CN111399340B - Colored photosensitive resin composition, color filter comprising same, and display device - Google Patents

Colored photosensitive resin composition, color filter comprising same, and display device Download PDF

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CN111399340B
CN111399340B CN202010140116.0A CN202010140116A CN111399340B CN 111399340 B CN111399340 B CN 111399340B CN 202010140116 A CN202010140116 A CN 202010140116A CN 111399340 B CN111399340 B CN 111399340B
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weight
resin composition
photosensitive resin
colored photosensitive
group
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CN111399340A (en
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金奉奎
李宪熙
李宗洙
金兑昱
张虎振
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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Priority claimed from KR20130099620A external-priority patent/KR20150022172A/en
Priority claimed from KR20130107036A external-priority patent/KR20150028463A/en
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Abstract

The invention relates to a coloring photosensitive resin composition, a color filter and a display device containing the same. The colored photosensitive resin composition comprises a colorant, an alkali-soluble resin, a photopolymerization compound, a photopolymerization initiator and a solvent, wherein the photopolymerization initiator comprises an oxime ester compound of the following chemical formula 1, and the solvent comprises 4-hydroxy-4-methyl-2-pentanone [ chemical formula 1 ]]The R is as described above 1 Is C1-C8 alkyl OR 3 A group, an aryl group having 6 to 10 carbon atoms substituted with a halogen group or an aralkyl group having 7 to 24 carbon atoms substituted with a halogen group, wherein R is 2 Is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, wherein R is 3 Is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

Description

Colored photosensitive resin composition, color filter comprising same, and display device
The present application is a divisional application of chinese patent application having a filing date of 2014, month 07, and 30, a filing number of 201410370141.2, and a name of "colored photosensitive resin composition, color filter and display device including the same".
Technical Field
The invention relates to a colored photosensitive resin composition, a color filter and a display device containing the colored photosensitive resin composition.
Background
Color filters are widely used in image pickup devices, liquid crystal display devices (LCDs), and the like, and the application range thereof is rapidly expanding. Color filters used in color liquid crystal display devices, image pickup devices, and the like are generally manufactured by spin coating a colored photosensitive resin composition containing pigments corresponding to various colors such as red, green, and blue on a substrate patterned in a black matrix, then exposing and developing a coating film formed by heat drying (hereinafter also referred to as "prebaking"), and further repeating a heat curing (hereinafter also referred to as "post baking") operation for each color as needed to form pixels of various colors. Here, the colored matrix forming the pattern is generally formed of a black photosensitive resin composition.
Such colored photosensitive resin compositions are often used as compositions containing pigments, binder resins, photopolymerizable compounds and photopolymerization initiators.
Recently, in order to improve the yield in engineering, a colored photosensitive resin composition having equivalent sensitivity and adhesiveness even with a small exposure amount has been demanded.
In addition, recently, a coloring material of a colored photosensitive resin composition has been micronized to meet performance requirements such as high color purity and high brightness. Therefore, when pixels are formed using the above-described organic compound, there is a problem that a colored layer formed on a substrate has a development residue which is not removed during development. In order to solve the problems, the conventional techniques are generally a method of adjusting the acid value and molecular weight of the binder resin or the acid value of the binder resin and the composition, but the range of application is limited, and when the acid value is too high, the adhesion is insufficient, which causes surface defects, and there is a limit that even residues remained on the metal oxide film and the silicon nitride film are difficult to solve.
Patent literature
Patent document 1: korean patent No. 10-1222390 specification
Disclosure of Invention
The purpose of the present invention is to manufacture color filters and display devices that have excellent storage stability, sensitivity and adhesion by manufacturing a colored photosensitive resin composition using a photopolymerization initiator containing an oxime ester compound and a solvent containing 4-hydroxy-4-methyl-2-pentanone.
In order to achieve the above object, there is provided a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, characterized in that the photopolymerization initiator comprises an oxime ester compound of the following chemical formula 1, and the solvent comprises 4-hydroxy-4-methyl-2-pentanone.
[ chemical formula 1]
The R is as described above 1 Is C1-C8 alkyl OR 3 A group, an aryl group having 6 to 10 carbon atoms substituted with a halogen group or an aralkyl group having 7 to 24 carbon atoms substituted with a halogen group,
the R is as described above 2 Is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 24 carbon atoms,
the R is as described above 3 Is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
The present invention also provides a color filter comprising the colored photosensitive resin composition.
Furthermore, the invention also provides a display device comprising the color filter.
The colored photosensitive resin composition of the present invention can produce a color filter excellent in storage stability, sensitivity and adhesion by containing the oxime ester compound of the aforementioned chemical formula 1 as a photopolymerization initiator and containing 4-hydroxy-4-methyl-2-pentanone as a solvent.
In addition, the color filter has the advantage that the short circuit of the pattern is difficult to occur in the developing process, and the productivity of the color filter can be improved.
Detailed Description
The present invention will be described in more detail below.
The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator comprises an oxime ester compound represented by the following chemical formula 1, and the solvent comprises 4-hydroxy-4-methyl-2-pentanone.
[ chemical formula 1]
The R is as described above 1 Is C1-C8 alkyl OR 3 A group, an aryl group having 6 to 10 carbon atoms substituted with a halogen group or an aralkyl group having 7 to 24 carbon atoms substituted with a halogen group,
the R is as described above 2 Is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 24 carbon atoms,
the R is as described above 3 Is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
When the photopolymerization initiator of the chemical formula 1 is used and the propylene glycol methyl ether acetate solution containing the photopolymerization initiator at a concentration of 0.01 wt% or more has an absorbance of 0.5 or more at 405nm, the initial efficiency is high when the color filter is patterned by exposure with a 405nm laser exposure device, and a high sensitivity and excellent reliability of the colored photosensitive resin composition can be obtained without using an excessive amount of the photopolymerization initiator.
In addition, the solubility of the aforementioned photopolymerization initiator can be increased by using a solvent containing 4-hydroxy-4-methyl-2-pentanone.
