CN104914669B - Blue photosensitive resin composition, blue filter and display device having the same - Google Patents
Blue photosensitive resin composition, blue filter and display device having the same Download PDFInfo
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Abstract
The present invention relates to a blue photosensitive resin composition, a blue filter and a display device having the blue filter, wherein the blue photosensitive resin composition comprises: a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin is contained in an amount of 20 to 80 wt% based on the total weight of solids of the blue photosensitive resin composition; the alkali-soluble resin includes 40 wt% to 100 wt% of an alkali-soluble resin having a molecular weight of 15000 or more, based on the total weight of the alkali-soluble resin; the photopolymerization initiator includes an oxime ester compound; and, the solvent includes more than 0 wt% and not more than 8 wt% of a solvent having a boiling point of 180 ℃ or higher, based on the total weight of the solvent.
Description
Cross Reference to Related Applications
The benefit of korean patent application KR 10-2014 0028436, filed 3/11/2014 and KR 10-2015 0026937, filed 26/2/2015, which are claimed in this application, are incorporated by reference in their entirety.
Technical Field
The present invention relates to a blue photosensitive resin composition, a blue filter and a display device having the blue filter.
Background
Optical filters are widely used for imaging devices, liquid crystal display devices (LCDs), and the like, and their applications are rapidly expanding. A color filter used in a color liquid crystal display device or an imaging device is manufactured in such a manner that a series of processes is repeated for each color to form pixels corresponding to the respective colors, the series of processes including: uniformly coating a colored photosensitive resin composition containing respective pigments corresponding to red, green and blue colors on a substrate patterned with a black matrix using spin coating; drying it with heat (hereinafter also referred to as "prebaking") to form a paint film, and then subjecting the paint film to photo-exposure and development; and optionally further performing heating (hereinafter also referred to as "post-baking"). Similarly, the black matrix formed with the pattern is usually formed of a photosensitive resin composition having a black color.
A composition containing a photopolymerizable compound and a photopolymerization initiator is widely used for a colored photosensitive resin composition along with a pigment and a binder resin. Recently, the content of coloring materials of display panels and the thickness of paint films are continuously increasing, reflecting the trend of high quality with high color reproduction and the expansion of use of image forming apparatuses, liquid crystal display apparatuses, and the like.
However, particularly, as the paint film thickens, the colored photosensitive resin composition providing blue pixels often generates pattern defects; and the problem of pattern flatness of the manufactured color filter continuously occurs. When the pattern flatness problem occurs, the color coordinates in one pixel are not equal, and thus, a visibility problem occurs, and it is difficult to manufacture a high-quality display device.
Therefore, research is required to solve the above problems.
Patent document 1: korean patent application laid-open No. 10-2010-0051395A
Disclosure of Invention
Therefore, in order to solve the above problems, it is an object of the present invention to provide a blue photosensitive resin composition which can maintain a constant color coordinate in one pixel by maintaining flatness without shortage of patterns even in a thickened pattern.
Further, another object of the present invention is to provide a high quality display device using the blue photosensitive resin composition.
In order to achieve the above object, the present invention provides a blue photosensitive resin composition comprising: a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin is contained in an amount of 20 to 80 wt% based on the total solid weight of the blue photosensitive resin composition; the alkali-soluble resin includes 40 wt% to 100 wt% of an alkali-soluble resin having a molecular weight of 15000 or more, based on the total weight of the alkali-soluble resin; the photopolymerization initiator includes a compound represented by the following chemical formula 1; and the solvent includes more than 0% by weight and not more than 8% by weight of a solvent having a boiling point of 180 ℃ or higher, based on the total weight of the solvent,
[ chemical formula 1]
Wherein R is1As represented by the following chemical formula 2,
R2is C1-C8 alkyl, phenyl, substituted or unsubstituted phenyl, or substituted or unsubstituted benzyl,
R3is a diphenylsulfide group, and
[ chemical formula 2]
-R4-R5
R4Is a C1 to C4 alkylene group, and
R5is C3-C8 alkyl, C3-C8 cycloalkyl, or C6-C8 aromatic hydrocarbon.
Further, the present invention provides a blue filter comprising the blue photosensitive resin composition.
Further, the present invention provides a display device including the blue filter.
The blue photosensitive resin composition according to the present invention does not cause shortage of patterns in blue patterns having a low content of a colorant and has an effect of improving flatness, and thus can be used for manufacturing a color filter which can obtain a constant color coordinate in one pixel.
Therefore, it has an effect of providing a color filter free from a problem of definition.
Detailed Description
Hereinafter, the configuration and operation of the present invention will be described in detail.
The invention relates to a blue photosensitive resin composition, which comprises the following components: a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin is contained in an amount of 20 to 80 wt% based on the total solid weight of the blue photosensitive resin composition; wherein the alkali-soluble resin includes 40 to 100 wt% of an alkali-soluble resin having a molecular weight of 15000 or more, based on the total weight of the alkali-soluble resin; wherein the photopolymerization initiator includes a compound represented by the following chemical formula 1; and wherein the solvent comprises more than 0 wt% and not more than 8 wt% of a solvent having a boiling point of 180 ℃ or higher, based on the total weight of the solvent,
[ chemical formula 1]
Wherein R is1As represented by the following chemical formula 2,
R2is C1-C8 alkyl, phenyl, substituted or unsubstituted phenyl, or substituted or unsubstituted benzyl,
R3is a diphenylsulfide group, and
[ chemical formula 2]
-R4-R5
R4Is a C1 to C4 alkylene group, and
R5is C3-C8 alkyl, C3-C8 cycloalkyl, or C6-C8 aromatic hydrocarbon.
