KR101401145B1 - Composition of photo sensitive resin - Google Patents
Composition of photo sensitive resin Download PDFInfo
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- KR101401145B1 KR101401145B1 KR1020130030229A KR20130030229A KR101401145B1 KR 101401145 B1 KR101401145 B1 KR 101401145B1 KR 1020130030229 A KR1020130030229 A KR 1020130030229A KR 20130030229 A KR20130030229 A KR 20130030229A KR 101401145 B1 KR101401145 B1 KR 101401145B1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
- G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
- G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
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- Materials For Photolithography (AREA)
Abstract
Description
The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition for forming a light-blocking insulating film included in an organic light emitting diode display.
With the development of the display industry, photosensitive resin compositions for organic light emitting diode displays are continuously required to have many characteristics such as relatively low dielectric constant, excellent resolution, low moisture absorption rate, and excellent thermal stability.
Polyimide has been extensively researched and developed as a polymer material having excellent physical properties capable of satisfying the above characteristics. However, since the conventional polyimide matrix structure corresponds to a polyamic acid having a hydrophilic carboxyl group, it is excessively dissolved in an alkali developing solution, and therefore, there is a problem that a membrane is reduced during development, The diamine structure having a hydroxyl group introduced into the hydrophilic carboxyl group has a sufficient solubility difference between the unexposed portion and the exposed portion in order to improve the degree of solubility, And the mechanical strength is weak.
In recent years, polyimide resin needs to be used as a partition wall for blocking light between cells. The polyimide resin has an advantage of having a relatively low moisture absorption rate, but has difficulty in dispersing the black pigment for blocking the light.
An object of the present invention is to provide a photosensitive resin composition capable of uniformly dispersing a black pigment which suppresses light leakage phenomenon from the inside.
(A) a polyimide binder represented by the following general formula (1), (b) a polyimide binder represented by the following general formula (1), a carbon black And a dispersant, (c) a photopolymerization initiator, and (d) an excess solvent,
Wherein the polyimide binder (a) and the black polyimide dispersion (b) have a volume ratio of 0.25 to 2.25: 1 and the photopolymerization initiator (c) comprises the polyimide binder (a) Has a ratio of 0.015 to 0.048 g per unit volume (ml) added.
Formula 1
delete
In the above formula (1), m, n, o ... ... and w and q are independently a hydrogen atom or an epoxy acrylate substituent represented by the following formula (2), R3 and R4 are each independently hydrogen or a urethane acrylate substituent represented by the following formula (3), X and Y are A hydrocarbon chain which is independently substituted or unsubstituted with a halogen, a hydroxyl group, a sulfone group, a nitro group or a cyano group, or a part of the carbon skeleton is a hetero chain substituted by N, O or S, or an aromatic ring is connected or fused, To R16 each independently represents an alkyl or alkoxy group having 1 to 30 carbon atoms which is optionally substituted with hydrogen, halogen, hydroxyl, carboxyl, sulfonic group, nitro group or cyano group, halogen, hydroxyl group, carboxyl group, sulfone group, Cyano group.
(2)
In the formula (2), R17 is a hydrocarbon group having 2 to 50 carbon atoms and a bonding number of 2.
(3)
In the above formula (3), R 18 is a hydrocarbon group having 2 to 50 carbon atoms and a bonding number of 2.
Here, the polyimide binder may include two or more kinds of moieties derived from an aromatic dianhydride, and the moiety (b) includes two or more kinds of moieties derived from an organic diamine,
Wherein at least one of R 1 and R 2 is substituted with an epoxy acrylate of Formula 2 and the number of moieties in a portion of Formula 1 is 2 to 50% of the total number of moieties derived from dianhydride, and at least one of R 3 and R 4 May be 2 to 50% of the number of the residues derived from the total organic diamine, wherein the number of the moieties of the moiety (b) of the formula (1) substituted with the urethane acrylate of the formula (3)
In one embodiment of the present invention, the black polyimide dispersion contains 2.00-17.00 wt% of the polyimide binder represented by Formula 1, 8.00-23.00 wt% of the carbon black, 0.01-0.70 wt% of the dispersing agent, . Here, the dispersant may be at least one selected from the group consisting of a polyethylene compound, a polyester compound, a polycarboxylic acid ester compound, an unsaturated polyamide compound, a polycarboxylic acid compound, a polycarboxylic acid alkyl salt compound, a polyacrylic compound, A polyurethane-based compound.
