KR101680198B1 - Photopolymerizable resin composition - Google Patents
Photopolymerizable resin composition Download PDFInfo
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- KR101680198B1 KR101680198B1 KR1020100095632A KR20100095632A KR101680198B1 KR 101680198 B1 KR101680198 B1 KR 101680198B1 KR 1020100095632 A KR1020100095632 A KR 1020100095632A KR 20100095632 A KR20100095632 A KR 20100095632A KR 101680198 B1 KR101680198 B1 KR 101680198B1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
- G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Abstract
The present invention relates to a method of forming a barrier rib (shielding film) that exhibits an appropriate optical density while exhibiting an appropriate optical density at the time of film formation and has an appropriate hydrophobicity and prevents jetting of color ink or displacement of color ink upon injection of color ink by a jetting method using an ink- A photosensitive resin composition is provided.
Description
The present invention relates to a photosensitive resin composition suitable for forming a light-shielding film of an image display device such as a liquid crystal display (hereinafter referred to as "LCD").
The liquid crystal display device displays an image using the optical anisotropy and birefringence characteristics of liquid crystal molecules. When an electric field is applied, the arrangement of liquid crystals changes, and the characteristics of transmission of light along the direction of the changed liquid crystal are also changed.
Generally, in a liquid crystal display device, two substrates on which electric field generating electrodes are respectively formed are arranged so that the surfaces on which the two electrodes are formed face each other, a liquid crystal material is injected between the two substrates, And the liquid crystal molecules are moved by the electric field generated by the liquid crystal molecules.
An example of a structure of a widely used thin film transistor liquid crystal display (TFT-LCD) includes a lower substrate, namely, an array substrate on which thin film transistors and pixel electrodes are arranged; On a substrate made of plastic or glass, a black matrix and three colored layers of red, green, and blue are repeated. On top of that, materials such as polyimide, polyacrylate, and polyurethane An overcoat layer (OVERCOAT) having a thickness of 1 to 3 μm and an ITO (Indium Tin Oxide) transparent conductive film layer to which a voltage for driving the liquid crystal is applied is formed on the overcoat layer; And a liquid crystal filled between the upper and lower substrates. Polarizing plates for linearly polarizing visible light (natural light) are attached to both sides of the two substrates, respectively. A voltage is applied to the gate of the TFT constituting the pixel by an external peripheral circuit so that the transistor is turned on and the image voltage is inputted to the liquid crystal, and then the image voltage is applied to the liquid crystal, After storing, turn off the transistor so that the charge stored in the liquid crystal charger and the auxiliary charger is preserved, and the image is displayed for a certain period of time. When a voltage is applied to the liquid crystal, the arrangement of the liquid crystal changes. When light passes through the liquid crystal in this state, the diffraction occurs. This light is transmitted through a polarizing plate to obtain a desired image.
In recent years, efforts are being made to form a color filter of a liquid crystal display device on an upper substrate, that is, a lower substrate, that is, an array substrate instead of a color filter substrate, thereby increasing the aperture ratio and reducing the manufacturing process.
Even considering such a structural change, a color filter manufacturing method commonly uses a dyeing method, a dispersion method, an electrodeposition method, a printing method, a jetting method, and the like, and a technique of manufacturing a color filter by a jetting method using an ink- There is an advantage that the manufacturing process of the color filter can be simplified and the manufacturing cost can be reduced. However, the color filters manufactured by the jetting method by the ink jet printing have the greatest difficulty in ensuring the uniformity in the display cells in the glass substrate. The cause of poor uniformity of the color filter is mainly caused by a difference in the amount of ink ejected from each nozzle of the inkjet printhead. The difference in the amount of ink ejected from each nozzle of the inkjet printhead is visually recognized as a blur as the amount of color ink filled in each pixel region is changed. Further, when the color ink is filled in the inner space corresponding to the pixel area defined by the light-shielding pattern, that is, the black matrix, the surface of the color ink bulges due to the repulsive force between the light-shielding pattern and the color ink and the surface tension of the color ink It can be in the form of a right dome. The color difference may be caused by the thickness of the color filter formed at the center of the pixel region and the thickness of the color filter formed at the edge of the pixel region due to the color ink filled in the inner space in the inner space. The unevenness of the color filter due to these factors ultimately degrades the display quality.