Generally, a color filter including the colored photosensitive resin composition is prepared by the steps of coating, vacuum drying, soft baking, photographic exposure, development, and hard baking. In order to ensure the flatness of the color filter, it is important to minimize the fluidity of the coating film in the soft baking and hard baking steps. It is particularly most important to ensure the pattern flatness in the soft baking step because if the pattern flatness cannot be ensured in the soft baking step, it is displayed to the finally produced color filter and thus non-uniform color coordinates are generated in one pixel.
In the present invention, 40 to 100% by weight of an alkali-soluble resin having a molecular weight of 15000 or more based on the total weight of the alkali-soluble resin is used, and thus the fluidity of the paint film can be suppressed in the soft baking step, pattern flatness can be obtained, and thus a blue filter that realizes a constant color coordinate in one pixel can be manufactured.
However, if the amount of the alkali-soluble resin having a molecular weight of 15000 or more is less than 40% by weight based on the total weight of the alkali-soluble resin, the fluidity of the paint film is improved in the soft baking step, and it is difficult to ensure pattern flatness, and thus it is difficult to achieve a constant color coordinate in one pixel.
Further, in the present invention, more than 0 wt% and not more than 8 wt% of the solvent having a boiling point of 180 ℃ or more is used based on the total weight of the solvent, so that the pattern flatness can be ensured.
If the amount of the solvent exceeds 8% by weight, the increased amount of the residual solvent makes it difficult to maintain the flatness of the pattern by improving the fluidity of the paint film in the soft baking step.
Hereinafter, the configuration and operation of the present invention will be described in detail.
Blue colorant (A)
The blue colorant comprises at least one pigment, at least one dye, or a combination thereof.
The pigment may include an organic pigment or an inorganic pigment commonly used in the art. Further, the pigment may be treated with a resin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced thereto, a grafting treatment of the surface of the pigment with a polymer compound or the like, an atomizing treatment by a sulfuric acid atomizing method or the like, a cleaning treatment for removing impurities using an organic solvent, water or the like, or a removal treatment for ionic impurities by an ion exchange method or the like, as required.
The organic pigment may include various pigments used in printing inks, inkjet inks, and the like, and specific examples thereof may include: water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.
Further, the inorganic pigment may include a metal compound such as a metal oxide or a metal complex, and specific examples thereof include: metal oxides or composite metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony; carbon black; an organic black pigment; titanium black; and black pigments obtained by mixing red, green and blue colors.
In particular, organic and inorganic pigments may specifically include compounds classified as pigments by color index (published by the association of colorists and colorists), more specific examples of which may include, but are not necessarily limited to, the following color index (c.i.) number of pigments:
c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
c.i. pigment blue 15(15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76, and so on.
One or more selected from the group consisting of c.i. pigment violet 23, c.i. pigment blue 15:3, and c.i. pigment blue 15:6 may be preferably used.
When a pigment is used as the colorant, it is preferable to use a pigment having a uniform particle diameter. An example of the method of making the particle diameter uniform may be a method of treating the distribution process by adding the pigment dispersant (a2), and according to this method, a pigment dispersion solution having a uniformly dispersed pigment state may be obtained.
Pigment dispersant (a2)
The pigment dispersant is added for deaggregating the pigment and maintaining the stability of the pigment, and specific examples of the pigment dispersant may be a surfactant or the like such as a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a polyester-based surfactant, a polyamine-based surfactant, and the like, which may be used alone or in combination of two or more.
Specific examples of the cationic surfactant may be amine salts or quaternary ammonium salts, etc., such as stearylamine hydrochloride and lauryltrimethylammonium chloride, etc.
Specific examples of the anionic surfactant may be higher alcohol sulfate salts such as sodium lauryl sulfate, sodium oleyl sulfate and the like; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and the like; and alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate and dodecylnaphthalene sulfonate, and the like.
Specific examples of the nonionic surfactant may be polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene alkylamines, and the like.
Furthermore, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, and the like can be used.
Further, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as "acrylate dispersant"), including: butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA).
Likewise, the acrylate dispersant preferably includes those prepared by existing control methods, and commercially available products of the acrylate dispersant may include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like. Examples of the acrylic dispersing agent as listed above may be used alone or in combination of two or more.
The pigment dispersant may include other resin type pigment dispersants in addition to the above-mentioned acrylate dispersant. Other resinous pigment dispersants may include: known resin-type pigment dispersants, particularly oily dispersants such as polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates and modified products thereof, or amides or salts thereof produced via a reaction between polyesters having free carboxyl groups and poly (lower alkyleneimines); water-soluble resin or polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, or polyvinyl pyrrolidone; a polyester; a modified polyacrylate; ethylene oxide/propylene oxide adducts; and phosphoric acid esters and the like.
Other commercially available products of resinous pigment dispersants may include cationic resin dispersants such as DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184 (both trade names available from BYK Chemie); 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 (all trade names sold under BASF); SOLSPERS-24000, SOLSPERS-32550 and NBZ-4204/10 (all commercially available as Lubirzol); HINACT T-6000, HINACT T-7000 and HINACT T-8000 (all trade names available from Kawaken Fine Chemicals); AJISPUR PB-821, AJISPUR PB-822, and AJISPUR PB-823 (both trade names commercially available from Ajinomoto); FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 (both trade names commercially available from Kyoeisha Chemical), and the like.
