KR20160046093A - Photosensitive resin composition for pixel - Google Patents
Photosensitive resin composition for pixel Download PDFInfo
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- KR20160046093A KR20160046093A KR1020140141456A KR20140141456A KR20160046093A KR 20160046093 A KR20160046093 A KR 20160046093A KR 1020140141456 A KR1020140141456 A KR 1020140141456A KR 20140141456 A KR20140141456 A KR 20140141456A KR 20160046093 A KR20160046093 A KR 20160046093A
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- acrylate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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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
- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
-
- 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
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
The present invention relates to a photosensitive resin composition excellent in adhesion and chemical resistance, a column spacer, a color filter, and a liquid crystal display device manufactured using the same.
Recently, the display industry has undergone drastic changes from CRTs to flat panel displays represented by PDPs, OLEDs, and LCDs. Among them, a liquid crystal display (LCD) is widely used as an image display device in almost all industries, and its application range is continuously expanding.
Generally, a liquid crystal display device includes a liquid crystal for light transmission control, a TFT array layer which is an electric signal device for driving the liquid crystal, a pixel pattern of red, green and blue on a substrate on which a black matrix is patterned, A color filter layer coated with an overcoat to give a flatness between the TFT array layer and the color filter layer, and a column spacer for holding the cell gap in the step of bonding the TFT array layer and the color filter layer. These members perform pattern formation through the photosensitive resin composition, or exhibit appropriate performance for various factors such as insulation, flatness, and chemical resistance. In order to exhibit appropriate adhesion, chemical resistance, pattern profile, etc., development has been progressed to introduce a suitable structure in a photosensitive resin or to exhibit necessary performance by using an additive component or the like.
As a factor for controlling the developing speed of the photosensitive resin composition, a method of controlling the molecular weight and the acid value of the resin has been proposed. If the acid value is increased beyond a certain range, the adhesive force is decreased, defects such as reverse taper are caused, and defects such as flatness are caused due to an increase in viscosity. In addition, the introduction of the rate control or the adhesion promoter through the additive has a disadvantage that fume is generated in the firing process and particles are generated.
The present invention is to provide a solution to the problems of the conventional art as described above, and it is an object of the present invention to provide a photosensitive resin composition excellent in adhesiveness to a substrate, chemical resistance, permeability and developability.
In addition,
It is an object of the present invention to provide an insulating film and a column spacer manufactured using the photosensitive resin composition, and a color filter and a liquid crystal display including the same.
According to the present invention,
(A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D)
The alkali-soluble resin (A)
Wherein the photosensitive resin composition comprises a monomer derived from the following formula (1).
[Chemical Formula 1]
In Formula 1,
X is a C1-C4 alkylene group;
R 'is hydrogen or a methyl group;
Y is hydrogen, an alkyl group of C20 or less, or an electron withdrawing group (EWG).
In addition,
And a color filter formed using the photosensitive resin composition.
The photosensitive resin composition of the present invention includes an alkali-soluble resin containing an acetoacetyl group, thereby providing a photosensitive resin composition excellent in adhesion with a substrate, developability and permeability. Also, a color filter having improved processability using the photosensitive resin composition of the present invention and a high-quality liquid crystal display device including the same can be provided.
Hereinafter, the present invention will be described in more detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.
According to the present invention,
(A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D)
The alkali-soluble resin (A)
There is provided a photosensitive resin composition comprising a monomer derived from a compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
X is a C1-C4 alkylene group;
R 'is hydrogen or a methyl group;
Y is hydrogen, an alkyl group of C20 or less, or an electron withdrawing group (EWG).
Hereinafter, the constituent elements of the present invention will be described in detail.
(A) an alkali-soluble resin
The alkali-soluble resin (A) contained in the photosensitive resin composition of the present invention serves to make the non-exposed portion of the photosensitive resin layer formed using the photosensitive resin composition of the present invention become alkali-soluble and to remove the exposed region, do.
The alkali-soluble resin (A) of the present invention is characterized by containing a monomer derived from a compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
X is a C1-C4 alkylene group;
R 'is hydrogen or a methyl group;
Y is hydrogen, an alkyl group of C20 or less, or an electron withdrawing group (EWG).