The colored photosensitive resin composition produced from the composition can be found to have high concentration and high transmittance, good dispersion stability, and excellent time-dependent properties, and can be effectively used as a raw material for forming a colored pattern constituting a color filter, and the colored photosensitive resin composition can contain an additional additive as required.
The components of the colored photosensitive resin composition of the present invention will be described in detail below.
(A) Coloring agent
The aforementioned colorants are characterized by comprising more than one pigment, more than one dye, or mixtures thereof.
(a1) Pigment
The aforementioned pigment may be an organic pigment or an inorganic pigment which is generally used in this field. The pigment may be subjected to a resin treatment, a surface treatment using a pigment derivative having an acid or basic group introduced therein, a grafting treatment in which a polymer compound or the like is grafted onto the surface of the pigment, a micronizing treatment by a sulfuric acid micronizing method or the like, a washing treatment in which impurities are removed by an organic solvent or water or the like, a removal treatment in which ionic impurities are removed by an ion exchange method or the like, if necessary.
The organic pigment may be any of various pigments used in printing inks, inkjet inks, and the like, and specifically includes water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, pyrene pigments, dioxazine pigments, anthraquinone pigments, anthrapyrimidine pigments, anthraquinones (anthanthrone) pigments, indanthrone pigments, flavanone pigments, pyranthrone pigments, and diketopyrrolopyrrole pigments.
The inorganic pigment may be a metal compound such as a metal oxide or a metal complex, and specifically, may be an oxide or a composite metal oxide of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, an organic black pigment, titanium black, or a pigment that is black by mixing red, green, and blue colors.
In particular, the organic pigment and the inorganic pigment are specifically compounds classified into pigments according to the color rendering index (The society of Dyers and Colourists publication), and more specifically, pigments having the color rendering index (c.i.) number as described below are exemplified, but the present invention is not limited thereto.
C.i. pigment yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185
C.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71
C.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264
C.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37, 38
C.i. pigment blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, 76
C.i. pigment green 7, 10, 15, 25, 36, 47, 58
C.i. pigment brown 28
C.i. pigment black 1, 7, etc.
Preferably, one or more selected from the group consisting of c.i. pigment yellow 138, 139, 150 and 185, c.i. pigment orange 38, c.i. pigment red 255, c.i. pigment violet 23, c.i. pigment blue 15:3, 15:6, c.i. pigment green 7, 36 and 58 are used.
The pigment is preferably a pigment dispersion having a uniform particle diameter. Examples of the method for uniformly dispersing the particle size of the pigment include a method in which a dispersion treatment is performed by containing the pigment dispersant (a 2), and according to the method, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.
(a2) Pigment dispersants
The pigment dispersant is added to maintain deflocculation and stability of the pigment, and specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and these pigment dispersants may be used alone or in combination of two or more.
Specific examples of the cationic surfactant include amine salts such as octadecylamine hydrochloride and lauryl trimethyl ammonium chloride, and quaternary ammonium salts.
Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleate sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylaryl sulfonate salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.
Examples of the other compounds include polyoxyethylene alkyl ethers, polyoxyethylene alkyl benzene ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethylene imines.
The pigment dispersant preferably contains an acrylic dispersant (hereinafter, acrylic dispersant) containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of the commercial products of the acrylic acid ester dispersants include DIPER BYK-2000, DIPER BYK-2001, DIPER BYK-2070 and DIPER BYK-2150, and the acrylic acid ester dispersants may be used singly or in combination.
The pigment dispersant may be other resin-based pigment dispersants in addition to the acrylic dispersant. Examples of the other resin pigment dispersant include: known resin-based pigment dispersants include, in particular, oil-based dispersants such as polycarboxylic acid esters represented by polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, hydroxy-polycarboxylic acid-containing acid esters and modified products thereof, or amides or salts thereof formed by the reaction of polyesters having free (free) carboxyl groups with poly (lower alkylene imines); a (meth) acrylic acid-styrene copolymer, a (meth) acrylic acid- (meth) acrylate copolymer, a styrene-maleic acid copolymer, a water-soluble resin such as polyvinyl alcohol or polyvinylpyrrolidone, or a water-soluble polymer compound; a polyester; modified polyacrylate; addition products of ethylene oxide and propylene oxide, phosphate esters, and the like.
Among the commercial products of the other resin type pigment dispersants, examples of the cationic resin dispersants include: BYK (pick) chemical trade name: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DIPER BYK-184; trade name of BASF company: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; trade name of Lubirzol corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanminshen fine chemicals Co., ltd: the microzyme is composed of a microzyme part (HINOACT) T-6000, HINOACTT-7000 and HINOACTT-8000; tradename of Weisu Corp.): one (AJISPUR) PB-821, AJISPURPB-822, AJISPURPB-823; trade name of co-Rong chemical Co., ltd.): and (3) FLORENE DOPA-17HF, FLORENEDOPA-15BHF, FLORENEDOPA-33, FLORENEEDOPA-44, etc.
In addition to the acrylic acid ester-based dispersant, other resin-based pigment dispersants may be used alone or in combination of two or more kinds, or may be used together with the acrylic acid ester-based dispersant.
The pigment dispersant is in the range of 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content in the pigment. When the content of the pigment dispersant exceeds 60 parts by weight, the viscosity increases, and when the content is less than 5 parts by weight, problems such as difficulty in atomizing the pigment and gelation after dispersion arise.
(a3) Dye
The aforementioned dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, a dye which has solubility to an organic solvent and can ensure reliability of solubility to an alkaline developer, heat resistance, solvent resistance, and the like is preferably used.
As the dye, a dye selected from the group consisting of an acid dye having an acid group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye with a nitrogen-containing compound, a sulfonamide of an acid dye, and the like, and a derivative thereof can be used, and in addition, azo-based, xanthene-based, phthalocyanine-based acid dyes, and derivatives thereof can be selected. Preferably, the foregoing dyes may be exemplified by: a compound classified as a dye in a color rendering index (The Society of Dyers and Colourists publication), or a known dye described in a dyeing note (dyeing company).