In one embodiment of the present invention, there is provided a photosensitive resin composition having an appropriate optical density and proper hydrophobicity at the time of forming a cured film. In particular, one embodiment of the present invention provides a photosensitive resin composition useful as a barrier rib material for forming a colored layer by a jetting method using an inkjet print.
One embodiment of the present invention is a photosensitive resin composition comprising a cadmium-based binder resin, wherein the cadmium-based binder resin contains a fluorine group.
In another embodiment of the present invention, the photosensitive resin composition is a photosensitive resin composition further comprising an alkali soluble acrylic binder resin.
In another embodiment of the present invention, the alkali-soluble acrylic binder resin is a photosensitive resin composition comprising a monomer containing an acid group as a raw material monomer and a monomer copolymerizable therewith.
Another embodiment of the present invention is a photosensitive resin composition wherein the alkali-soluble acrylic binder resin contains an epoxy group-containing monomer as a raw material monomer.
In another embodiment of the present invention, the photosensitive resin composition comprises a multifunctional monomer having an ethylenically unsaturated double bond; A photopolymerization initiator; Pigments; And a solvent.
In another embodiment of the present invention, the content of the alkali-soluble acrylic binder resin is 5 to 50% by weight based on the total solid content of the photosensitive resin composition.
Another embodiment of the present invention is a photosensitive resin composition wherein the pigment comprises carbon black having a particle size of 50 to 150 nm.
Another embodiment of the present invention is a photosensitive resin composition wherein the fluorine content per g of the cured film is 5 to 50 wt% when the cured film is formed.
Another embodiment of the present invention is a method for producing a cured film, which comprises forming a cured film having an optical density (OD) of 2.0 or more per 1.0 mu m of a unit thickness, a contact angle to water of 85 DEG or more, and a contact angle to 2-ethoxyethanol of 35 DEG or more Sensitive resin composition.
Another embodiment of the present invention is a color filter substrate comprising a black matrix formed by photolithography using the above photosensitive resin composition.
Another embodiment of the present invention is a thin film transistor substrate including a black matrix formed by photolithography using the above photosensitive resin composition.
Another embodiment of the present invention is an image display device including the color filter substrate as an upper substrate.
Another embodiment of the present invention is an image display device including the thin film transistor substrate as a lower substrate.
The photosensitive resin composition according to the present invention exhibits appropriate optical density and proper hydrophobicity at the time of forming a cured film, so that when a pattern having light shielding property is formed using the same, a jetting method using an inkjet printing It is possible to solve the problem that the color ink is mixed over the light shielding pattern or deviated from the position. As a result, it is easy to form the colored layer by the jetting method using the ink jet printing, and ultimately the display defect can be reduced.
According to one embodiment of the present invention, there is provided a photosensitive resin composition comprising a cationic binder resin, wherein the cationic binder resin contains a fluorine group.
The present invention will be described in more detail as follows.
In a color filter manufacturing method, a jetting method using an inkjet print is a method in which a light shielding pattern is formed by a photolithographic method using a light-shielding photosensitive resin composition, and then each color ink Red, green, blue) is jetted to form a colored layer.
When the colored layer is formed by such a method, the process can be simplified and the cost can be reduced as compared with the method of forming the red, green and blue colored layers by photolithography. Also, the color reproducibility can be increased according to the injection amount of the color ink, so that the color reproducibility is excellent and the pattern and the composition of the pattern can be kept constant. In addition, it is easier to implement a fine circuit pattern, and it is also easy to apply to a flexible display or the like. In addition, there is little waste of photoresist, solvent, and energy, which is environmentally friendly.
However, the jetting method by inkjet printing requires the accuracy and capability of inkjet printing and requires a related material for inkjet printing.
The present invention relates to a photosensitive resin composition capable of forming a light-shielding pattern useful for forming a colored layer by a jetting method using such an inkjet print.
From this point of view, the photosensitive resin composition according to one embodiment of the present invention includes a cadmium-based binder resin, and the cadmium-based binder resin contains a fluorine group.