In one embodiment of the present invention, it is preferred that the polyimide precursor has a glass transition temperature (Tg) of 210 캜 to 380 캜.
The photopolymerization initiator used in the present invention may be an acetophenone based or benzophenone based triene based and / or oxime based photopolymerization initiator as a commonly used photopolymerization initiator.
For example, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone , Benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, 2,2'- 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 1,2-octanedione- Benzoylbenzoic acid, methyl benzoyl benzoate, 4-phenylbenzoyl benzoate, benzoyl benzoic acid, methyl benzoyl benzoate, methyl benzoyl benzoate, (Diethylamino) benzophenone, 2,4,6-trichloro-s-tri (methoxymethyl) benzophenone, 4,4'- Bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-dihydroxy- Bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- Methyl) -s-triazine, bis (trichlorobetyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2-4-trichloromethyl (piperonyl) -6-triazine, 2 (4-methoxynaphtho- 4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like. And it is added in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the entire composition depending on the kind and use of the product.
The acrylic photopolymerizable monomer used in the present invention is, for example, glycol monomethacrylate, trimethylolpropane triacrylate, epoxy acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, diethylene glycol Dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate , 1,9-nonanediol dimethacrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorenedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and the like. The acrylic photopolymerizable monomer is added in an amount of 1 to 20 parts by weight based on 100 parts by weight of the entire photosensitive resin composition.
The solvent used in the present invention is usually tetrahydrofuran, xylene, dichlorobenzene, propylene glycol methyl ether, gamma butyrolactone and the like in addition to dimethylformamide, N-methylpyrrolidone, dimethylacetamide and dimethyl disulfoxide. Or a mixture of two or more thereof. Ethyl lactate or 4-butoxyethanol may be added to improve coating properties.
In the present invention, a polyimide precursor composition may contain a silane coupling agent for improving adhesion with a substrate. Examples of the polyimide precursor composition include silane coupling agents having a reactive functional group such as carboxyl group, methacryloyl group, isocyanate group, More specifically, it may include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanate propyltriethoxysilane,? -Glycidyl Isopropyltrimethoxysilane, 2- (3 ', 4'-epoxycyclohexyl) ethyltrimethoxysilane, and the like. The silane coupling agents may be used alone or in admixture of two or more. The silane coupling agent may be adjusted in a proportion of 1% by weight or less based on the whole photosensitive resin composition.
The photosensitive resin composition according to an embodiment of the present invention may further include a leveling agent, a photosensitizer, a thermal polymerization inhibitor, a defoaming agent or a sensitizer.
An example of an additive which can be added is a leveling agent for improving the coatability. R-08, R-475, R-30 (manufactured by DIC), BM-1000, BM-1100 (manufactured by BM CHEMIE), Fluoride FC-135, FC- S-131, S-141, S-145, S-112, S-113, S-131, S- (Manufactured by Asahi Glass Co., Ltd.), SH-28 PA, SH-190, SH (available from Asahi Glass Co., Ltd.), SC-101, SC-102, SC- Fluorine-based or silicone-based surfactants such as S-603, S-603, SF-8428, DC-57 and DC-190 (manufactured by Toray Silicone Co., Ltd.) These leveling agents may be used alone or in combination of two or more. The leveling agent is used in an amount of 1% by weight or less based on the entire photosensitive resin composition.
In the photosensitive resin composition according to the present invention thus prepared, a high-sensitivity, high-resolution resin composition having a low dielectric constant, fast development, low film reduction rate, excellent heat resistance, adhesive force, flatness and light shielding effect can be obtained.
