviolet-visible spectrophotometer (SIMADZU UV-2550 model manufactured by Shimadzu Corporation) to measure the transmittance T ₁ at the wavelength of 365nm and the wavelength of 550nm The light transmittance T ₂ , calculate the ratio T ₁ /T _{2 of the two} . The results are shown in Table 1.

[Measurement of number average molecular weight Mn and weight average molecular weight Mw of (A) component and (E) component] The Mn and Mw of (A) component, (E) component copolymer, and (E) component polymer synthesized according to the following synthesis examples are using GPC equipment manufactured by Shimadzu Science Co., Ltd. (tube columns KF803L and KF804L) As the precipitation solvent, tetrahydrofuran was flowed through the column (column temperature 40°C) at a flow rate of 1 mL/min to perform the measurement. In addition, the following number average molecular weight (hereinafter referred to as Mn.) and weight average molecular weight (hereinafter referred to as Mw.) are expressed in terms of polystyrene.

＜Synthesis example 1＞ As the monomer components constituting the copolymer, MAA (30.0g) and MMA (120.0g) were used, and AIBN (6.4g) was used as the radical polymerization initiator. The polymerization reaction was performed at 90°C for 16 hours to obtain a copolymer solution P1 of the component (A) (copolymer concentration: 35% by mass). The Mn series of the obtained copolymer was 9,700, and the Mw series was 21,500.

＜Synthesis example 2＞ As the monomer components constituting the copolymer, PFHMA (5.00g), KBM-503 (3.83g) and HEMA (1.51g) are used. As the radical polymerization initiator, AIBN (0.52g) is used. (25.32g), the polymerization reaction was performed at 80 degreeC for 16 hours, and the copolymer solution P2 of (E) component (copolymer concentration: 30 mass %) was obtained. The Mn series of the obtained copolymer was 4,800, and the Mw series was 6,700.

＜Synthesis example 3＞ Using PFPE1 (1.19g) and BEI (0.48g), DOTDD (0.017g) was used as a catalyst, and they were reacted in a solvent MEK (1.67g) at room temperature (about 23°C) for 24 hours to obtain ( E) Component polymer solution P3 (polymer concentration: 50% by mass). The Mn series of the obtained P3 was 2,500, and the Mw series was 3,000.

<Preparation of pigment dispersion> The black pigment, solvent, and dispersant were mixed at the blending ratios described in Table 2. The solution was subjected to a dispersion treatment with Mix Rotor for 8 hours. As the balls, use 0.5mmφ silicon beads, and add 5 times the mass of the dispersion. After the dispersion is completed, the balls and the dispersion are separated by a filter to prepare a pigment dispersion.

<Examples 1 to 3, Comparative Examples 1 to 2> According to the composition shown in Table 3 below, in the solution of (A) component, mix (B) component, (C-1) component, (F) component solvent, optional component, (D) component and (E) component , And stirred at room temperature for 3 hours to prepare resin compositions of Examples and Comparative Examples.

With respect to the obtained resin compositions of Examples 1 to 3 and Comparative Examples 1 to 2, the transmittance measurement and pattern shape observation were performed, respectively.

[Evaluation of transmittance and optical density (OD value)] After coating the resin composition on an alkali-free glass (substrate) using a spin coater, it is pre-baked on a hot plate at 100°C for 120 seconds. A coating film (film thickness 14 μm) was formed. The obtained coating film was irradiated with ultraviolet rays having a light intensity of 5.5 mW/cm ² at 365 nm at 140 mJ/cm ² using an ultraviolet irradiation device PLA-600FA manufactured by Canon Co., Ltd. After that, spray development was performed for 180 seconds with a 0.033% by mass potassium hydroxide aqueous solution, and then, running water washing was performed for 30 seconds with ultrapure water. Next, using an oven, the coating film was heated at 230°C for 30 minutes and post-baked to obtain a cured film (film thickness 10 μm).