The electron withdrawing group (EWG) includes, as specific examples, carbonyl (-C═O-), nitrile (-CN), nitro (-NO 2 ), sulfuryl (-SO 2 ) COOH), and the like, but the present invention is not limited thereto.
The alkali-soluble resin (A) may contain the reactive alkali-soluble resin (A ') and the non-reactive alkali-soluble resin (A ") either singly or in combination. A ') and the non-reactive alkali-soluble resin (A'') are preferably in a weight ratio of 8: 2 to 2: 8, more preferably 7: 3 to 3: 7. When the weight ratio is the same as above, the residual film ratio and the degree of curing are excellent, and the taper attraction in the column spacer can be reduced.
The reactive alkali-soluble resin (A ') contained in the alkali-soluble resin (A) exhibits reactivity to the photopolymerization initiator or UV irradiation.
The reactive alkali-soluble resin (A ') is a copolymer obtained by polymerization of compounds containing (A1), (A2), (A3) and (A4) A3) with (A4). Also included in the scope of the present invention is the case where other monomers are included and polymerized in addition to the monomers derived from the compounds (A1) to (A4).
The (A1) contained in the reactive alkali-soluble resin (A ') is not limited as long as it is a compound containing an unsaturated bond and an acetoacetyl group in one molecule. When such an acetoacetyl group is contained, the effect of increasing the acid value and controlling the alkali-soluble characteristics can be provided. As an example of a compound containing an unsaturated bond and an acetoacetyl group in the above-mentioned one molecule,
Acetoacetylmethyl (meth) acrylate; Acetoacetylethyl (meth) acrylate; Acetoacetylpropyl (meth) acrylate; Acetoacetyl butyl (meth) acrylate; Acetoacetylalkyl (meth) acrylates such as acetoacetylhexyl (meth) acrylate;
(Meth) acrylate, acetoacetoxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, acetoacetoxyethyl Acetoacetoxyalkyl (meth) acrylate such as acetoacetoxyhexyl (meth) acrylate;
Acetoacetate compounds such as styryl acetoacetate, isopropenyl acetoacetate, hex-5-enyl acetoacetate, allylacetoacetate or vinylacetoacetate;
Acetoacetoxyalkyl crotonate such as acetoacetoxyethyl crotonate or acetoacetoxypropyl crotonate, and the like, but the present invention is not limited thereto. .
(A2) contained in the reactive alkali-soluble resin (A ') is not limited as long as it is a compound containing an unsaturated bond and a carboxylic acid group in one molecule,
Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;
Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid;
Anhydrides of the dicarboxylic acids;
(meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like. These may be used alone or in combination of two or more. Among these compounds, acrylic acid and / or methacrylic acid are preferred because of their excellent copolymerization reactivity and solubility in a developing solution.
The (A3) contained in the reactive alkali-soluble resin (A ') is not limited as long as it is a compound containing an unsaturated bond polymerizable with (A1) and (A2)
Specific examples of the unsaturated carboxylic acid include unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) Unsubstituted or substituted alkyl ester compounds;
(Meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, pentadienyl An unsaturated carboxylic acid ester compound containing an alicyclic substituent group such as a phenanthryl (meth) acrylate, adamanthyl (meth) acrylate, norbornyl (meth) acrylate or pinenyl (meth) acrylate;
3-ethyloxetane, 3 - ((meth) acryloyloxymethyl) oxetane, 3 - ((meth) acryloyloxymethyl) Unsaturated carboxylic acid ester compounds containing thermosetting substituents such as oxetane and 3 - ((meth) acryloyloxymethyl) -2-trifluoromethyloxetane;
Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;
Unsaturated carboxylic acid ester compounds having a substituted or unsubstituted aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
Aromatic vinyl compounds such as styrene,? -Methylstyrene, vinyltoluene, and N-benzylmaleimide;
Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl propionate;
(Meth) acrylonitrile, and? -Chloroacrylonitrile. Of these, aromatic vinyl compounds are preferable for the purpose of improving sensitivity and reducing outgas.
These may be used alone or in combination of two or more. The (meth) acrylate recorded in this specification means acrylate and / or methacrylate.
(A4) contained in the reactive alkali-soluble resin (A ') is not limited as long as it is a compound containing an unsaturated bond and an epoxy group in one molecule, and specific examples thereof include glycidyl (meth) acrylate, 3,4-epoxycyclo Acrylate, hexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate and the like, more preferably glycidyl These may be used alone or in combination of two or more.