The photosensitive resin composition applied to the substrate may be provided as a barrier rib or the like that is formed of a polyimide film by imidizing by baking the remaining pattern through a photolithography process and can suppress the light leakage phenomenon between OLED cells depending on the use purpose .
Hereinafter, the photosensitive resin composition according to an embodiment of the present invention will be described in detail with reference to tables, synthesis examples and examples. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.
The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.
On the other hand, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
Synthesis Example 1 Synthesis of polyimide precursor [PI1]
23.6 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 81.58 g of gamma-butyrolactone, and 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride 25.17 g of rye, 0.63 g of maleic anhydride, 5.80 g of diaminophenyl ether and 8.46 g of 4,4'-oxydianiline were placed and stirred at room temperature for 4 hours and 30 minutes to obtain a polyimide precursor [PI1].
Synthesis Example 2 Synthesis of urethane acrylate [UA1]
After adding 25 g of diphenylmethane diisocyanate, 7.5 g of 2-hydroxyethyl methacrylate, 1.0 mg of dibutyltin dilaurate and 3.0 mg of butylated hydroxytoluene and reacting at 60 ° C. for 4 hours to obtain urethane acrylate [UA1 ].
Synthesis Example 3 Synthesis of epoxy acrylate [EA1]
After diluting 4630 mg of ethylene glycol diglycidyl ether with 20 ml of gamma-butyrolactone, 0.76 ml of acrylic acid, 60 mg of tetrabutylphosphonium bromide and 2.4 mg of 2,6-di-tert-butyl-4-methylphenol were added, Was reacted with stirring at 110 캜 for 12 hours to obtain an epoxy acrylate [EA1].
Synthesis Example 4 Synthesis of [PI1 + UA1]
5 g of [UA1] obtained in Synthesis Example 1 was added to 40 g of [PI1] obtained in the above Synthesis Example 5, and 0.8 mg of dibutyltin dilaurate and 1.5 mg of butylated hydroxytoluene were added thereto, followed by reaction at 60 ° C. for 4 hours A polyimide precursor [PI1 + UA1] having urethane acrylate substituted in the hydroxyl group of the polyimide precursor was obtained.
Synthesis Example 5 Synthesis of [PI1 + EA1 + UA1]
1.5 g of [EA1] obtained in Synthesis Example 3 was added to 25 g of [PI1 + UA1] obtained in Synthesis Example 6, and 38 mg of tetrabutylphosphonium bromide and 1.6 mg of 2,6-di-tert- And then reacted for 12 hours at a temperature of 110 ° C with stirring to obtain a polyimide precursor [PI1 + EA1 + UA1] of the present invention in which an epoxy acrylate was substituted for the carboxyl group of [PI1].
Example 1
(Production of black polyimide dispersion [A1]
230 g of carbon black (Special Black 550, Ebonic Gosei, Germany), 0.1 g of dispersant (DISPER BYK-111, BYK-chemie, Germany) and 20 g of [PI1 + UA1] 749.9 g of lactone was subjected to a dispersion process for 10 minutes using a vertical type high energy milling equipment (beads mill, UAM-015, KOTOBUKI, Japan) using a ZrO 2 bead having a diameter of 0.2 mm to obtain a black polyimide dispersion [A1] was obtained.
(Preparation of photosensitive resin composition [PR1]) [
100 ml of the solution of the black polyimide dispersion [A1] obtained above was placed in 10 ml of the binder [PI1 + UA1] obtained from Synthesis Example 4, 1.0 g of 1-hydroxycyclohexyl phenyl ketone was added as a photopolymerization initiator, 2.0 g of polyfunctional monomer dipentaerythritol hexaacrylate was added as a polymerization initiator, 60 mL of solvent gamma butyrolactone was added, 0.01 g of? -Glycidoxypropyltrimethoxysilane was added as a silane coupling agent, and R-08 Was added to prepare a photosensitive resin composition [PR1] of the present invention.