In addition to the above-mentioned acrylate dispersant, examples of other resin-type pigment dispersants are used alone or in combination of two or more, and may be used together with the acrylate dispersant.
The amount of the pigment dispersant is 5 to 60 parts by weight, and preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment. If the amount of the dispersant exceeds 60 parts by weight, the viscosity may increase. In contrast, if the amount of the dispersant is less than 5 parts by weight, it is difficult to make the pigment fine or gelation may occur after the dispersion treatment.
Dye (a3)
Any dye may be used without limitation so long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and capable of ensuring solubility in an alkaline developer and having reliability such as heat resistance, solvent resistance and the like is useful.
The dye may be selected from acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfone amide products of acid dyes and derivatives thereof, and may also be selected from azo-type acid dyes, xanthene-type acid dyes, phthalocyanine-type acid dyes and derivatives thereof.
The dyes preferably include compounds classified as dyes by color index (published by the association of colorists and colorists), or known dyes disclosed in the notes on dyes (published by Dyeing Note, shikisnsha).
Specific examples of the dye may include c.i. solvent dyes as follows:
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, etc.;
among the c.i. solvent dyes, preferably useful are c.i. solvent blues 35, 36, 44, 45 and 70; and c.i. solvent violet 13.
Further, examples of the c.i. acid dye are as follows:
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, etc.;
among the c.i. acid dyes, preferably useful are c.i. acid blue 80, 90; and c.i. acid violet 60.
Also, examples of the c.i. direct dye include:
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, etc.
These dyes may be used alone or in a combination of two or more.
The amount of the dye of the blue colorant is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, and further preferably 1 to 50% by weight, based on the total weight of the solid content of the blue colorant. When the amount of the additional dye of the colorant falls within the above range of 0.5 to 80 wt%, the problem of deterioration in reliability due to dissolution of the dye in an organic solvent occurring after pattern formation can be prevented, and high sensitivity can be generated.
The amount of the blue colorant is set to 5 to 60% by weight, and preferably 10 to 45% by weight, based on the total weight of the solid content of the blue photosensitive resin composition. The use amount of the colorant is desirably 5 to 60 wt% based on the foregoing, because the pixel portion has sufficient color density even when a film is formed, and the peeling of the non-pixel portion is not reduced at the time of development, so that the residue is hardly generated.
As used herein, the total solid content of the blue photosensitive resin composition means the total amount of the components of the blue photosensitive resin composition excluding the solvent.
Alkali soluble resin (B)
The alkali-soluble resin of the present invention is characterized by comprising 40 to 100% by weight of an alkali-soluble resin having a molecular weight of 15000 or more, based on the total weight of the alkali-soluble resin. The above amount is desirable because it can suppress the fluidity of the paint film in the soft baking step, which is one of the manufacturing steps of the color filter, pattern flatness can be obtained, and therefore a blue filter realizing a constant color coordinate in one pixel can be produced.
In contrast to this, if the amount is less than 40% by weight, the fluidity of the paint film is improved in the soft baking step, and it is difficult to ensure the pattern flatness, and thus it is difficult to achieve a constant color coordinate in one pixel.
Further, in order to ensure the compatibility of the blue photosensitive resin composition with a dye and the storage stability, the acid value of the alkali-soluble resin is preferably 30 to 150 mgKOH/g. If the acid value of the alkali-soluble resin is less than 30mgKOH/g, it is difficult to ensure a sufficient development rate of the blue photosensitive resin composition. In contrast to this, if the acid value of the alkali-soluble resin exceeds 150mgKOH/g, the adhesion to the substrate may decrease, so that shortage of patterns is liable to be caused and compatibility with the dye is incurred, and thereby the dye in the blue photosensitive resin composition may precipitate or the storage stability of the blue photosensitive resin composition may deteriorate, thus increasing the viscosity, which is undesirable.
Further, in order to achieve solubility in an alkaline developing solution used in a developing process at the time of forming a pattern, an alkali-soluble resin is prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group (b 1).
Further, in order to add a hydroxyl group to the alkali-soluble resin, (1) the alkali-soluble resin may be prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group (b1) with an ethylenically unsaturated monomer having a hydroxyl group (b2), and (2) the alkali-soluble resin may be prepared by additionally reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group (b1) with a compound having a glycidyl group (b 3). (3) Alternatively, the resin may be prepared by additionally reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group (b1) and an ethylenically unsaturated monomer having a hydroxyl group (b2) with a compound having a glycidyl group (b 3).
Specific examples of the ethylenically unsaturated monomer having a carboxyl group (b1) include: monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and the like; dicarboxylic acids such as fumaric acid, mesaconic acid, itaconic acid, and the like; dicarboxylic anhydrides thereof; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends thereof, such as ω -carboxy polycaprolactone mono (meth) acrylate, and the like. Acrylic acid and methacrylic acid are preferably useful.
Specific examples of the ethylenically unsaturated monomer having a hydroxyl group (b2) include: hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide, and the like.
Specific examples of the monomer having a glycidyl group (b3) 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, glycidyl methacrylate, and the like are preferably useful, and butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate, which may be used in combination of two or more kinds, are preferably useful.
In preparing the alkali-soluble resin, a copolymerizable unsaturated monomer (b4) other than the ethylenically unsaturated monomer having a hydroxyl group (b2) and the compound having a glycidyl group (b3) may be additionally added to the ethylenically unsaturated monomer having a carboxyl group (b1) for copolymerization.
The copolymerizable unsaturated monomer (b4) is exemplified by, but not limited to, the following.