In specific examples of the foregoing dyes, as c.i. solvent dyes,
c.i. solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, and 179;
c.i. solvent blues 5, 35, 36, 37, 44, 59, 67 and 70;
c.i. solvent violet 8, 9, 13, 14, 36, 37, 47, and 49;
c.i. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162;
c.i. solvents orange 2, 7, 11, 15, 26 and 56;
c.i. solvents green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.
C.i. solvent red 8, 49, 89, 111, 122, 132, 146, 179 in the c.i. solvent dye; c.i. solvent blue 35, 36, 44, 45, 70; the c.i. solvent violet 13 is excellent in solubility to an organic solvent, and c.i. solvent red 8, 122, 132 is preferable.
Further, as the c.i. acid dye, there are listed: c.i. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422 and 426;
C.i. acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, and 251;
c.i. acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, and 173;
c.i. acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335 and 340;
c.i. acid violet 6B, 7, 9, 17, 19 and 66;
c.i. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109.
Of the acid dyes, c.i. acid red 92; c.i. acid blue 80, 90; c.i. acid violet 60 is excellent in solubility in organic solvents.
Further, as the c.i. direct dye, there are listed: c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, and 250;
c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138 and 141;
c.i. direct oranges 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, and 107;
c.i. direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;
C.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;
c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.
Further, as the c.i. mordant dye, there are listed: c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65;
c.i. mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, and 95;
c.i. mordant oranges 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, and 48;
c.i. mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84;
c.i. mordant violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, and 58;
c.i. mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53.
The above dyes can be used singly or in combination of two or more.
The content of the dye in the colorant is 0.5 to 80% by weight, preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight, based on the total weight of the solid content of the colorant. When the dye content in the colorant is 0.5 to 80 wt%, the problem of degradation of the reliability of dye elution by an organic solvent after patterning can be prevented, and the sensitivity is increased.
The content of the colorant is 5 to 60% by weight, preferably 10 to 45% by weight, based on the total weight of the solid components in the colored photosensitive resin composition. When the colorant is 5 to 60% by weight, the color density of the pixel is sufficient even if a thin film is formed, and the defect of the non-pixel portion is not reduced during development, so that residue is hardly generated.
In the present invention, the weight of the solid component in the colored photosensitive resin composition means the total content of the remaining components after the solvent is removed from the colored photosensitive resin composition.
(B) Alkali-soluble resin
In order to be soluble in an alkaline developer used in a development treatment step for patterning, the developer is produced by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component.
Specific examples of the ethylenically unsaturated monomer having a carboxyl group include: monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; anhydrides of dicarboxylic acids; preferred examples of the mono (meth) acrylate include acrylic acid and methacrylic acid, and polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxyl polycaprolactone mono (meth) acrylate.
In order to secure the developability added to the alkali-soluble resin, a hydroxyl group may be provided. The method for providing hydroxyl groups is as follows: a method for producing an ethylenically unsaturated monomer having a carboxyl group by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group; a method in which a copolymer of an ethylenically unsaturated monomer having a carboxyl group is additionally reacted with a compound having a glycidyl group; and a method for producing the copolymer by additionally reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group with a compound having a glycidyl group.
Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxy and acrylamide, and among them, 2-hydroxyethyl (meth) acrylate is preferable. The aforementioned ethylenically unsaturated monomers having hydroxyl groups may be used in combination of two or more.
Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl-4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, and glycidyl methacrylate, and preferably butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate, and two or more of the compounds having a glycidyl group may be used in combination.
The unsaturated monomer copolymerizable at the time of producing the alkali-soluble resin may be exemplified as follows, but is not necessarily limited thereto.
Specific examples of the polymerizable monomer having a copolymerizable unsaturated bond include aromatic vinyl compounds such as styrene, vinyltoluene, α -methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether;
N-substituted maleimides such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide;
alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate; alicyclic (meth) acrylates such as cyclopentylacrylate, cyclohexylacrylate, 2-methylcyclohexylacrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate, 2-dicyclopentyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;
hydroxyethyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and N-hydroxyethyl acrylamide;
Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
unsaturated oxetane compounds such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane.
The above exemplified monomers may be used singly or in combination of two or more.
In order to ensure compatibility with the dye of the alkali-soluble resin and storage stability of the colored photosensitive resin composition, the acid value is preferably 30 to 150mgKOH/g. When the acid value of the alkali-soluble resin is less than 30mgKOH/g, the development rate of the colored photosensitive resin composition is low, and when it exceeds 150mgKOH/g, the adhesion to the substrate is lowered, pattern short-circuiting is likely to occur, compatibility with the dye is caused, the dye in the colored photosensitive resin composition is precipitated, the storage stability is lowered, and the viscosity is increased.
The content of the alkali-soluble resin is 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the solid components in the colored photosensitive resin composition. When the content of the alkali-soluble resin is 10 to 80% by weight, the resin is excellent in solubility in a developer, and is easily patterned, and the film of the pixel portion of the exposure portion is prevented from being reduced during development, so that the defect of the non-pixel portion is improved.
(C) Photopolymerizable compound
The photopolymerizable compound (C) may be any compound capable of polymerizing by the following photopolymerization initiator (D).
The number of functional groups is not particularly limited, but a polyfunctional photopolymerizable compound having a double function or more is preferably used, and a trifunctional or more polyfunctional photopolymerizable compound having excellent polymerizability and sufficiently cured is more preferably used.
Specific examples of the difunctional photopolymerizable compound include 2-hydroxy-1, 3-dimethylacryloyloxypropane and 2-hydroxy-1-acryloyloxy-3-methylacryloyloxypropane.
Specific examples of the above-mentioned trifunctional or higher-functional photopolymerizable compound include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like, and two or more kinds of the above-mentioned trifunctional or higher-functional photopolymerizable compounds may be used in combination. Commercially available products include trade names 701 (NK ESTER), 701A (NK ESTER), A-TMM-3L (NK ESTER), KAYARAD DPHA (Japanese chemical).
The photopolymerizable compound (C) is 5 to 45% by weight, preferably 7 to 45% by weight, based on the total weight of the solid components in the colored photosensitive resin composition. When the photopolymerizable compound (C) is 5 to 45 wt%, the strength and smoothness of the pixel portion are good.