Example 2
(Preparation of Black Polyimide Dispersion [A2]) [
180 g of carbon black (Special Black 550, Ebonic Gose Co., Germany), 7.0 g of dispersant (DISPER BYK-111, BYK-chemie, Germany), 70 g of Gamma butyrolactone as a solvent were added to 70 g of [PI1 + UA1] 743.0 g of lactone was dispersed using a vertical type high energy milling equipment (beads mill, UAM-015, KOTOBUKI, Japan) for 10 minutes by using a ZrO 2 bead having a diameter of 0.2 mm to obtain a black polyimide dispersion [A2] was obtained.
(Preparation of photosensitive resin composition [PR2]) [
The photosensitive resin composition [PR2] of the present invention was prepared in the same manner as in Example 1 except that 10 ml of the black polyimide dispersion solution [A2] obtained above was added to 45 ml of the binder [PI1 + UA1] obtained from Synthesis Example 4 .
Example 3
(Production of black polyimide dispersion [A3]
130 g of carbon black (SPECIAL BLACK 550, Ebonite KK, Germany), 1.5 g of a dispersant (DISPER BYK-111, BYK-chemie, Germany), 120 g of [PI1 + UA1] obtained in Synthesis Example 4, 748.5 g of lactone was dispersed using a vertical type high energy milling machine (beads mill, UAM-015, KOTOBUKI, Japan) for 10 minutes by using a ZrO 2 bead having a diameter of 0.2 mm to obtain a black polyimide dispersion [A3].
(Preparation of photosensitive resin composition [PR3]) [
The photosensitive resin composition [PR3] of the present invention was prepared in the same manner as in Example 1, except that 10 ml of the black polyimide dispersion solution [A3] solution obtained above was added to 25 ml of the binder [PI1 + UA1] obtained from <Synthesis Example 4> .
Example 4
(Preparation of Black Polyimide Dispersion [A4]
80 g of carbon black (Special Black 550, Ebonic Gosei, Germany), 0.5 g of a dispersing agent (DISPER BYK-111, BYK-chemie, Germany), 170 g of [PI1 + UA1] obtained in Synthesis Example 4, 749.5 g of lactone was dispersed using a vertical type high energy milling equipment (beads mill, UAM-015, KOTOBUKI, Japan) using a ZrO 2 bead having a diameter of 0.2 mm for 10 minutes to obtain a black polyimide dispersion [A4] was obtained.
(Preparation of photosensitive resin composition [PR4]) [
The photosensitive resin composition [PR4] of the present invention was prepared in the same manner as in Example 1, except that 10 ml of the black polyimide dispersion solution [A4] obtained above was added to 5 ml of the binder [PI1 + UA1] obtained from Synthesis Example 4 .
Example 5
(Production of black polyimide dispersion [B1]
230 g of carbon black (Special Black 550, Ebonic GmbH, Germany), 0.1 g of a dispersing agent (DISPER BYK-111, BYK-chemie, Germany) and 20 g of gamma -butyrolactone were dissolved in 20 g of [PI1 + UA1 + EA1] 749.9 g of butyrolactone was dispersed for 10 minutes using a vertical type high energy milling machine (beads mill, UAM-015, KOTOBUKI, Japan) using a ZrO 2 bead having a diameter of 0.2 mm for 10 minutes, To obtain a mid dispersion [B1].
(Preparation of photosensitive resin composition [PR5]) [
20 ml of the solution of the black polyimide dispersion [B1] obtained above was placed in 10 ml of the binder [PI1 + UA1 + EA1] obtained from Synthesis Example 5 and the photopolymerization initiator 2-methyl-1- [4- (methylthio) -Morpholino-propan-1-one was added thereto, 2.0 g of dipentaerythritol hexaacrylate as a polyfunctional monomer was added as an acrylic photopolymerizable monomer, 60 mL of solvent gamma butyrolactone was added, 0.01 g of glycidoxypropyltrimethoxysilane was added and 0.01 g of R-08 as a leveling agent was added to prepare the photosensitive resin composition [PR5] of the present invention.