Specific examples of the polymerizable monomer (b4) having a copolymerizable unsaturated bond include: aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, 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, p-vinylbenzyl glycidyl ether, indene, and the like;
n-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-tolylmaleimide, N-m-tolylmaleimide, N-p-tolylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide and the like;
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, tert-butyl (meth) acrylate, and the like;
alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate isobornyl (meth) acrylate, and the like;
aryl (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, and the like; and
unsaturated oxetane compounds such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane and the like.
The exemplified monomers may be used alone or in combination of two or more.
The amount of the alkali-soluble resin (B) is 20 to 80% by weight, and preferably 20 to 70% by weight, based on the total weight of the solid content of the blue photosensitive resin composition. When the amount of the alkali-soluble resin is 20 to 80 wt% based on the above, a pattern is easily formed due to sufficient solubility in a developing solution, and at the time of development, a film of a pixel portion of a photographic exposure portion is prevented from becoming small, and thus a lack of a non-pixel portion is improved.
Photopolymerizable compound (C)
In the present invention, the photopolymerizable compound should be a compound which can be polymerized by the action of the photopolymerization initiator (D) described below. In the present invention, a monofunctional monomer, a bifunctional monomer, or a polyfunctional monomer may be used, and a bifunctional monomer may be preferably used, but is not limited thereto.
Specific examples of monofunctional monomers include, but are not limited to: nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpyrrolidone, and the like.
Specific examples of difunctional monomers include, but are not limited to: 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, or the like.
Specific examples of the multifunctional monomer include, but are not limited to: trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, or the like.
The amount of the photopolymerizable compound used is set to 5 to 45% by weight, and preferably 7 to 45% by weight, based on the total weight of the solid content of the blue photosensitive resin composition. When the amount of the photopolymerizable compound falls within the range of 5 to 45 wt% based on the foregoing, the strength or smoothness of the pixel portion can be improved.
Photopolymerization initiator (D)
The photopolymerization initiator of the present invention is characterized by comprising an oxime ester compound represented by the following chemical formula 1.
[ chemical formula 1]
Wherein R is1As represented by the following chemical formula 2,
R2is C1-C8 alkyl, phenyl, substituted or unsubstituted phenyl, or substituted or unsubstituted benzyl,
R3is a diphenylsulfide group, and
[ chemical formula 2]
-R4-R5
R4Is a C1 to C4 alkylene group, and
R5is C3-C8 alkyl, C3-C8 cycloalkyl, or C6-C8 aromatic hydrocarbon.
The above oxime ester compound represented by chemical formula 1 preferably includes one or more selected from the group consisting of 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (o-benzoyloxime) and 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (o-benzoyloxime) (1,2-octanedione,1- [4- (phenylthio) phenyl ] -,2- (o-benzoyloxyimine)).
The photopolymerization initiator including the compound represented by chemical formula 1 prevents sensitivity and light transmittance from being lowered due to the dye, and thus exhibits effective photopolymerization performance in the blue photosensitive resin composition including the dye as a colorant.
Further, the content of the photopolymerization initiator is 10 to 100% by weight, preferably 20 to 100% by weight, based on the total weight. If the amount of chemical formula 1 is less than 10 wt%, the decreased sensitivity cannot be overcome due to the dye, and a shortage of patterns is liable to occur during the development process.
In addition to the above photopolymerization initiator, a photopolymerization initiator may be further added within a range not hindering the effect of the present invention. Preferably useful is at least one selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, bisimidazoles and thioxanthone-based compounds.
Specific examples of the acetophenone-based compound may include: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and mixtures thereof, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
Examples of the benzophenone-based compound include: benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenylsulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, and the like.
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 bisimidazoles include 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) bisimidazole, 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetrakis (trialkoxyphenyl) biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, imidazole compounds in which the 4,4',5,5' position of the phenyl group is substituted with an alkoxycarbonyl group, and the like. Among these biimidazole compounds, preferably useful are 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenylbiimidazole and 2, 2-bis (2, 6-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole.
Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.
Further, in order to improve the sensitivity of the blue photosensitive resin composition according to the present invention, the photopolymerization initiator may further include a photo-initiation assistant. The blue photosensitive resin composition according to the present invention may have further improved sensitivity due to the photo-initiation aid contained therein, thereby improving productivity.
The photoinitiating adjuvant preferably includes, for example, an amine compound or a carboxylic acid compound.
The amine compound may include, for example: aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; and aromatic amine compounds such as 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 known as michler's ketone), 4' -bis (diethylamino) benzophenone, and the like. And an aromatic amine compound may be preferably used.
The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.
The amount of the photopolymerization initiator may be set to 0.1 to 30% by weight, and preferably 1 to 20% by weight, based on the total solid weight of the blue photosensitive resin composition. When the amount of the photopolymerization initiator falls within the above range of 0.1 to 30 wt%, the sensitivity of the photosensitive resin composition may increase and the photographic exposure time may decrease, thereby improving productivity and maintaining high resolution. Further, in the case where the composition is used under the above-mentioned conditions, the intensity and surface smoothness of the formed pixel portion can be improved.
In the case where the photo initiation assistant is additionally used, the photo initiation assistant may be set to 0.1 to 30% by weight, and preferably 1 to 20% by weight, based on the total solid weight of the blue photosensitive resin composition. When the amount of the photo-initiation assistant falls within the above range of 0.1 to 30% by weight, it is preferable because the sensitivity of the blue photosensitive resin composition is further increased and the productivity of a color filter formed using the above composition can be improved.