(D) Photopolymerization initiator
The photopolymerization initiator (D) is characterized by comprising an ethylcarbazole structure represented by the following chemical formula 1, which is substituted with NO 2 Oxime ester compound (d 1). The propylene glycol methyl ether acetate solution containing the photopolymerization initiator at a concentration of 0.01% by weight or more must have an absorbance at 405nm of 0.5 or more.
[ chemical formula 1]
The R is as described above 1 Is C1-C8 alkyl OR 3 A group, an aryl group having 6 to 10 carbon atoms substituted with a halogen group or an aralkyl group having 7 to 24 carbon atoms substituted with a halogen group,
the R is as described above 2 Is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 24 carbon atoms,
the R is as described above 3 Is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
When the propylene glycol methyl ether acetate solution containing the photopolymerization initiator of the oxime ester compound of chemical formula 1 at a concentration of 0.01 wt% or more has an absorbance of 0.5 or more at 405nm, the initial efficiency becomes high when the pattern is formed by exposure with a laser light exposure device of 405nm, and a high sensitivity and excellent reliability of the colored photosensitive resin composition can be obtained without using an excessive amount of photopolymerization initiator.
The photopolymerization initiator (d 2) other than the above may be used in addition to the above-mentioned one within a range not to impair the effects of the present invention. Examples of the photopolymerization initiator (d 2) preferably include at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, and thioxanthone compounds.
Specific examples of the acetophenone compound include: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylsulfanyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
Examples of the benzophenone compound include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methylbenzenesulfide, 3', 4' -tetra (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone.
Specific examples of the triazine compound include: 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.
Specific examples of the above-mentioned bisimidazole compound include: 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetra (alkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', imidazole compounds obtained by replacing phenyl groups at the 5,5' -tetrakis (trialkoxyphenyl) biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -biimidazole and 4,4', 5' positions with alkoxycarbonyl groups, and the like. Of these, 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenyl-biimidazole and 2, 2-bis (2, 6-dichlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -biimidazole are preferred.
Examples of the thioxanthone compound include: 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.
In order to improve the sensitivity of the colored photosensitive resin composition of the present invention, the photopolymerization initiator may further contain a photopolymerization initiator auxiliary agent (d 3). The colored photosensitive resin composition of the present invention contains the photopolymerization initiator aid (d 3) to improve the sensitivity and thus to improve the productivity.
For example, the photopolymerization initiator (d 3) may preferably be one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organosulfur compounds having a thiol group.
As the amine compound, an aromatic amine compound is preferably used, and specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone (commonly referred to as Michler's ketone), 4' -bis (diethylamino) benzophenone, and the like can be used.
The carboxylic acid compound is preferably an aromatic heteroaromatic acid, and specifically, examples thereof include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.
Specific examples of the organic sulfur compound having a thiol group include: 2-mercaptobenzothiazole, 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like.
The photopolymerization initiator is preferably used in an amount of 0.1 to 30% by weight, and more preferably 1 to 20% by weight, based on the total weight of the solid components in the colored photosensitive resin composition of the present invention. When the photopolymerization initiator is in the range of 0.1 to 30 wt%, the sensitivity of the colored photosensitive resin composition is increased, the exposure time is shortened, the productivity is improved, and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition and the smoothness of the surface of the pixel portion are improved.
The oxime ester compound (d 1) of the chemical formula 1 is contained in an amount of 10 to 100% by weight, preferably 20 to 100% by weight, based on the total weight of all photopolymerization initiators. When the proportion of the oxime ester compound (d 1) of chemical formula 1 in the total photopolymerization initiator is less than 10% by weight, the decrease in sensitivity due to the dye cannot be overcome, and a short circuit of the pattern is likely to occur in the developing step.
In the case where the photopolymerization initiator auxiliary (d 3) is used in addition, the photopolymerization initiator auxiliary (d 3) is preferably 0.1 to 30% by weight, and more preferably 1 to 20% by weight, based on the total weight of the solid components in the colored photosensitive resin composition of the present invention. When the content of the photopolymerization initiator (d 3) is in the range of 0.1 to 30 wt%, the sensitivity of the colored photosensitive resin composition is further improved, and the productivity of a color filter formed using the composition is improved.
(E) Solvent(s)
In the present invention, the solvent is characterized by necessarily comprising 4-hydroxy-4-methyl-2-pentanone.
The solvent used in the general colored photosensitive resin composition may be used without any particular limitation as long as it effectively dissolves other components contained in the colored photosensitive resin composition, and particularly, ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like are preferable.
Examples of the ethers include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dipropyl ether, diethylene glycol dibutyl ether, and the like.
Examples of the aromatic hydrocarbon include: benzene, toluene, xylene, trimethylbenzene, and the like.
Examples of the ketones include: methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.
Examples of the alcohols include: ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and the like.
Examples of the esters include: 3-ethoxypropionic acid ethyl ester, 3-methoxypropionic acid methyl ester, methyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, 3-methoxymethyl propionate, propylene glycol monomethyl ether acetate, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3-propanediol, ethyl lactate, propylene glycol, n-propyl ether, 3-ethoxyethyl propionate, propylene glycol monobutyl ether, 3-methoxy-1-butyl acetate, ethylene glycol monobutyl ether diethylene glycol methyl ethyl ether, 1, 2-propylene glycol diacetate, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, dipropylene glycol monoethyl ether, gamma-butyrolactone, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether, 1, 3-butanediol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol ethylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, gamma-butyrolactone, and the like.
Among the solvents exemplified above, organic solvents having a boiling point of 100 to 200℃are preferable from the viewpoint of coatability and drying properties, and for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used.
The solvents exemplified above may be used alone or in combination of two or more, and may be contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. When the solvent is in the range of 60 to 90 wt%, the coating device such as a roll coater, a spin coater, a slot coater (also referred to as a slot film coater) or an inkjet coater is used to provide an effect of good coatability.