(OD) of 2.0 or more per unit thickness of 2.0 m or more at the time of forming the cured film from the photosensitive resin composition, a contact angle to water when the cured film is formed is 85 or more, and a contact angle to 2-ethoxyethanol of 35 Deg.] Or more, preferably a contact angle to water when forming a cured film is 85 to 110 [deg.], And a contact angle with respect to 2-ethoxyethanol when the cured film is formed is 35 to 50 .
If the optical density (OD) per unit thickness of 2 占 퐉 of the cured film obtained from the photosensitive resin composition is less than 2.0, even if the thickness is somewhat thick, it may be difficult to exhibit a proper shielding effect. It can not be sufficiently expressed and may not be shielded from light which is transmitted through the transparent pixel electrode other than the transparent pixel electrode.
The cured film formed from the photosensitive resin composition according to the present invention may have a contact angle to water of 85 ° or more and a contact angle to 2-ethoxyethanol of 35 ° or more.
When forming a cured film, when the contact angle to water is less than 85 °, there may be a problem in that ink jetting may cause problems such as overflow of the ink liquid in the pixel region or the amount of filled color ink.
When the contact angle with respect to 2-ethoxyethanol is less than 35 DEG, there may be a problem that the amount of color ink to be filled or the amount of ink to be filled may be varied due to overflow of the ink liquid in the pixel area upon ink jetting.
Since the light shielding pattern is usually formed on the glass surface and the color ink is injected into the light shielding pattern, the surface tension of the glass surface in terms of prevention of color mixing prevention and position deviation after injection of the color ink is larger than the surface tension of the color ink At least, and the surface tension of the light shielding pattern should be smaller than that of the color ink.
From this viewpoint, it is preferable that the photosensitive resin composition according to one embodiment of the present invention has a contact angle to water of 85 to 110 ° at the time of forming a cured film, and when the contact angle with respect to 2-ethoxyethanol is 35 To 50 [deg.].
On the other hand, as the alkali soluble acrylic resin binder among the binders constituting the photosensitive resin composition, a copolymer formed by copolymerization of a monomer containing an acid functional group and a monomer copolymerizable with the monomer can be used. In the case of such copolymerization, the strength of the film can be made higher than that of the resin produced by homopolymerization. Or a polymer compound produced by a polymer reaction of the formed copolymer and an ethylenically unsaturated compound containing an epoxy group may be used.
That is, as the alkali-soluble resin binder, a copolymer formed by copolymerization of a monomer containing an acid group and a monomer copolymerizable with the monomer can be used. In addition to the copolymer, a polymer compound formed by bonding an ethylenically unsaturated compound containing an epoxy group to the copolymer structure may be used together.
Non-limiting examples of the monomer including the acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, Carboxylic acids and the like. These may be used alone or in combination of two or more.
In particular, in consideration of the property of the cured film resistant to alkali resistance, it may be preferable to use a binder resin containing an epoxy group. From this point, it may be preferable to use an epoxy group-containing monomer in addition to the monomer containing an acid group in the production of an alkali- .
Examples of the epoxy group-containing monomer include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate, glycidyl? -N-butyl acrylate, Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl,? -Ethylacrylic acid- o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like, but are not limited thereto.
The alkali-soluble acrylic binder resin may also contain a fluorine group from the viewpoint of exhibiting hydrophobicity upon formation of a cured film by the photosensitive resin composition of the present invention.
The fluorine-containing monomer which can be used at this time is not particularly limited as long as it is copolymerizable with other monomers and has one carbon double bond. Examples thereof include CH 2 = CHC (O) OCHCH 2 (CF 2 ) xCF 3 (wherein x is an integer of 1 to 12).
Such a content of the fluorine group-containing monomer can be controlled according to the fluorine group content of the monomer, and it is possible to satisfy the above-mentioned contact angle and the contact angle with respect to 2-ethoxyethanol, without deteriorating developability, coating property and dispersion stability It may be desirable to adjust the fluorine content of the alkali-soluble acrylic binder to 5 to 50% by weight.
The content of the alkali-soluble acrylic binder resin containing the fluorine group may be increased to 5 to 50% by weight based on the total solid content of the photosensitive resin composition, have.