Example 6
(Production of Black Polyimide Dispersion [B2]
180 g of carbon black (Special Black 550, Ebonic Gose Co., Germany), 7.0 g of a dispersant (DISPER BYK-111, BYK-chemie, Germany), 70 g of gamma -butyrolactone were dissolved in 70 g of [PI1 + UA1 + EA1] 743.0 g of butyrolactone was dispersed for 10 minutes using a vertical type high energy milling equipment (beads mill, UAM-015, KOTOBUKI, Japan) using a ZrO 2 bead having a diameter of 0.2 mm for 10 minutes, To obtain a mid dispersion [B2].
(Preparation of photosensitive resin composition [PR6]) [
The same procedure as in Example 5 was carried out except that 20 ml of the black polyimide dispersion solution [B2] solution obtained above was added to 45 ml of the binder [PI1 + UA1 + UA1] obtained from Synthesis Example 5 to obtain the photosensitive resin composition [PR6 ].
Example 7
(Production of black polyimide dispersion [B3]
130 g of carbon black (Special Black 550, Ebonix KK), 1.5 g of a dispersing agent (DISPER BYK-111, BYK-chemie, Germany), 120 g of gamma -butyrolactone were dissolved in 120 g of [PI1 + UA1 + EA1] 748.5 g of butyrolactone was dispersed for 10 minutes using a vertical type high energy milling machine (beads mill, UAM-015, KOTOBUKI, Japan) using a ZrO 2 bead having a diameter of 0.2 mm for 10 minutes, To obtain a mid dispersion [B3].
(Preparation of photosensitive resin composition [PR7]) [
The same procedure as in Example 5 was carried out except that 20 ml of the black polyimide dispersion solution [B3] obtained above was added to 25 ml of the binder [PI1 + UA1 + UA1] obtained from Synthesis Example 5 to obtain the photosensitive resin composition [PR7 ].
Example 8
(Production of black polyimide dispersion [B4]
80 g of carbon black (Special Black 550, Ebonic Gose Co., Germany), 0.5 g of dispersant (DISPER BYK-111, BYK-chemie, Germany), 170 g of [PI1 + UA1 + EA1] obtained in Synthesis Example 5, 749.5 g of butyrolactone was dispersed for 10 minutes using a vertical type high energy milling machine (beads mill, UAM-015, KOTOBUKI, Japan) using a ZrO 2 bead having a diameter of 0.2 mm for 10 minutes, MeD dispersion [B4].
(Preparation of photosensitive resin composition [PR8]) [
The same procedure as in Example 5 was carried out except that 20 ml of the black polyimide dispersion solution [B4] solution obtained above was added to 5 ml of the binder [PI1 + UA1 + UA1] obtained from Synthesis Example 5, ].
Comparative Example 1
A photosensitive resin composition (PR9) for a black matrix obtained by dispersing a black pigment and using a copolymer resin of an acrylic carboxylic acid monomer and a fluorene derivative having an ethylenically unsaturated bond as a binder.
Comparative Example 2
Acrylic copolymer as a binder and a photosensitive resin composition (PR10) without using a black pigment.
The compositions for Examples 1 to 8 and Comparative Examples are shown in Table 1 below.
/0.01
The black polyimide dispersion in Table 1 is shown in Table 2 below.
(Special Black 550) / g
(DISPER BYK-111)
(Gamma butyrolactone)
The photosensitive polyimide precursor composition solution obtained from the above Examples and Comparative Examples is subjected to a photolithography process to form a pattern. That is, a glass substrate was used as the transparent substrate used for forming the pattern, and the composition was applied to a thickness of 1.5 um, and then heated (prebaked) at 100 DEG C for 60 seconds. Then, , Ultraviolet rays of mixed wavelengths of g, h and i-lines were exposed to 80 mJ / cm 2, developed with 0.042 wt% aqueous solution of potassium hydroxide solution at 25 ° C for 60 seconds, washed with pure water for 1 minute, And then heated in an oven at 230 DEG C for 30 minutes to form a pattern.