The total weight of the solvent in the colored photosensitive resin composition of the present invention is preferably 5 to 20% by weight of the 4-hydroxy-4-methyl-2-pentanone. When the content of 4-hydroxy-4-methyl-2-pentanone is less than 5% by weight, the dye in the colored photosensitive resin composition precipitates and foreign matter is generated, and the contrast is lowered. When the content exceeds 20% by weight, the dispersibility of the colored photosensitive resin composition is lowered and the viscosity is increased.
(F) Additive agent
The additive may be optionally added as needed, and may include one or more selected from the group consisting of other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an ultraviolet absorber, and a deflocculant, for example.
Specific examples of the other polymer compounds include: curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane, and the like.
The curing agent is used for the purpose of improving the deep curing and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.
Among the above-mentioned curing agents, examples of the epoxy compound include bisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolak type epoxy resin, other aromatic type epoxy resin, alicyclic type epoxy resin, glycidyl ester type resin, glycidyl amine type resin or brominated derivatives of the above-mentioned epoxy resin, aliphatic alicyclic or aromatic epoxy compounds other than epoxy resin and brominated derivatives thereof, epoxide of butadiene (co) polymer, epoxide of isoprene (co) polymer, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.
Among the above-mentioned curing agents, the oxetane compounds include, for example, carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, terephthalic acid dioxetane, cyclohexanedicarboxylic acid di-oxetane, and the like.
The curing agent may be used in combination with a curing agent to form an epoxy group of an epoxy compound or a curing auxiliary compound for ring-opening polymerization of an oxetane skeleton of an oxetane compound. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators. The carboxylic acid anhydride may be a commercially available product as an epoxy resin curing agent. Specific examples of the epoxy resin curing agent include a pair of harpoons EH-700 (manufactured by the electric company of the sun), a pair HH (manufactured by the chemical company of new japan), and a pair MH-700 (manufactured by the chemical company of new japan). The curing agents of the foregoing examples may be used alone or in combination of two or more.
The surfactant can be used to further improve the film forming property of the photosensitive resin composition, and silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric surfactants and the like can be preferably used. Specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkyl benzene ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene imines, and the like can be cited. The silicone-based surfactant may be, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning silicone Co., ltd, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc. of GE Toshiba silicone Co., ltd. As the fluorine-based surfactant, for example, there are, as commercial products, koch of Japanese ink chemical industry Co., ltd., F-470, F-471, F-475, F-482, F-489 and the like. Other commercially available Products that can be used include KP (manufactured by Xinyue chemical industry Co., ltd.), POLYFLOW (manufactured by Kyowa chemical Co., ltd.), EFTOP (manufactured by Tochem Products Co., ltd.), MEGAFAC (manufactured by Dain ink chemical industry Co., ltd.), flourad (manufactured by Sumitomo 3M Co., ltd.), asahi guard, surflon (manufactured by Asahi Nitsu corporation, above), SOLSPERSE (manufactured by Jiekang Co., ltd.), EFKA (manufactured by EFKA chemical Co., ltd.), PB821 (manufactured by Weisu Co., ltd.), disperbyk-series (BYK-chemi), and the like. The surfactants of the foregoing examples can be used singly or in combination of two or more kinds.
The kind of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include: vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, and the like. The adhesion promoters of the foregoing examples can be used singly or in combination of two or more kinds, respectively. The adhesion promoter is usually 0.01 to 10% by weight, and preferably 0.05 to 2% by weight, based on the total weight of the solid components in the colored photosensitive resin composition.
The type of the ultraviolet absorber is not particularly limited, and specific examples that can be used include: 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.
The type of the deflocculant is not particularly limited, and specific examples that can be used include sodium polyacrylate.
The method for producing the colored photosensitive resin composition of the present invention is described below.
First, the pigment (a 1) in the colorant (a) is mixed with the solvent (E), and dispersed by using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, a part or all of the pigment dispersant (a 2), the alkali-soluble resin (B), or the dye (a 3) may be mixed, dissolved, or dispersed together with the solvent (E) as necessary.
The colored photosensitive resin composition of the present invention can be produced by further adding the dye (a 3), the balance of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and if necessary, the additive (F) and the solvent (E) to the above-described mixed dispersion to a predetermined concentration.
Further, the present invention provides a color filter manufactured from the aforementioned colored photosensitive resin composition and a display device including the color filter.
The display device can be manufactured by applying the colored photosensitive resin composition to a substrate, and performing photo-curing and development to form a pattern as described below.
First, after the colored photosensitive resin composition is coated on a substrate (usually glass) or a layer formed in advance and composed of a solid component of the colored photosensitive resin composition, volatile components such as a solvent are removed by heating and drying, and a smooth coating film is obtained.
The coating method may be performed by, for example, spin coating, flexible coating, roll coating, slit spin coating, slit coating, or the like. The solvent and other volatile components are volatilized by heating and drying (prebaking) after coating or heating after drying under reduced pressure. The heating temperature is usually 70 to 200℃and preferably 80 to 130 ℃. The thickness of the coating film after heat drying is usually about 1 to 8. Mu.m. The thus obtained coating film is irradiated with ultraviolet rays through a mask for forming a target pattern. In this case, the exposure portion is uniformly irradiated with parallel light, and a mask aligner, a stepper, or the like is preferably used to align the mask and the substrate to a correct position. If ultraviolet rays are irradiated, the portion irradiated with the ultraviolet rays is cured.
The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The irradiation amount of ultraviolet rays may be appropriately selected according to need, and the present invention is not limited thereto. The cured coating film is brought into contact with a developer to dissolve the non-exposed portion and developed, whereby a target pattern shape can be formed.
The developing method may be any one of a liquid adding method, a dipping method, a spraying method, and the like. In addition, the substrate may be tilted at an arbitrary angle during development. The developer is typically an aqueous solution containing an alkaline compound and a surfactant. The basic compound may be any of inorganic and organic basic compounds. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonium borate, and the like. Specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine.
These inorganic and organic basic compounds may be used singly or in combination of two or more kinds. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.