The alkali-soluble acrylic binder resin thus obtained may not only be included as a binder resin but may also exhibit hydrophobicity by adding a small amount of the binder resin in a colorant preparation process described later.
If the alkali-soluble acrylic binder resin containing a fluorine group is added in the colorant, the content thereof may be preferably 1 to 30% by weight based on the solid content, in terms of pigment dispersion and hydrophobic development.
On the other hand, when a photosensitive resin composition is prepared using only an alkali-soluble acrylic binder, a large amount of a multifunctional monomer should be used in forming a light-shielding film having a thickness of 2.2 μm or more. Thus, surface hardening by photocuring occurs rapidly, There may be occasions that occur. In this regard, the photosensitive resin composition according to one embodiment of the present invention includes a binder resin as a binder resin, and the compound of the cadmium-based binder resin refers to an acrylate-based binder resin containing a fluorene group in the main chain There is no particular limitation on the structure.
Examples of the cationic binder resin include compounds represented by the following formula (1).
≪ Formula 1 >
In the above formula, X may be a compound represented by the following general formula (2). The above-mentioned n is an integer of 1 to 100.
(2)
The Y may be selected from the group consisting of maleic anhydride, succinic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, , 5,6-tetrahydrophthalic anhydride, phthalic anhydride, itaconic anhydride, 1,2,4-benzenetricarboxylic anhydride (1, 2,4-benzenetricarboxylic anhydride, methyl-tetrahydrophthalic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene 1-cyclopentene-1,2-dicarboxylic anhydride, cis (5-norbornene-endo-2,3-dicarboxylic anhydride (cis-5-Norbonene-endo-2,3 -Dicarboxylic anhydride, and 1,8-naphthalic anhydride.
Further, the Z may be 1,2,4,5-benzene tetracarboxylic dianhydride, 4,4'-biphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, pyromelitic dianhydride, 1,4,5,8-naphthalene, Tetracarboxylic acid dianhydride, 1,2,4,5-tetracarboxylic anhydride, methylnorbornene-2,3-di Methylnorbonene-2,3-dicarboxylic anhydride, 4,4 '- [2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] diphthalic anhydride (4,4' - [ 2,2,2-Trifluoromethyl Ethylidene Diphthalic Anhydride, 4,4'-Oxydiphthalic Anhydride and Ethylene Glycol Bis (Ethylene Glycol Bis (Anhydro Trimelitate) < / RTI > One can.
A functional group capable of manifesting hydrophobicity can be introduced into the structure of the cadmium-based binder resin. In particular, a fluorine group can be introduced as described above.
There is no limitation on the method of introducing the fluorine group during the production process of the cadmium-based binder resin and the compound which can be used for introduction, and a specific example is the compound obtained from the following reaction formula 1.
Scheme 1
Wherein R is an alkyl group having 1 to 12 carbon atoms.
The above-mentioned Reaction Scheme 1 is only for introducing a fluorine group into an example of a cadmium-based binder resin, and is not intended to limit the fluorine-containing cadmium-based binder resin usable in the present invention.
The cadmium binder resin is preferably 1 to 40% by weight, more preferably 20 to 30% by weight based on the total solid content of the photosensitive resin composition. If a cocatalyst binder resin containing a fluorine group is used, it may preferably be used in an amount of 5 to 10% by weight based on the total solid content of the photosensitive resin composition, considering hydrophobicity, developability, coating property and dispersion stability .
However, when a photosensitive resin composition is prepared using only a cadmium binder resin, a cured film having a thickness of 2.2 탆 or more is reacted with a multifunctional monomer having an ethylenically unsaturated double bond by photo-curing to cause surface hardening only quickly, Wrinkles may occur due to internal shrinkage at the time.
The photosensitive resin composition according to one embodiment of the present invention may include a multifunctional monomer having an ethylenically unsaturated double bond, which forms a photoresist image by light. Examples thereof include propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexane Diol acrylate tetraethylene glycol methacrylate, bisphenoxy ethyl alcohol diacrylate, trishydroxy ethylisocyanurate trimethacrylate, trimethylpropane trimethacrylate, pentaerythritol trimethacrylate, penta Tetramethacrylate, erythritol tetramethacrylate, and dipentaerythritol hexamethacrylate. In the present invention, it is also possible to use a mixture of two or more selected from the group consisting of tetramethacrylate, erythritol tetramethacrylate and dipentaerythritol hexamethacrylate.