Solvent (E)
The solvent of the present invention is characterized by comprising more than 0% by weight and not more than 8% by weight of a solvent having a boiling point of 180 ℃ or higher, based on the total weight of the solvent.
If the amount of the solvent exceeds 8% by weight, the increased amount of the residual solvent causes fluidity of the paint film formed in the soft baking step, and thus it is difficult to maintain the flatness of the pattern.
The solvent having a boiling point of 180 ℃ or higher includes one or more selected from the group consisting of dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol dibutyl ether, 1, 2-propylene glycol diacetate, and the like, and preferably includes one or more selected from the group consisting of dipropylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, and 1, 2-propylene glycol diacetate.
Further, any solvent used in a general blue photosensitive resin composition may be additionally mixed and used as long as it can effectively dissolve other components. Among these solvents, ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, or the like are preferable.
Ethers may include, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and the like.
Aromatic hydrocarbons may include, for example: benzene, toluene, xylene, mesitylene, and the like.
The ketones may include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.
Alcohols may include, for example: ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and the like.
Esters may include, for example: ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methylcellosolve acetate, ethylcellosolve acetate, ethyl acetate, butyl acetate, pentyl 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, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3-propanediol, ethyl lactate, propylene glycol, n-propyl ether, ethyl 3-ethoxypropionate, propylene glycol monobutyl ether, 3-methoxy-1-butyl acetate, methyl cellosolve acetate, n-butyl acetate, n, Ethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, 1, 2-propylene glycol diacetate, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, γ -butyrolactone, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether, 1, 3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, ethylene carbonate, and propylene carbonate and γ -butyrolactone, and the like.
The above-listed solvents may be used alone or in combination of two or more.
Further, among the exemplified solvents, preferred in terms of applicability and drying ability are organic solvents having a boiling point of 100 to 200 ℃, and more preferred are, 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.
Further, most preferably, the solvent of the present invention comprises: one or more selected from the group consisting of dipropylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, and 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher, and propylene glycol monomethyl ether acetate.
Further, the solvent may be used in an amount of 60 to 90 wt%, and preferably 70 to 85 wt%, based on the total weight of the blue photosensitive resin composition according to the present invention. When the amount of the solvent falls within the above range of 60 to 90 wt%, applicability can be improved when coating is performed using a coater such as a roll coater, a spin coater, a slit-spin coater, a slit coater (also referred to as a pattern coater), a spray coater, reverse printing, gravure printing, screen printing, pad printing, inkjet, and the like.
Additive (F)
Additives may be selectively added as needed, and may include, for example: selected from one or more of other polymer compounds, curing agents, adhesion promoters, UV absorbers, polymerization inhibitors, and the like.
Specific examples of the other polymer compounds may include: curable resins such as epoxy resins, maleimide resins, and the like; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, perfluoroalkyl acrylate, polyester, polyurethane, etc., but not limited thereto.
The curing agent is for curing the core and improving mechanical strength, and may include, for example: epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.
Among the curing agents, specific examples of the epoxy compound may include, but are not limited to: bisphenol a type epoxy resins, hydrogenated bisphenol a type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol F type epoxy resins, novolac epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, epoxidized butadiene (co) polymers, epoxidized isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate, and the like.
Among the curing agents, specific examples of the oxetane compound may include: carbonate dioxetane, xylene dioxetane, adipate dioxetane, terephthalate dioxetane, cyclohexane dicarboxylic acid dioxetane, and the like.
The curing agent may further include an auxiliary curing compound which, together with the curing agent, causes the epoxy group of the epoxy compound and the oxetane backbone of the oxetane compound to undergo a ring-opening polymerization reaction.
The auxiliary curing compound may include, for example, polycarboxylic acids, polycarboxylic anhydrides, acid generators, and the like. The polycarboxylic acid anhydride may include those commercially available as curing agents for epoxy resins. Examples of commercially available epoxy resin curing agents include: adeka hardner EH-700 (available from Adeka), Rikacid HH (available from New Japan Chemicals), MH-700 (available from New Japan Chemicals), and the like.
The above-listed examples of the curing agent and the auxiliary curing compound may be used alone or in combination of two or more.
The adhesion promoter is not particularly limited, and specific examples thereof are: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylo, 3-isocyanatopropyltriethoxysilane, and the like.
The above-listed adhesion promoters may be used alone or in combination of two or more.
The adhesion promoter may be used in an amount of 0.01 to 10 wt%, and preferably 0.05 to 2 wt%, based on the total weight of solids of the blue photosensitive resin composition.
Specific examples of UV absorbers include, but are not limited to: 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.
Specific examples of aggregation inhibitors include, but are not limited to: sodium polyacrylate, and the like.
The method for preparing the blue photosensitive resin composition according to the present invention is as follows.
Specifically, the pigment (a1) of the blue colorant (a) is mixed with the solvent (E) and dispersed using a ball mill until the average particle diameter of the pigment is 0.2 μm or less. Similarly, part or all of the pigment dispersant (a2), the alkali-soluble resin (B), or the dye (a3) may be mixed with the solvent (E) and dissolved or dispersed as necessary.
The dye (a3), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), and the photopolymerization initiator (D) and optional additives (F), and the solvent (E) were further added to the mixed dispersion solution at a predetermined concentration, thereby preparing a blue photosensitive resin composition according to the present invention.
In addition, the present invention provides a blue filter prepared by the blue photosensitive resin composition and a display device equipped with the same.
First, a smooth paint film is obtained by coating a blue photosensitive resin composition on a substrate (usually glass) or on a layer made of a blue photosensitive resin composition in a predetermined solid content, and thereafter removing volatile components such as a solvent by heating and drying.