The surfactant in the alkali developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants, and cationic surfactants.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene alkylamines, and the like.
Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleate sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylaryl sulfonate salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.
Specific examples of the cationic surfactant include amine salts such as octadecylamine hydrochloride and lauryl trimethyl ammonium chloride, and quaternary ammonium salts. These surfactants may be used singly or in combination of two or more.
The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight. After development, the film is washed with water, and if necessary, post-baked at 150 to 230℃for 10 to 60 minutes.
The colored photosensitive resin composition of the present invention can be used to form a specific pattern on a substrate through the above steps.
Hereinafter, the present invention will be described in detail with reference to examples. The embodiments to which the present invention relates may be modified in various forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the present invention are provided to more fully illustrate the invention to those skilled in the art.
<Production of pigment-dispersed composition>
Production example 1 production of pigment-dispersed composition (M1)
13.5 parts by weight of pigment C.I. pigment Red 254, 5.0 parts by weight of pigment dispersant DISPERBYK-2001 (manufactured by BYK Co.) and 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 20 parts by weight of 4-hydroxy-4-methyl-2-pentanone were mixed by a bead mill for 12 hours, and dispersed to prepare a pigment-dispersion composition M1.
Production example 2 production of pigment-dispersed composition (M2)
13.5 parts by weight of pigment C.I. pigment green 58, 5.0 parts by weight of pigment dispersant DISPERBYK-2001 (manufactured by BYK Co.) and 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 20 parts by weight of 4-hydroxy-4-methyl-2-pentanone were mixed by a bead mill for 12 hours, and dispersed to prepare a pigment-dispersion composition M2.
Production example 3 production of pigment-dispersion composition (M3)
13.5 parts by weight of pigment C.I. pigment Red 254, 5.0 parts by weight of pigment dispersant DISPERBYK-2001 (manufactured by BYK Co.) and 81.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed by a bead mill for 12 hours, and dispersed to prepare a pigment-dispersion composition M3.
Synthesis example 1 Synthesis of alkali-soluble resin
120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate, 3 parts by weight of n-dodecyl mercaptan were added to a flask comprising a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and replaced with a nitrogen atmosphere. After that, stirring was performed to raise the temperature of the reaction solution to 110℃and react for 6 hours. The solid content acid value of the alkali-soluble resin produced by the above method was 100.2mgKOH/g, and the weight average molecular weight Mw measured by GPC was 15110.
Synthesis example 2 Synthesis of photopolymerization initiator (d 1)
Step 1
37.3g of AlCl 3 And 112.0g of dichloroethane were added to a reactor under a nitrogen atmosphere, stirred at a temperature of 5℃and 240.3g of dichloroethane and 48.1g of nitrocarbazole were dissolved in 17.27g of acetyl chloride solution, and the above-mentioned dissolved solution was dropped into the reactor over 1 hour. After that, the temperature was raised to 15 ℃ and stirred for a further 2 hours. Will be Distilled water was placed in the above reactor, washed and separated, and then the solvent was dried to obtain a reaction product 1 having a purity of 94%.
Step 2
35.0g of the aforementioned reactant 1, 11.1g of hydroxylamine hydrochloride, 15.1g of sodium acetate, 90g of ethanol and 30g of distilled water were charged into a reactor under a nitrogen atmosphere, kept at a temperature of 80℃and stirred for 5 hours. Then, distilled water was added thereto, and the precipitate was separated and dried to obtain a reaction product 2 having a purity of 92%.
Step 3
26.0g of reactant 2 and 78g of methylene chloride were charged into a reactor under a nitrogen atmosphere, and stirred at room temperature. Thereafter, a mixed solution of acetic anhydride diluted with 15.0g of dichloroethane was added dropwise to the reactor over 1 hour, followed by stirring for 1 hour. After stirring, distilled water was added to the mixture to wash the mixture several times, and then dichloromethane was evaporated to obtain chemical formula 2 having a purity of 90%. In addition, formula 2 is R of formula 1 1 And R is 2 The structure of the methyl group can be represented as follows. Further, the absorbance at 405nm of the compound of the following chemical formula 2 was measured as 0.523 using a propylene glycol methyl ether acetate solution having a concentration of 0.01% by weight.
[ chemical formula 2]
<Production of colored photosensitive resin composition>
Example 1
The colored photosensitive resin composition of example 1 was produced by mixing 38.89 parts by weight of the pigment-dispersion composition M1 produced in production example 1, 10.65 parts by weight of the resin produced in production example 1, 3.55 parts by weight of KAYARAD DPHA (Japanese chemical Co., ltd.) as a photopolymerizable compound, 0.71 parts by weight of a photopolymerization initiator produced in production example 2 (the absorbance of propylene glycol monomethyl ether acetate solution containing the photopolymerization initiator at 405nm is 0.52) at a concentration of 0.01% by weight or more), 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 45.48 parts by weight of propylene glycol monomethyl ether acetate.
Example 2
The colored photosensitive resin composition of example 2 was produced by mixing 38.89 parts by weight of the pigment-dispersion composition M2 produced in production example 2, 10.65 parts by weight of the resin produced in synthesis example 1, 3.55 parts by weight of KAYARAD DPHA (japan chemical) as a photopolymerizable compound, 0.71 part by weight of a photopolymerization initiator produced in synthesis example 2 (the absorbance of propylene glycol monomethyl ether acetate solution containing the photopolymerization initiator at 405nm is 0.52 at a concentration of 0.01% by weight or more), 0.72 part by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 45.48 parts by weight of propylene glycol monomethyl ether acetate.
Example 3
36.94 parts by weight of the pigment-dispersion composition M1 produced in production example 1, 0.26 part by weight of C.I. solvent yellow 21 as a dye, 10.79 parts by weight of the resin produced in production example 1, 3.59 parts by weight of KAYARAD DPHA (Japanese chemical) as a photopolymerizable compound, 0.72 part by weight of the photopolymerization initiator produced in production example 2 (absorbance of propylene glycol monomethyl ether acetate solution containing the photopolymerization initiator at 405nm is 0.52 at a concentration of 0.01% by weight or more), 1.11 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 46.59 parts by weight of propylene glycol monomethyl ether acetate were mixed to produce a colored photosensitive resin composition of example 3.