The content is 0.1 to 99 parts by weight based on 100 parts by weight of the compound represented by the general formula (1), because of the cross-linking due to the radical reaction of the photoinitiator due to UV, the pattern formation and the bonding strength between the pigment and the particle component are increased, .
In one embodiment of the present invention, a monomer capable of imparting hydrophobicity can be further added. As the monomer, a monomer may be selected so as not to impair the coating property, adhesion, and leveling property of the photosensitive resin composition and to realize hydrophobicity .
Examples thereof include a fluorinated epoxy compound categorized into CH 2 (O) CHCH 2 (CF 2 ) xCF 3 (where x is an integer of 1 to 12) and a siloxane-based compound containing a fluorine group, such as CF 3 CF 2 ) ySi (OMe) 3 (wherein y is an integer of 1 to 12).
When such a monomer is added as an additive, the content thereof may be varied in consideration of coating property, adhesion strength, leveling property, and hydrophobicity, and may be preferably 1 to 12 wt% based on the total solid content.
Examples of the photopolymerization initiator include 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime)), 1- 2-octanedione-1 [(4-phenylthio) phenyl] -2-benzoyl-oxime) and thioxanthone , 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, dimethoxyacetoxy Methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2- 2-diethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy- Ethoxy) phenyl- (2-hydroxy-2- ) Ketone, ketones such as 1-hydroxycyclohexyl phenyl ketone; Quinones such as anthraquinone and 1,4-naphthoquinone; Tri (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2- chlorophenyl) Halogen compounds such as phenoxy) -s-triazine, phenacyl chloride, tribromomethylphenylsulfone, and tris (trichloromethyl) -s-triazine; Peroxide such as di-t-butyl peroxide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and other acylphosphine oxides.
Such a photopolymerization initiator is usually contained in an amount of 1 to 30% by weight based on the total photosensitive resin composition.
The photosensitive resin composition according to one embodiment of the present invention may include a solvent. Examples of the solvent include propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, methyl But are not limited to, cellosolve acetate, ethylcellosolve acetate, diethylglycolmethyl acetate, ethylethoxypropionate, methylethoxypropionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methyl isobutyl ketone, Amide, N, N'-dimethylacetamide, N-methylpyrrolidinone, dipropylene glycol methyl ether, toluene, methyl cellosolve and ethyl cellosolve.
The content thereof may generally be about 20 to 60% by weight in the entire photosensitive resin composition.
In addition, conventional additives may be further included if necessary.
The photosensitive resin composition according to one embodiment of the present invention may contain at least two kinds of pigment mixed components which are mixed and can substantially express black, in the colorant exhibiting shading properties.
The photosensitive resin composition for normally exhibiting light shielding properties includes a black pigment, for example, carbon black or titanium black can be used. Examples of the black pigment include, but are not limited to, carbon black or titanium black.
Such a pigment mixture component may contain 10 to 50% by weight of the red pigment, 10 to 50% by weight of the blue pigment, 1 to 20% by weight of the yellow pigment and 1 to 20% by weight of the green pigment based on the solid content in the total weight of the colorant . Wherein the violet pigment may comprise from 1 to 20% by weight based on the solids content in the total weight of the colorant. The black pigment may also be present in the total weight of the colorant, By weight or less and 10% by weight or less. In the case of a black pigment, since it often has electrical conductivity, there may arise a problem that the dielectric constant increases and the electrical characteristics of the cured film may be deteriorated. When a black pigment is included, it is preferable to select a pigment having high resistance, It is more preferable that the amount thereof is 15% by weight or less based on the solid content in the total weight of the colorant.