Coating methods may include, for example: spin coating, flexible coating, roll coating, slot spin coating, or slot coating.
Volatile components such as solvents are volatilized by heating and drying after coating (prebaking) or by heating after drying under reduced pressure.
Similarly, the heating temperature is usually 70 to 200 ℃, preferably 80 to 130 ℃.
The thickness of the paint film after heating and drying is usually about 1 to 8 μm. UV light is irradiated on the obtained paint film using a mask for forming a desired pattern. Also, it is preferable to use devices such as a mask aligner and a lithography machine (stepper) so that parallel beams can be irradiated on the entire photographically exposed portion and also the mask and the substrate can be properly aligned. When irradiated with UV, the UV-irradiated area is cured.
For UV, g line (wavelength: 436nm), h line, i line (wavelength: 365nm), etc. can be used. The dose of UV irradiation may be appropriately selected as needed, but is not limited to the present invention. When curing is complete, the paint film is brought into contact with a developing solution and the non-photographically exposed portions are dissolved, and spacers (spacers) having the shape of the target pattern can thus be obtained.
The developing method is not particularly limited, and is a liquid addition method, a dipping method, a spraying method, or the like.
Further, the substrate may be inclined at any angle at the time of development. The developing solution is usually an aqueous solution containing an alkaline compound and a surfactant.
The basic compound is not particularly limited, and is an organic basic compound or an inorganic basic compound. The inorganic basic compound may include, for example: sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, diammonium hydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia and the like.
Further, the organic basic compound may include, for example: tetramethylammonium hydroxide, 2-hydroxyethyltrimethyl, ammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like.
Both the inorganic basic compound and the organic basic compound may be used alone or in combination of two or more. The concentration of the alkali compound in the developing solution is set to 0.01 to 10% by weight, and preferably 0.03 to 5% by weight, based on the total weight of the developing solution.
As the surfactant in the developing solution, one or more selected from the above-mentioned nonionic surfactants, anionic surfactants and cationic surfactants may be used. The concentration of the surfactant in the developing solution is set to 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight, based on the total weight of the developing solution.
After the development, the resultant is washed with water, and then post-baking is carried out at 150 to 230 ℃ for 10 to 60 minutes as required.
By performing the above-mentioned treatments using the blue photosensitive resin composition of the present invention, a specific pattern can be formed on a substrate.
The invention is described in more detail below by way of the following examples which are set forth for purposes of illustration and are not to be construed as limiting the invention. The scope of the present invention has been shown in the claims, and furthermore, it has the meaning equivalent to the description of the claims and all modifications within the scope thereof.
< preparation of pigment-dispersed composition >
[ preparation example 1]: preparation of pigment Dispersion compositions
A pigment dispersion composition was prepared by mixing/dispersing 12.0 parts by weight of c.i. pigment blue 15:6 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (available from BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent for 12 hours by a ball mill.
< Synthesis of alkali-soluble resin >
Synthesis example 1: synthesis of alkali soluble resins
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, 13.0 parts by weight of methacrylic acid, 10 parts by weight of benzyl methacrylate, 57 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercaptan were placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping distributor (dropping lot), and a nitrogen supply tube, and the interior of the flask was purged with nitrogen. Thereafter, the resultant mixture was stirred, the temperature of the reaction mixture was increased to 110 ℃, and the reaction was allowed to proceed for 6 hours, and thereby an alkali-soluble resin was synthesized. The solid of the alkali-soluble resin thus synthesized had an acid value of 100.2mgKOH/g and a weight average molecular weight of about 15110 as measured by Gel Permeation Chromatography (GPC).
Synthesis example 2: synthesis of alkali soluble resins
200 parts by weight of propylene glycol monomethyl ether acetate, 45 parts by weight of propylene glycol monomethyl ether, 4 parts by weight of Azobisisobutyronitrile (AIBN), 15 parts by weight of acrylic acid, 70 parts by weight of benzyl methacrylate, 15 parts by weight of styrene and 3 parts by weight of n-dodecylmercaptan were put into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping distributor and a nitrogen supply tube, and the inside of the flask was purged with nitrogen. Thereafter, the resultant mixture was stirred, the temperature of the reaction mixture was increased to 110 ℃, and the reaction was allowed to proceed for 2 hours, and thereby an alkali-soluble resin was synthesized. The solid of the alkali-soluble resin thus synthesized had an acid value of 110.4mgKOH/g and a weight-average molecular weight of about 8900 as measured by GPC.
< preparation of colored photosensitive resin composition >
Example 1
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment-dispersion composition prepared in preparation example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (an oxime ester compound; available from TRONLY) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher.
Example 2
A photosensitive blue resin composition was prepared by mixing 27.9 parts by weight of the pigment-dispersion composition prepared in preparation example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of OXE-01 (an oxime ester compound; available from BASF) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher.
Example 3
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment-dispersion composition prepared in preparation example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 0.6 parts by weight of OXE-01 (oxime ester compound; available from BASF) as a photopolymerization initiator, 0.6 parts by weight of TR-PBG-305 (oxime ester compound; available from TRONLY), 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher.
Example 4
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment-dispersion composition prepared in preparation example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (an oxime ester compound; available from TRONLY) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of dipropylene glycol monomethyl ether as a solvent having a boiling point of 180 ℃ or higher.
Example 5
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment-dispersion composition prepared in preparation example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (an oxime ester compound; available from TRONLY) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of dipropylene glycol methyl ether acetate as a solvent having a boiling point of 180 ℃ or higher.