The compound (A4) having an unsaturated bond and an epoxy group in one molecule is preferably reacted in an amount of 5 to 80 mol% based on the molar amount of the compound (A1), more preferably 10 to 80 mol%. (A4) is within the above-mentioned range, it has an advantage of excellent exposure sensitivity and developability.
In the present invention, when the reactive alkali-soluble resin (A ') is obtained by copolymerizing the compounds (A1) to (A4), for example, the following method can be used.
A solvent in an amount of 0.5 to 20 times the total mass of (A1) to (A3) was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube and the atmosphere in the flask was replaced with nitrogen in air . Thereafter, after raising the temperature of the solvent to 40 to 140 캜, a predetermined amount of (A1) to (A3), a solvent of 0 to 20 times the total mass of (A1) to (A3), and a solvent of azobisisobutyl A solution in which 0.1 to 10 mol% of a polymerization initiator such as nitrile or benzoyl peroxide is added to the total molar amount of (A1) to (A3) (stirring or dissolving at room temperature or under heating) is carried out for 0.1 to 8 hours And the mixture is stirred at 40 to 140 DEG C for 1 to 10 hours.
(A4) in a proportion of 5 to 80% by mole with respect to the constitutional unit derived from (A1) in the copolymer by polymerization of the compounds including (A1) to (A3), as a reaction catalyst of a carboxyl group and an epoxy group, For example, tris-dimethylaminomethylphenol is added in an amount of 0.01 to 5% by weight based on the total weight of (A1) to (A4) and 0.001 to 5% by weight of hydroquinone as a polymerization inhibitor, To 130 ° C for 1 to 10 hours, the above-mentioned copolymer can be reacted with (A4).
Further, alpha -methylstyrene dimer or mercapto compound may be used as a chain transfer agent to control molecular weight or molecular weight distribution. The amount of the? -methylstyrene dimer or mercapto compound to be used is 0.005 to 5% by weight based on the total weight of (A1) to (A4). The above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization and the like.
On the other hand, the reactive alkali-soluble resin (A ') contained in the photosensitive resin composition of the present invention is not particularly limited as long as another monomer is further contained in the copolymer resulting from the polymerization of the compounds (A1) to (A4) And are included in the scope of the invention.
That is, by adding other monomers to the copolymer by polymerization of the compounds including (A1) to (A4), light / thermosetting property can be imparted to the alkali-soluble resin to improve heat resistance and chemical resistance.
In the present invention, the reactive alkali-soluble resin (A ') preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the reactive alkali-soluble resin (A ') is in the range of 3,000 to 100,000, film reduction of the exposed portion is unlikely to occur at the time of development and the solubility of the unexposed portion tends to be good.
The acid value of the reactive alkali-soluble resin (A ') may preferably be in the range of 30 to 200 mgKOH / g based on the solid content. When the acid value is less than 30 mgKOH / g, the solubility in an alkaline developer is lowered and there is a fear of leaving residues on the substrate. If the acid value exceeds 200 mgKOH / g, the possibility of pattern peeling may increase.
The molecular weight distribution of the reactive alkali-soluble resin (A ') may preferably be 1.0 to 6.0, more preferably 1.5 to 4.0. When the molecular weight distribution is 1.0 to 6.0, it may be preferable since the developing property is excellent.
The reactive alkali-soluble resin (A ') can be prepared by reacting (A1), (A2), (A3) and (A4) (A2), (A3) and (A4) in the following range.
(A1): 10 to 60 mol%
(A2): 20 to 70 mol%
(A3): 10 to 60 mol%
(A4): 10 to 60 mol%
When the composition ratio is within the above range, a good balance of alkali solubility and heat resistance is obtained, and thus a preferable copolymer can be obtained.
The non-reactive alkali-soluble resin (A ") which can be contained in the alkali-soluble resin (A) exhibits non-reactivity with the photopolymerization initiator and the UV irradiation, and the compounds (A1), (A2) However, as a non-reactive alkali-soluble resin, a copolymer obtained by polymerization of compounds containing (A1) to (A3) as a polymerizable unsaturated double and / or poly It is a copolymer without a triple bond.