On the other hand, depending on the degree of dispersion of the pigment, the optical density and electrical resistance of the light-shielding film formed from the photosensitive resin composition may vary. In this respect, the colorant may include a pigment dispersant. Examples of the pigment dispersant include polymer dispersants such as modified polyurethanes, modified polyacrylates, modified polyesters and modified polyamides, and surfactants such as phosphoric acid esters, polyesters and alkyl amines. Disperbyk-2000, Disperbyk-2001, LP-N-21116 and LP-N-21208 of BYK chemie, EFKA-4300, EFKA-4330, EFKA-4340 and EFKA of Ciba -4400, EFKA-4401, EFKA-4402, EFKA-4046 or EFKA-4060 may be more advantageous in view of stable implementation of dispersion stability, optical density and electrical properties.
However, when the pigment dispersant is contained in an excessive amount, the dispersion stability may be deteriorated or the pattern stability may be deteriorated due to the degeneration of a specific functional group. In this respect, the content of the pigment dispersant may vary depending on the solid content in the total weight of the colorant By weight, preferably 3 to 20% by weight.
The total amount of the colorant is preferably 20 to 80% by weight, more preferably 30 to 66% by weight based on the total weight of the photosensitive resin composition. When the content of the mixed pigment is less than 20% by weight, the optical density of the formed light-shielding film is low and the light-shielding property is not sufficient. When the content exceeds 80% by weight, the amount of the photosensitive resin component decreases and the curing is defective, There may be a problem that residue is generated.
Such a photosensitive resin composition is a photosensitive resin composition comprising (a) a pigment mixture, (b) an alkali soluble acrylic binder resin, (c) a cadmium binder resin, (d) a polyfunctional monomer having an ethylenically unsaturated double bond, (e) , The organic additive and the solvent (f) may be mixed by a stirrer and filtered through a 5 탆 membrane filter to prepare a photosensitive resin composition.
Such a photosensitive resin composition is coated on a glass substrate having a clean surface or a glass substrate (for example, ITO or IZO deposited glass substrate) including a transparent electrode layer by a spin coater Non-contact type coating apparatus.
In the preparation and application, a silane coupling agent may be blended or applied to the substrate to improve adhesion between the substrate and the photosensitive resin composition.
After the application, the coated substrate is dried with a hot plate at a temperature of 80 to 120 DEG C, preferably 80 to 100 DEG C for 60 to 150 seconds, or left at room temperature for several hours to several days, or in a hot air heater, (Aka, pre-bake) coating film thickness is adjusted to be in the range of 1.0 to 5 mu m by removing the solvent for several hours, and then an active ray energy line such as ultraviolet rays is irradiated through the mask at an irradiation energy dose of 30 to 1000 mJ / cm < 2 >. The irradiation energy dose may vary depending on the type of the light-shielding film photosensitive composition to be used. The film obtained by exposure is developed with a developing solution by a dipping method, a spraying method or the like to form a cured film pattern. Examples of the developing solution used in the development include organic solvents such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.
Post-baking may be performed after development, and more specifically, it may be preferable to perform post-baking at 150 to 250 ° C for 20 to 40 minutes.
The light-shielding film obtained according to one embodiment of the present invention preferably satisfies appropriate light-shielding properties while having a proper light-shielding property when the fluorine content per 1 g of the cured film is about 5 to 50% by weight.
The cured film thus obtained has an appropriate light shielding property and satisfies appropriate hydrophobicity, and can be particularly useful for forming a light shielding pattern in forming a colored layer by a jetting method using an inkjet print.
A liquid crystal display device is mainly described above, but the present invention is not limited thereto. For example, various display devices requiring a colored layer include a plasma display panel A display device, an EL display device, and a display device such as a CRT display device.
The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices. The display device of the present invention can be applied to various display devices such as Electronically Controlled Birefringence (ECB), Twisted Nematic (TN), In-Plane Switching (IPS), Ferroelectric Liquid Crystal (FLC), Optically Compensatory Bend (OCB), Supern Twisted Nematic Aligned), HAN (Hybrid Aligned Nematic), and GH (Guest Host). It goes without saying that the display device having the colored layer formed by the photosensitive resin composition of the present invention can also be applied to a large screen display device such as a notebook display or a television monitor.
Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.