Example 6
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment-dispersion composition prepared in preparation example 1, 10.7 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (an oxime ester compound; available from TRONLY) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher.
Comparative example 1
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment-dispersion composition prepared in preparation example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 2, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (an oxime ester compound; available from TRONLY) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher.
Comparative example 2
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment-dispersion composition prepared in preparation example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (an oxime ester compound; available from TRONLY) as a photopolymerization initiator, 38 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 8.2 parts by weight of 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher.
Comparative example 3
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment-dispersion composition prepared in preparation example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of Irgacure 369 (an oxime ester compound; available from BASF) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher.
Comparative example 4
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment dispersion prepared in preparation example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (oxime ester compound; available from TRONLY) as a photopolymerization initiator, and 46.2 parts by weight of propylene glycol monomethyl ether acetate as a solvent.
Comparative example 5
A blue photosensitive resin composition was prepared by mixing 27.9 parts by weight of the pigment dispersion prepared in preparation example 1, 6.0 parts by weight of the alkali-soluble resin prepared in Synthesis example 1, 12.5 parts by weight of the alkali-soluble resin prepared in Synthesis example 2, 6.2 parts by weight of KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (oxime ester compound; available from TRONLY) as a photopolymerization initiator, 41.0 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher.
Test example 1: production of blue Filter and evaluation of adhesion
Each of the blue photosensitive resin compositions of examples 1 to 6 and comparative examples 1 to 5 was coated on a glass substrate ("EAGLE XG"; available from Corning) having a 2-inch angle using spin coating, and vacuum-dried in a vacuum drying apparatus under reduced pressure until 65 Pa. Thereafter, the glass substrate was placed on a hot plate and held at 100 ℃ for 3 minutes, thereby forming a thin film. Subsequently, a test photomask having a line width/space pattern of 1 μm to 100 μm was placed on the thin film, and UV light was applied at a space of 300 μm from the test photomask. Likewise, a 1KW high pressure mercury lamp containing all the rays g, h and i was used at 40mJ/cm2The UV light is irradiated and no specific optical filter is used. The UV-irradiated film was immersed in an aqueous KOH solution having a pH of 10.5 as a developing solution for 2 minutes, thereby being developed. The glass substrate coated with the thin film was washed with distilled water, dried with nitrogen, and heated in an oven at 220 ℃ for 25 minutes, thereby manufacturing a blue filter.
The film thickness of the blue filter thus manufactured was 3.4 μm.
The adhesion of the blue filter prepared above was evaluated as follows. The defect count of the 20 μm pattern of the blue filter was evaluated by using an optical microscope. The results are shown in Table 1 below.
< number of defects >
O: no pattern defect
And (delta): 1 to 3 pattern defects
X: 4 or more pattern defects
Test example 2: production of blue Filter and evaluation of Pattern flatness
Each of the blue photosensitive resin compositions of examples 1 to 6 and comparative examples 1 to 5 was coated with a 2-inch angle by spin coatingA black matrix of 100 μm line width/space was formed on the patterned glass substrate, and vacuum drying was carried out in a vacuum drying apparatus under reduced pressure until 65 Pa. Thereafter, the glass substrate was placed on a hot plate and held at 100 ℃ for 3 minutes, thereby forming a thin film. Subsequently, UV light is applied to the film without using a photomask. Likewise, a 1KW high pressure mercury lamp containing all the rays g, h and i was used at 40mJ/cm2The UV light is irradiated and no specific optical filter is used. The UV-irradiated film was immersed in an aqueous KOH solution having a pH of 10.5 as a developing solution for 2 minutes, thereby being developed. The glass substrate coated with the thin film was washed with distilled water, dried with nitrogen, and heated in an oven at 220 ℃ for 25 minutes, thereby manufacturing a blue filter.
The film thickness of the blue filter thus manufactured was 3.4 μm.
The flatness of the blue filter prepared above was evaluated as follows. The blue filters prepared on the black matrix were measured using a colorimeter (OSP-200, available from Olympus). The color of a dot at a distance of 50 μm from the black matrix pattern and the color of a dot at a distance of 10 μm from the black matrix pattern were measured, and the color difference (By) between the two dots is listed in table 1 below. The correlation between the color difference (By) and the pattern flatness is as follows.
< comparison threshold of color difference (By) and pattern flatness >
O: 1/10000< color difference (By) <9/10000
X: color difference (By) ≥ 10/10000
[ Table 1]
| Species of | Adhesion Property | Flatness of pattern | Color difference |
| Example 1 | ○ | ○ | 0.0005 |
| Example 2 | ○ | ○ | 0.0006 |
| Example 3 | ○ | ○ | 0.0007 |
| Example 4 | ○ | ○ | 0.0005 |
| Example 5 | ○ | ○ | 0.0007 |
| Example 6 | ○ | ○ | 0.0008 |
| Comparative example 1 | △ | × | 0.002 |
| Comparative example 2 | ○ | × | 0.003 |
| Comparative example 3 | × | × | 0.002 |
| Comparative example 4 | ○ | × | 0.003 |
| Comparative example 5 | △ | × | 0.003 |
Comparative example 1 is a blue photosensitive resin composition prepared using an alkali-soluble resin having a molecular weight of less than 15000, comparative example 2 is a blue photosensitive resin composition containing more than 8% by weight of a blue photosensitive resin composition having a boiling point of 180 ℃ or higher based on the total weight of a solvent, and comparative example 3 is a blue photosensitive resin composition prepared using a photopolymerization initiator not containing an oxime ester compound. Further, comparative example 4 is a blue photosensitive resin composition not containing a blue photosensitive resin composition having a boiling point of 180 ℃ or more, and comparative example 5 is a blue photosensitive resin composition containing less than 40% by weight of an alkali soluble resin having a molecular weight of 15000 or more based on the total weight of the alkali soluble resin.