For the cured film obtained above, an ultraviolet-visible spectrophotometer (SIMADZU UV-2550 model manufactured by Shimadzu Corporation) was used to measure the transmittance at a wavelength of 200 to 800 nm, and the optical density (OD value) at 550 nm was calculated. In addition, the OD value is a numerical value indicating the light-shielding ability, and the larger the value, the higher the light-shielding ability. The results obtained are shown in Table 3.

[Evaluation of patterning] After coating the resin composition on an alkali-free glass (substrate) using a spin coater, it is pre-baked on a hot plate at 100°C for 120 seconds to form a coating film (film thickness 14μm) . For this coating film, with a mask of 10μm line and blank pattern, using a Canon (stock) ultraviolet irradiation device PLA-600FA, the 365nm light intensity is 5.5 mW/cm ² of ultraviolet light to 140 mJ/cm ² Perform irradiation. After that, spray development was performed for 180 seconds with a 0.033% by mass potassium hydroxide aqueous solution, and then, running water washing was performed for 30 seconds with ultrapure water. Next, using an oven, the coating film was heated at 230°C for 30 minutes to perform post-baking and harden it. The cross-sectional shape of the hardened line and the blank pattern was observed using a scanning electron microscope S-4800 manufactured by Hitachi Advanced Technologies, and the pattern resolution was evaluated based on the following criteria. The results obtained are shown in Table 4. <Evaluation Criteria> ○: Pattern can be formed without residual film ×: Pattern cannot be formed, or pattern can be formed but residual film is present

According to the results of Table 4, in Examples 1 to 3, it is shown that the shielding properties of visible light are excellent, and the resolution is also excellent. On the other hand, in Comparative Example 1, the shielding properties of visible light were insufficient, and in Comparative Example 2, the pattern could not be formed.

Claims (12)

A resin composition, which is characterized in that it contains: (A) an alkali-soluble copolymer; (B) having two or more acrylate groups, methacrylate groups, vinyl groups, and allyl groups. Selected at least one polymerizable compound; (C) Photoinitiator: (C-1) has an oxime ester group, and the absorption coefficient in methanol or acetonitrile at 365nm is 5,000 ml/g·cm The above photoinitiator; (D) Black pigment: The absorption coefficient of (A) component, (B) component, (C-1) component, (C-2) in methanol or acetonitrile at 365nm is 100 ml/g·cm or less of the photoinitiator, (D) black pigment, (E) liquid-repellent component, (F) solvent, and (G) thiol compound, based on 100 parts by mass of (A) component (D) component is 10 parts by mass dispersed in (F) component dispersion liquid coated on a glass substrate and dried to form a film with a thickness of 10μm, so that light with a wavelength of 365nm penetrates was T _1, so that the light transmittance of the wavelength of 550nm is ₂ T, T ₁ / T is 0.3 or more of the black pigment _2; (E) repellent composition; and (F) a solvent. The resin composition according to claim 1, wherein the content of the component (D) is 1 to 50 parts by mass relative to 100 parts by mass of the component (A). The resin composition according to claim 1 or 2, wherein the number average molecular weight of the component (A) is 2,000 to 50,000 in terms of polystyrene. The resin composition as described in any one of claims 1 to 3, wherein the component (A) is composed of acrylic acid, methacrylic acid, maleic anhydride, and maleimide. A copolymer of at least one monomer mixture selected. The resin composition according to any one of claims 1 to 4, wherein the content of the component (C-1) is 0.3 to 5 parts by mass relative to 100 parts by mass of the component (A). The resin composition according to any one of claims 1 to 5, wherein the content of the component (B) is 10 to 150 parts by mass relative to 100 parts by mass of the component (A). The resin composition according to any one of claims 1 to 6, wherein the component (C-1) is a photoinitiator having a carbazole structure. A cured film obtained from the resin composition described in any one of claims 1 to 7. A partition wall for a self-luminous display is formed of the resin composition described in any one of claims 1 to 7. A wavelength conversion layer of a self-luminous display is provided with the partition wall as described in claim 9. An organic electroluminescence element comprising the wavelength conversion layer as described in claim 10. A Micro LED element is provided with the wavelength conversion layer as described in claim 10.