& Lt ; Preparation Examples 1 to 5 > Examples of synthesis of a cadmium-based binder resin
A 1L four-necked flask was charged with bisphenol fluorene type epoxy compound, acrylic acid, perfluoroheptanoic acid, triethylamine and hydroquinone in propylene glycol methyl ether acetate (PGMEA) as a solvent, Lt; 0 > C. The solution was slowly heated in a cloudy state and completely dissolved at 100 ° C. When completely dissolved, the temperature was maintained at 90 ° C, and nitrogen was injected at a rate of 25 ml / min, which required 12 hours until the acid value reached the target.
The acid value was measured, and heating and stirring were continued until it was less than 3.0 mg KOH / g. The mixture was cooled to room temperature to obtain a colorless transparent bisphenol fluorene-type epoxy acrylate. The content unit shown in Table 1 is g.
acid
32.57 g of 1,2,3,6-tetrahydrophthalic anhydride was added to 300 g of bisphenol fluorene-type epoxy acrylate thus obtained, and the mixture was gradually heated to react at 120 DEG C for 20 hours to obtain a cationic binder resin ( Production Examples 1 to 5) were obtained.
(3)
<Production Example 6> An example of the alkali-soluble acrylic binder resin synthesis
The components shown in Table 2 below were placed in a 1000 ml four-necked flask, and stirred for 30 minutes while blowing nitrogen therein. Next, the temperature was slowly raised, and the reaction was carried out at 65 ° C for 4 hours. The temperature was raised to 80 ° C and further reacted for 2 hours to synthesize an alkali-soluble acrylic binder resin. The content unit shown in the following Table 2 is g.
(Note) MAA: methacrylic acid, MMA: methyl methacrylate, Sty: styrene
KBM503: 3- (methacryloxypropyl) trimethoxysilane, Shin-Etsu Chemical product
Initiator: Azobisisobutyronitrile
PGMEA: Propylene glycol monomethyl ether acetate
<Examples>
(KLBK-103, manufactured by Mikuni, particle size of 80 to 120 nm, manufactured by Mikuni Co., Ltd.) was added to the alkali-soluble acrylic binder resin obtained from Production Example 6 and the cationic binder resin obtained from Production Examples 1 to 5 as shown in Table 3 below. one) were dissolved, a polyfunctional monomer (dipentaerythritol to pentaerythritol hexaacrylate), placed into a photo-polymerization initiator, a solvent (propylene glycol methyl ether acetate (PGMEA)) and other additives (fluorine-based surfactant and coupling agent) to put 3 hours Followed by stirring to prepare a photosensitive resin composition.
In Table 3, parts by weight are expressed in terms of the content relative to 100 parts by weight of the total binder resin (cadmium binder resin and acrylic binder resin) solids content.
And
Comparative Example
Binder resin
(Production Examples 1 to 5)
Binder resin
Production Example 6
(KLBK-
103)
(PGMEA)
(DPHA)
(GPTMS)
Resin component: 18 wt%
DPHA: dipentaerythritol hexaacrylate
Carbon black: having a particle size of 90 nm to 110 nm
PGMEA: Propylene glycol methyl ether acetate
GPTMS: Glycidoxypropyltrimethoxysilane (Shin-Etsu)
The development start time, pattern line width (resolution), development pattern stability, pattern profile, optical density and the like of the photosensitive resin composition prepared according to the above examples were measured by the following methods, and the results are shown in Table 4 below.
(1) Cured film forming method
Using the thus-obtained photosensitive resin composition, a cured film pattern was formed by the following method; A glass substrate having a clean surface was coated with a spin coater at 500 rpm to form a resin coated layer. After the application, the coated film was dried at 100 DEG C for 100 seconds on a hot plate to give a coating film thickness of 1.5 mu m. Subsequently, active ray energy lines such as ultraviolet rays were exposed through the mask (gap: 100 mu m) to an irradiation energy dose of 30 mJ / cm < 2 >. The exposed film was developed (developing time: 60 seconds) using a developing solution (0.032% KOH aqueous solution, 25 캜) to form a cured film pattern. After development, post-baking was performed for 30 minutes after putting in a 230 ° C convection oven.