Then, various evaluations were carried out by the following methods.
(1) Shading property (OD)
The light-shielding property was evaluated by post-baking the photosensitive resin composition coated on the glass substrate at 25 캜 with 1.0 탆 for 30 minutes in a convection oven at 250 캜 and then using an OD meter (X-rite 3000, And the light shielding properties were measured. The OD value is preferably 3.4 to 3.6. The reference table is as follows.
? 3.6, 3.6?? 3.4, 3.4?? 3.2, 3.2? X
(2) black polyimide dispersion particle side (nm)
The black polyimide dispersion was diluted 100 times with isopropyl alcohol, and then the average particle size dispersed in the black polyimide dispersion was measured using NICOMP 380 (manufacturer: PSS.NICOMP, USA). It can be said that the measured value is in the range of 150 to 500 nm. The reference table is as follows.
150?, 150?? <500, 500??? 1500, X? 1500
(3) Evaluation of resolution
The photolithography process was performed to confirm the formation of fine patterns. At this time, when a pattern of 10 um to 15 um is formed, it can be said that it is good. The reference table is as follows.
10 >>, 10 < 0 < 15, 15 &
(4) Measurement of dielectric constant
The polyimide precursor composition was coated on the substrate on which the ITO electrode was wired to form a thin film having a thickness of 1.5 um and a photolithography process was performed. Then, platinum was deposited on the thin film and electrodes were connected to measure the dielectric constant. 3.8 range, it can be said that it is good. The reference table is as follows.
3.6?, 3.6?? <3.8, 3.8?? <4.2, X? 4.2
(5) Evaluation of heat resistance
A cured film was formed in the same manner as in the formation of the spacer except that the photomask was not used. The cured film was further heated in an oven at 230 캜 for 30 minutes, and the obtained glass transition temperature was measured using a DSC analyzer. When the temperature at this time is 210 to 270 占 폚, it is preferable. The reference table is as follows.
? 270, 270?? 250, 250? 220, 220? X
6) Resistivity
The above photosensitive resin composition was coated on a glass substrate to form a thin film having a thickness of 1.5 μm, and the resistivity was measured using MCP-HT450 (Mitubishi) after the photolithography process. 10 13 Ω / cm 2 or more. The reference table is as follows.
≥ 10 ^ 13, 10 ^ 13> ≥ 10 ^ 10, 10 ^ 10> △ ≥ 10 ^ 6, 10 ^ 6> X
The evaluation results of the above items (1) to (6) are shown in [Table 3].
Good: Good: Fair: Fair: Fair: Bad: Good
While the present invention has been described in connection with what is presently considered to be practical and exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
(b) a black polyimide dispersion comprising a polyimide binder represented by the following formula (1), carbon black and a dispersant;
(c) a photopolymerization initiator; And
(d) an excess solvent,
Wherein the polyimide binder (a) and the black polyimide dispersion (b) have a volume ratio of 0.25 to 2.25: 1 and the photopolymerization initiator (c) comprises the polyimide binder (a) Is in the range of 0.015 to 0.048 g per unit volume (ml) of the photosensitive resin composition.
Formula 1
In the above formula (1), m, n, o ... ... and w and q are independently a hydrogen atom or an epoxy acrylate substituent represented by the following formula (2), R3 and R4 are each independently hydrogen or a urethane acrylate substituent represented by the following formula (3), X and Y are A hydrocarbon chain which is independently substituted or unsubstituted with a halogen, a hydroxyl group, a sulfone group, a nitro group or a cyano group, or a part of the carbon skeleton is a hetero chain substituted by N, O or S, or an aromatic ring is connected or fused, To R16 each independently represents an alkyl or alkoxy group having 1 to 30 carbon atoms which is optionally substituted with hydrogen, halogen, hydroxyl, carboxyl, sulfonic group, nitro group or cyano group, halogen, hydroxyl group, carboxyl group, sulfone group, Cyano group.