As is apparent from Table 1, the blue filters using the blue photosensitive resin compositions of examples 1 to 6 exhibited excellent adhesion, good color difference (By), and excellent pattern flatness. In particular, the pattern flatness is excellent, and thus constant color coordinates can be obtained in one pixel.
On the other hand, the blue filters prepared using the blue photosensitive resin compositions of comparative examples 1 to 5 had high color difference (By) because pattern flatness could not be obtained even though it was excellent in adhesion.
Therefore, the blue photosensitive resin of the present invention does not cause pattern separation even with low photographic exposure due to excellent adhesiveness, and has an excellent effect that a constant color coordinate can be realized in one pixel because pattern flatness is excellent.
Claims (8)
1. A blue photosensitive resin composition for improving adhesion, comprising: a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
wherein the alkali soluble resin is contained in an amount of 20 to 80 wt% based on the total solid weight of the blue photosensitive resin composition;
wherein the alkali-soluble resin includes 40 to 100 wt% of an alkali-soluble resin having a molecular weight of 15000 or more, based on the total weight of the alkali-soluble resin;
wherein the photopolymerization initiator includes one or more selected from the group consisting of 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (o-benzoyloxime) and 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (o-benzoyloxime); and the number of the first and second electrodes,
wherein the solvent comprises more than 0 wt% and not more than 8 wt% of a solvent having a boiling point of 180 ℃ or higher, based on the total weight of the solvent,
wherein the solvent having a boiling point of 180 ℃ or higher is composed of one or more selected from the group consisting of dipropylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, and 1, 2-propanediol diacetate.
2. The blue photosensitive resin composition according to claim 1, wherein the blue colorant comprises one or more pigments, one or more dyes, or a combination thereof.
3. The blue photosensitive resin composition according to claim 1, wherein the alkali-soluble resin has an acid value of 30mgKOH/g to 150 mgKOH/g.
4. The blue photosensitive resin composition according to claim 1, wherein the solvent comprises: one or more selected from the group consisting of dipropylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, and 1, 2-propylene glycol diacetate as a solvent having a boiling point of 180 ℃ or higher, and propylene glycol monomethyl ether acetate.
5. The blue photosensitive resin composition according to claim 1, comprising:
based on the total solid weight of the blue photosensitive resin composition,
0.5 to 60% by weight of the blue colorant,
5 to 45% by weight of the photopolymerizable compound, and
0.1 to 30% by weight of the photopolymerization initiator; and
based on the total weight of the blue photosensitive resin composition,
60 to 90% by weight of the solvent.
6. The blue photosensitive resin composition according to claim 5, wherein the photopolymerization initiator comprises 10 to 100% by weight of one or more selected from the group consisting of: 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (o-benzoyloxime) and 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (o-benzoyloxime).
7. A blue filter comprising the blue photosensitive resin composition according to claim 1.
8. A display device comprising the blue filter according to claim 7.
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| KR20140028436 | 2014-03-11 | ||
| KR10-2014-0028436 | 2014-03-11 | ||
| KR1020150026937A KR101988696B1 (en) | 2014-03-11 | 2015-02-26 | A blue photosensitive resin composition, blue color filter and display device comprising the same |
| KR10-2015-0026937 | 2015-02-26 |
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| CN104914669A CN104914669A (en) | 2015-09-16 |
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| JP6755822B2 (en) * | 2016-03-30 | 2020-09-16 | 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． | A green photosensitive resin composition, a color filter manufactured by using the green photosensitive resin composition, and a display element including the color filter. |
| TWI657311B (en) * | 2017-12-29 | 2019-04-21 | 住華科技股份有限公司 | Photosensitive resin composition, and color resistor structure and display using the same |
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| CN101154038A (en) * | 2006-09-29 | 2008-04-02 | 富士胶片株式会社 | Curing colouration composition, color filtering device and liquid crystal display using the color filtering device |
| KR20090023924A (en) * | 2007-09-03 | 2009-03-06 | 제일모직주식회사 | Ink composition for color filter, method for manufacturing picture element of color filter, and color filter |
| CN101419404A (en) * | 2007-10-23 | 2009-04-29 | Jsr株式会社 | Radiation-sensitive composition for blue color filter, color filter and liquid crystal display device |
| JP2013088711A (en) * | 2011-10-20 | 2013-05-13 | Nippon Zeon Co Ltd | Photosensitive resin composition |
| CN103360788A (en) * | 2012-03-29 | 2013-10-23 | 阪田油墨股份有限公司 | Blue pigment dispersion composition for color filter and blue pigment dispersion anti-corrosion composition for color filter containing the same |
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| CN101154038A (en) * | 2006-09-29 | 2008-04-02 | 富士胶片株式会社 | Curing colouration composition, color filtering device and liquid crystal display using the color filtering device |
| KR20090023924A (en) * | 2007-09-03 | 2009-03-06 | 제일모직주식회사 | Ink composition for color filter, method for manufacturing picture element of color filter, and color filter |
| CN101419404A (en) * | 2007-10-23 | 2009-04-29 | Jsr株式会社 | Radiation-sensitive composition for blue color filter, color filter and liquid crystal display device |
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