(2) Development start time
The development start time was visually confirmed when the resin black matrix was developed in the development process after the resin black matrix was coated on the glass substrate-prebaked-exposing process and the pattern started to be formed.
(3) Pattern line width (resolution)
The pattern line width was determined by coating a resin black matrix on a glass substrate. - Pre-baking - Exposure - Development - After post-baking, arbitrary 10 locations with a line width of 30 um were designed on the mask of the substrate. Line width was measured.
(4) Optical density
The optical density of the cured film obtained as described above was measured using PMT equipment manufactured by Otsuka Electronics Co., Ltd. using a reference having an optical density of 2.4.
(5) Method of measuring contact angle of cured film
5 쨉 l of water (deionized water) was dropped on the cured film obtained as above using a syringe to measure the contact angle with water (deionized water).
The contact angle to 2-ethoxyethanol was also measured using 2-ethoxyethanol (99%, manufactured by Aldrich) instead of water. The contact angle measuring instrument was a product of Kruss (Model E-EM03-T13-01).
(6) Measurement of pattern profile
The taper angle of the obtained cured film pattern was measured by SEM.
(7) Residue
SEM was used to confirm the presence of residues after development.
(8) Development pattern stability
The development pattern stability can be evaluated by the fact that the resin black matrix is coated on the glass substrate-pre-baking-exposing process, and then the development is performed for a predetermined time after the resin black matrix is developed and the pattern starts to be formed The line width of the pattern and the straightness of the pattern were confirmed through a microscope. A period in which the line width of the pattern is reduced to 1 m or less with the developing time of 5 s is confirmed.
And
Example
stability
(/ 탆)
ethanol
From the results shown in Table 4, the contact angles of the cured films obtained from Examples 1, 5 and 9 were increased as the fluorine content in the cadmium binder increased from the results of contact angle measurement with respect to water and 2-ethoxyethanol.
When the color ink is injected by the jetting method using the inkjet print after the light shielding film is formed, the cured films of Examples 2, 3, 4, 6, 7, 8, 10, 11, It is possible to assume that the color ink does not cause problems such as the color ink passing over the partition wall or the color ink deviating from the position defined by the partition wall.
Further, the pattern development stability of Examples 4, 8, and 12 using the cadmium-based binder resin of Production Example 5 is less than 5 seconds, which is worse than the other Examples. When a fluorine content of a certain level or more is added, It can be assumed that it is disadvantageously operated.
In addition, as the content of the alkali soluble acrylic binder resin in the black matrix composition increases, the pattern profile increases (compared with Comparative Examples 1, 2 and 3 and Examples 1, 5 and 9) 11) is comparatively disadvantageous.
As a result, it was found that the contact angle to water was not less than 85 °, the contact angle of 2-ethoxyethanol was not less than 40 °, and the color ink passed through the barrier ribs between the barrier ribs of the cured film, And the most optimal embodiment for preventing or minimizing damage to other evaluation values is 2, 3, 6, 10, and so on.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (13)
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| KR1020100095632A KR101680198B1 (en) | 2010-09-30 | 2010-09-30 | Photopolymerizable resin composition |
| TW100135059A TW201213474A (en) | 2010-09-30 | 2011-09-28 | Photopolymerizable resin composition |
| PCT/KR2011/007208 WO2012044099A2 (en) | 2010-09-30 | 2011-09-30 | Photosensitive resin composition |
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| KR101686567B1 (en) | 2013-10-23 | 2016-12-14 | 제일모직 주식회사 | Photosensitive resin composition and light blocking layer using the same |
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| KR100725023B1 (en) * | 2006-10-16 | 2007-06-07 | 제일모직주식회사 | Cardo type resin-containing resist composition and method for preparing a pattern by the same and a color filter using the same |
| KR100838452B1 (en) * | 2007-03-22 | 2008-06-16 | 제일모직주식회사 | Cardo-based resin having amide bond and photosensitive resin composition comprising the same and black matrix prepared therefrom |
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| KR100838452B1 (en) * | 2007-03-22 | 2008-06-16 | 제일모직주식회사 | Cardo-based resin having amide bond and photosensitive resin composition comprising the same and black matrix prepared therefrom |
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