(2)
In the formula (2), R17 is a hydrocarbon group having 2 to 50 carbon atoms and a bonding number of 2.
(3)
In the above formula (3), R 18 is a hydrocarbon group having 2 to 50 carbon atoms and a bonding number of 2.
Wherein at least one of R 1 and R 2 is substituted with an epoxy acrylate of Formula 2 and the number of moieties in a portion of Formula 1 is 2 to 50% of the total number of moieties derived from dianhydride, and at least one of R 3 and R 4 Is substituted with urethane acrylate of the above formula (3) is 2 to 50% of the number of residues derived from the total organic diamine.
2.00-17.00 wt% of the polyimide binder represented by Formula 1;
8.00-23.00 wt% of carbon black;
0.01-0.70 wt% dispersant; And
Wherein the photosensitive resin composition further comprises an excess solvent.
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| KR1020130030229A KR101401145B1 (en) | 2013-03-21 | 2013-03-21 | Composition of photo sensitive resin |
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| KR1020130030229A KR101401145B1 (en) | 2013-03-21 | 2013-03-21 | Composition of photo sensitive resin |
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| KR101401145B1 true KR101401145B1 (en) | 2014-06-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017122912A (en) * | 2016-01-06 | 2017-07-13 | Jnc株式会社 | Photosensitive composition |
| TWI621916B (en) * | 2016-12-01 | 2018-04-21 | 三星Ｓｄｉ股份有限公司 | Photosensitive resin composition,black pixel defining layer using the same and display device |
| US20180231889A1 (en) * | 2017-02-16 | 2018-08-16 | Samsung Sdi Co., Ltd. | Photosensitive resin composition, black pixel defining layer using the same and display device |
| CN115353624A (en) * | 2022-09-30 | 2022-11-18 | 杭州乐一新材料科技有限公司 | Preparation method and dissolution method of photosensitive polyimide oligomer and photosensitive polyimide 3D printing material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110111640A (en) * | 2010-04-05 | 2011-10-12 | 주식회사 이그잭스 | Photo-sensitive resin composition containing a polyimide precursor |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110111640A (en) * | 2010-04-05 | 2011-10-12 | 주식회사 이그잭스 | Photo-sensitive resin composition containing a polyimide precursor |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017122912A (en) * | 2016-01-06 | 2017-07-13 | Jnc株式会社 | Photosensitive composition |
| TWI621916B (en) * | 2016-12-01 | 2018-04-21 | 三星Ｓｄｉ股份有限公司 | Photosensitive resin composition,black pixel defining layer using the same and display device |
| CN108132583A (en) * | 2016-12-01 | 2018-06-08 | 三星Sdi株式会社 | Photosensitive polymer combination defines layer and display device using its black picture element |
| KR20180062770A (en) * | 2016-12-01 | 2018-06-11 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black pixel defining layer using the same and display device |
| US10394120B2 (en) * | 2016-12-01 | 2019-08-27 | Samsung Sdi Co., Ltd. | Photosensitive resin composition, black pixel defining layer using the same and display device |
| CN108132583B (en) * | 2016-12-01 | 2021-06-08 | 三星Sdi株式会社 | Photosensitive resin composition, black pixel defining layer using same, and display device |
| US20180231889A1 (en) * | 2017-02-16 | 2018-08-16 | Samsung Sdi Co., Ltd. | Photosensitive resin composition, black pixel defining layer using the same and display device |
| TWI655504B (en) * | 2017-02-16 | 2019-04-01 | 南韓商三星Ｓｄｉ股份有限公司 | Photosensitive resin composition, black pixel defining layer using the same, and display device |
| US10558118B2 (en) | 2017-02-16 | 2020-02-11 | Samsung Sdi Co., Ltd. | Photosensitive resin composition, black pixel defining layer using the same and display device |
| CN115353624A (en) * | 2022-09-30 | 2022-11-18 | 杭州乐一新材料科技有限公司 | Preparation method and dissolution method of photosensitive polyimide oligomer and photosensitive polyimide 3D printing material |
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