Example 4
36.94 parts by weight of the pigment-dispersion composition M2 produced in production example 2, 0.26 part by weight of C.I. solvent yellow 21 as a dye, 10.79 parts by weight of the resin produced in synthesis example 1, 3.59 parts by weight of KAYARAD DPHA (Japanese chemical) as a photopolymerizable compound, 0.72 part by weight of the photopolymerization initiator produced in synthesis example 2 (absorbance of propylene glycol monomethyl ether acetate solution containing the photopolymerization initiator at 405nm is 0.52 at a concentration of 0.01% by weight or more), 1.11 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 46.59 parts by weight of propylene glycol monomethyl ether acetate were mixed to produce a colored photosensitive resin composition of example 4.
Comparative example 1
A colored photosensitive resin composition of comparative example 1 was produced by mixing 38.89 parts by weight of the pigment-dispersion composition M1 produced in production example 1, 10.65 parts by weight of the resin produced in production example 1, 3.55 parts by weight of KAYARAD DPHA (Japanese chemical) as a photopolymerizable compound, 0.71 parts by weight of Irgacure OXE-01 (propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more, absorbance at 405nm, BASF corporation) as a photopolymerization initiator, 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 45.48 parts by weight of propylene glycol methyl ether acetate.
Comparative example 2
A colored photosensitive resin composition of comparative example 2 was produced by mixing 38.89 parts by weight of the pigment-dispersion composition M1 produced in production example 1, 10.65 parts by weight of the resin produced in production example 1, 3.55 parts by weight of KAYARAD DPHA (Japanese chemical) as a photopolymerizable compound, 0.71 parts by weight of Irgacure OXE-02 (propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more, absorbance at 405 nm: 0.004; BASF corporation), 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 45.48 parts by weight of propylene glycol methyl ether acetate.
Comparative example 3
The colored photosensitive resin composition of comparative example 3 was produced by mixing 38.89 parts by weight of the pigment-dispersion composition M1 produced in production example 1, 10.65 parts by weight of the resin produced in production example 1, 3.55 parts by weight of KAYARAD DPHA (Japanese chemical) as a photopolymerizable compound, and 0.71 part by weight of 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent and 45.48 parts by weight of propylene glycol monomethyl ether acetate as a photopolymerization initiator (the absorbance at 405nm of propylene glycol monomethyl ether acetate solution containing the photopolymerization initiator at a concentration of 0.01% by weight or more, manufactured by Asahi electric Co., ltd.).
Comparative example 4
A colored photosensitive resin composition of comparative example 4 was produced by mixing 38.89 parts by weight of the pigment-dispersion composition M2 produced in production example 2, 10.65 parts by weight of the resin produced in production example 1, 3.55 parts by weight of KAYARAD DPHA (Japanese chemical) as a photopolymerizable compound, 0.71 parts by weight of Irgacure OXE-01 (propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more, absorbance at 405nm, BASF corporation) as a photopolymerization initiator, 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 45.48 parts by weight of propylene glycol methyl ether acetate.
Comparative example 5
A colored photosensitive resin composition of comparative example 5 was produced by mixing 38.89 parts by weight of the pigment-dispersion composition M2 produced in production example 2, 10.65 parts by weight of the resin produced in production example 1, 3.55 parts by weight of KAYARAD DPHA (Japanese chemical) as a photopolymerizable compound, 0.71 parts by weight of Irgacure OXE-02 (propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more, absorbance at 405 nm: 0.004; BASF corporation), 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 45.48 parts by weight of propylene glycol methyl ether acetate.
Comparative example 6
A photosensitive colored resin composition of comparative example 6 was produced by mixing 36.94 parts by weight of the pigment-dispersion composition M1 produced in production example 1, 0.26 part by weight of c.i. solvent yellow 21 as a dye, 10.79 parts by weight of the resin produced in synthesis example 1, KAYARAD DPHA (japan chemical) 3.59 parts by weight of a photopolymerizable compound, and 0.72 part by weight of Irgacure OXE-02 (absorbance at 405nm of propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more, basf company) as a photopolymerization initiator, 1.11 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 46.59 parts by weight of propylene glycol monomethyl ether acetate.
Comparative example 7
36.94 parts by weight of the pigment-dispersion composition M1 produced in production example 1, 0.26 part by weight of C.I. solvent yellow 21 as a dye, 10.79 parts by weight of the resin produced in synthesis example 1, KAYARAD DPHA (Japanese chemical) 3.59 parts by weight of a photopolymerizable compound, and N-1919 as a photopolymerization initiator (the absorbance of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at 405nm is 0.015 at a concentration of 0.01% by weight or more, asahi electric Co.) 0.72 parts by weight, 1.11 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 46.59 parts by weight of propylene glycol monomethyl ether acetate were mixed to produce a colored photosensitive resin composition of comparative example 7.
Comparative example 8
The colored photosensitive resin composition of comparative example 8 was produced by mixing 38.89 parts by weight of the pigment-dispersion composition M3 produced in production example 3, 10.65 parts by weight of the resin produced in production example 1, 3.55 parts by weight of KAYARAD DPHA (Japanese chemical) as a photopolymerizable compound, and 0.71 part by weight of propylene glycol monomethyl ether acetate as a solvent, with N-1919 (propylene glycol monomethyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more) having an absorbance of 0.015 at 405 nm.
Comparative example 9
36.94 parts by weight of the pigment-dispersion composition M3 produced in production example 3, 0.26 part by weight of C.I. solvent yellow 21 as a dye, 10.79 parts by weight of the resin produced in Synthesis example 1, 3.59 parts by weight of KAYARAD DPHA (Japanese chemical) as a photopolymerizable compound, 0.72 part by weight of the photopolymerization initiator produced in Synthesis example 2 (absorbance of a propylene glycol monomethyl ether acetate solution containing the photopolymerization initiator at 405nm is 0.52 at a concentration of 0.01% by weight or more), and 47.7 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to produce a colored resin composition of comparative example 9.
Experimental example 1 production of color Filter
The colored photosensitive resin compositions of the foregoing examples 1 to 4 and comparative examples 1 to 9 were coated on a 2 square inch glass substrate (manufactured by corning corporation, "EAGLE XG") by a spin coating method, and then placed on a heating plate and kept at a temperature of 100 ℃ for 3 minutes to form a film. Next, a test photomask having a pattern with a stepwise change in light transmittance in the range of 1 to 100% and a line width/space pattern of 1 μm to 50 μm was placed on the film, and ultraviolet light was irradiated while the space between the test photomask and the test photomask was set to 300 μm. At this time, the ultraviolet light source causes40mJ/cm of the total radiation of g, h and i is used by a 1KW high-pressure mercury lamp 2 The illumination is performed without using a special filter. The film irradiated with the ultraviolet rays was immersed in a KOH aqueous developing solution having a pH of 10.5 for 2 minutes, and developed. After washing the glass plate coated with the thin film using distilled water, nitrogen was blown in to dry, and the glass plate was heated in a heating furnace at 230 ℃ for 25 minutes, thereby manufacturing a color filter. The film thickness of the color filter manufactured as described above was 2.3 μm.
Experimental example 2 production of color Filter
Color filters were manufactured in the same manner as in experimental example 1, respectively, except that the test photomask was not used.
Physical property measurement of color filters of Experimental example 3, experimental example 1 and Experimental example 2
The adhesiveness and pattern line width were measured for each color filter manufactured in experimental example 1, and the solvent resistance was measured for each color filter manufactured in experimental example 2. The results of the physical properties are shown in Table 1 below.
(1) Adhesion properties
When the generated pattern was observed by an optical microscope, the degree of peeling phenomenon on the pattern was evaluated.
O: no spalling on the pattern
Delta: 1 to 3 spalling layers on the pattern
X: the pattern has more than 4 spalling
(2) Line width of pattern
The line width of the generated pattern was measured by a scanning electron microscope. When the line width of the pattern is measured to be equal to or larger than the line width of the photomask, the sensitivity of the colored photosensitive resin composition is sufficient, and the line width is enlarged.
(3) Solvent resistance
After immersing the color filter in an NMP solution at normal temperature for 30 minutes, the color filter was washed with ultrapure water and dried on a hot plate heated to 120 ℃ for 2 minutes, and then chromaticity before and after immersing was measured. The expression used in this case is calculated by the following expression 1 indicating the color change in the three-dimensional colorimeter defined by L, a, and b, and it is possible to manufacture a highly reliable color filter as the color change value decreases.
[ mathematics 1]
△Eab＊＝[(△L＊)2+(△a＊)2+(△b＊)2]＾0.5
TABLE 1
Classification Adhesion properties Line width of pattern Solvent resistance
Example 1 ○ +10 2.9
Example 2 ○ +21 2.4
Example 3 ○ +9 3.5
Example 4 ○ +11 2.9
Comparative example 1 × -2 17.5
Comparative example 2 × -8 18.8
Comparative example 3 × -3 14.1
Comparative example 4 × -5 15.4
Comparative example 5 △ +10 3.8
Comparative example 6 × +3 4.1
Comparative example 7 × +1 5.2
Comparative example 8 × -4 16.7
Comparative example 9 ○ +8 3.7
With the above results, the color filters of examples 1 to 4, which used the colored photosensitive resin composition of the present invention comprising the compound of chemical formula 2 produced in the foregoing synthesis example 2 as a photopolymerization initiator and 4-hydroxy-4-methyl-2-pentanone as a solvent, exhibited excellent results in any of the performances of adhesion, pattern line width and solvent resistance, as compared with the color filters of comparative examples 1 to 9.
Therefore, it is found that the colored photosensitive resin composition of the present invention has more excellent effects in storage stability, sensitivity and adhesion.

Claims (9)

1. A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, characterized in that,
the colored photosensitive resin composition contains 5 to 60% by weight of the colorant relative to the total weight of solid components in the colored photosensitive resin composition,
the photopolymerization initiator contains an oxime ester compound of the following chemical formula 1,
The solvent comprises 5 to 20 wt% of 4-hydroxy-4-methyl-2-pentanone relative to the total weight of the solvent,
[ chemical formula 1]
The R is as described above 1 Is C1-C8 alkyl OR 3 A group, an aryl group having 6 to 10 carbon atoms substituted with a halogen group or an aralkyl group having 7 to 24 carbon atoms substituted with a halogen group,
the R is as described above 2 Is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 24 carbon atoms,
the R is as described above 3 Is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
2. The colored photosensitive resin composition according to claim 1, wherein the absorbance of the propylene glycol methyl ether acetate solution containing the photopolymerization initiator containing the oxime ester compound of chemical formula 1 at a concentration of 0.01% by weight or more is 0.5 or more at 405 nm.
3. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition comprises 10 to 80% by weight of the alkali-soluble resin, 5 to 45% by weight of the photopolymerizable compound and 0.1 to 30% by weight of the photopolymerization initiator relative to the total weight of the solid components in the colored photosensitive resin composition, and comprises 60 to 90% by weight of the solvent relative to the total content of the colored photosensitive resin composition.
4. The colored photosensitive resin composition according to claim 3, wherein the photopolymerization initiator comprises 10 to 100% by weight of the compound of formula 1 according to claim 1 relative to the total weight of the photopolymerization initiator.
5. The colored photosensitive resin composition according to claim 1, wherein the colorant comprises one or more pigments or one or more dyes.
6. The colored photosensitive resin composition according to claim 1, wherein the acid value of the alkali-soluble resin is 30 to 150mgKOH/g.
7. The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator further comprises one or more compounds selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, and thioxanthone compounds.
8. A color filter, characterized in that the color filter comprises the colored photosensitive resin composition according to claim 1.
9. A display device comprising the color filter of claim 8.
CN202010140116.0A 2013-08-22 2014-07-30 Colored photosensitive resin composition, color filter comprising same, and display device Active CN111399340B (en)

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