The above-mentioned non-reactive alkali-soluble resin (A ") is also included in the scope of the present invention when, after polymerization, other monomers which do not have an unsaturated bond polymerizable in the chain are further contained.
The non-reactive alkali-soluble resin (A ") used in the present invention may be prepared in the same manner as the above-mentioned reactive alkali-soluble resin (A ' (A4) contained in the reactive alkali-soluble resin (A ') can not be included because the polymerization should be carried out in the absence of an unsaturated double bond capable of photopolymerization with the radical photoinitiator. (A1) compound having an acetoacetyl group, a compound (A2) having an unsaturated bond and a carboxylic acid group in one molecule, and a compound (A3) having a polymerizable unsaturated bond and the above-mentioned (A1) ≪ / RTI > The method example is the same as the general synthesis example of the reactive alkali-soluble resin (A '). The compounds (A1) to (A3) may be the same as those exemplified above as the components (A1) to (A3).
In the present invention, the (A ") non-reactive alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 40,000. When the weight average molecular weight of the (A ") non-reactive alkali-soluble resin is in the range of 3,000 to 100,000, film reduction of the exposed portion is unlikely to occur during development and the solubility of the unexposed portion tends to be good.
If the acid value is less than 30 mgKOH / g, the solubility in an alkali developing solution is lowered, and if the acid value of the non-reactive alkali-soluble resin falls below 30 mgKOH / g, If the acid value exceeds 200 mgKOH / g, there is a possibility that pattern peeling may occur.
The molecular weight distribution of the (A ") non-reactive alkali-soluble resin may be preferably 1.0 to 6.0, more preferably 1.5 to 4.0. If the molecular weight distribution is 1.0 to 6.0, have.
(A1), (A2) and (A3), and the proportion of the component derived from each of (A1), (A2) and (A3) (A1) to (A3) in the following range.
(A1): 10 to 70 mol%
(A2): 20 to 80 mol%
(A3): 10 to 70 mol%
When the composition ratio is within the above range, a good balance of alkali solubility and heat resistance is obtained, and thus a preferable copolymer can be obtained.
The alkali-soluble resin (A) generally ranges from 20 to 85% by weight, preferably from 40 to 75% by weight, based on the solid content in the photosensitive resin composition. When the content of the alkali-soluble resin (A) is 20 to 85% by weight based on the above-mentioned criteria, the solubility in the developer is sufficient and development residue is hardly generated on the substrate of the non-pixel portion, , And the solubility of the unexposed portions tends to be good.
The alkali-soluble resin preferably has a weight average molecular weight of 5,000 to 30,000 in view of the chemical resistance and durability of the cured film, and the acid value of 50 to 200 mgKOH / g may be preferable in terms of solubility and adhesion.
(B) Photopolymerization compound
The photopolymerizable compound (B) contained in the photosensitive resin composition of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers .
Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone And the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of A, and 3-methylpentanediol di (meth) acrylate.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol Acrylate, trimethylolpropane trimethacrylate, tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Of these, polyfunctional monomers having two or more functionalities can be preferably used, and more preferably, polyfunctional monomers having five or more functionalities can be used.
The photopolymerizable compound (B) may be used in an amount of usually 10 to 60% by weight, preferably 20 to 50% by weight based on the solid content in the photosensitive resin composition. When the photopolymerizable compound (B) is in the range of 10 to 60% by weight based on the above-mentioned criteria, the strength of the pixel portion, the residual film ratio according to the progress of the process, and the contact hole characteristics tend to be favorable.
(C) Photopolymerization initiator
The photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention is not particularly limited, but is at least one compound selected from the group consisting of triazine-based compounds, acetophenone-based compounds, nonimidazole-based compounds and oxime compounds. The photosensitive resin composition containing the photopolymerization initiator (C) described above has a high sensitivity, and therefore the film formed using this composition has good strength and contact hole characteristics of the pixel portion.
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, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one oligomers and the like. Further, a compound represented by the following general formula (2) can be mentioned.
(2)
In Formula 2,
R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group substituted or unsubstituted with an alkyl group.
Specific examples of the compound represented by Formula 2 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan- (4-morpholinophenyl) propane-1-one, 2-amino-2- 2-methyl-2-methylamino (4-morpholinophenyl) propane-1-one, 1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan- have.
Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4' An imidazole compound substituted by a haloalkoxy group, and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 5,5'-tetraphenylbiimidazole is preferably used.
Examples of the oxime compounds include the following formulas (3), (4) and (5).
(3)
[Chemical Formula 4]
[Chemical Formula 5]
Further, as long as the effect of the present invention is not impaired, other photopolymerization initiators generally used in this field can be further used in combination. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.
Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-di (N, N'-dimethylamino) -benzophenone.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .
Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .
Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other photopolymerization initiators.
According to a preferred embodiment of the present invention, when the photopolymerization initiator (C-1) is used in combination with the photopolymerization initiator (C-1), the photosensitive resin composition containing the photopolymerization initiator becomes more sensitive, The productivity in the formation can be improved.
The above-mentioned (C-1) photopolymerization initiator which can be used in combination with the photopolymerization initiator (C) of the present invention is preferably at least one compound selected from the group consisting of an amine compound and a carboxylic acid compound.
Specific examples of the amine compound in the above (C-1) photopolymerization initiation assistant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine;
4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4- Aromatic amine compounds such as bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone; And the like. As the amine compound, an aromatic amine compound is preferably used.
Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenyl And aromatic heteroacetic acids such as thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
The content of the photopolymerization initiator (C) in the photosensitive resin composition of the present invention may be from 0.1 to 20% by weight, preferably from 1 to 10% by weight based on the total solid content in the photosensitive resin composition, and (C-1) The amount of the initiator aid to be used may be generally from 0.1 to 20% by weight, preferably from 1 to 10% by weight, based on the above criteria.
When the amount of the photopolymerization initiator (C) to be used is within the above range, the photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion and the smoothness on the surface of the pixel portion tend to be favorable. When the amount of the photopolymerization initiator (C-1) is in the above range, the sensitivity of the photosensitive resin composition is further increased, and the productivity of the color filter formed using the composition tends to be improved. .
(D) Solvent
The solvent (D) contained in the photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of the photosensitive resin composition can be used.
Specific examples of the solvent (D) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as? -butyrolactone; And the like.
Among the above solvents, organic solvents having a boiling point of 100 ° C to 200 ° C in the solvent are preferably used from the viewpoint of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3- Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3- (3-methoxypropionate) and the like, and more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Ethyl ethoxypropionate, methyl 3-methoxypropionate, and the like.
These (D) solvents may be used alone or in combination of two or more.
The content of the solvent (D) in the photosensitive resin composition of the present invention may be generally 60 to 90% by weight, preferably 70 to 85% by weight based on the total amount of the photosensitive resin composition containing the solvent. When the content of the solvent (D) is in the range of 60 to 90% by weight based on the above criteria, it may be applied by a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) It may be preferable since the coating property tends to be good.
(E) Additive
The photosensitive resin composition of the present invention may further include UV stabilizers, fillers, other polymer compounds, curing agents, dispersants, adhesion promoters, antioxidants, and antiflocculants as necessary in addition to the above components.
The UV stabilizer can be included in the photosensitive resin composition to secure the light resistance.
Specific examples of the UV stabilizer include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives.
Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- Dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone.
Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, p-tart-butylphenyl salicylate, 2,4-di-tart- -4-hydroxybenzoate, and hexadecyl-3,5-di-tart-butyl-4-hydroxybenzoate.
Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- 5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di- Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tart-amylphenyl) benzotriazole and the like .
Specific examples of the triazine derivatives include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.
The UV stabilizer may also be a commercially available one such as TINUVIN PS, TINUVIN 99-2, INUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVIN 1577 , CHIMASSORB81 (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name), and the like.
The UV stabilizer may preferably have a maximum absorption region at 350 nm or less (inclusive of j-line) in the wavelength region. A UV stabilizer having a maximum absorption region of 350 nm or more may weaken the irradiation intensity of i-line. From the viewpoint of the structure of the UV stabilizer, benzophenone derivatives and triazine derivatives have a good absorption region at 350 nm or less. Commercially available products include TINUVIN 400, TINUVIN 1577, CHIMASSORB81, and the like.
The above-mentioned UV stabilizers can be used alone or in combination of two or more kinds, and the light resistance and yellowing of the photosensitive resin composition of the present invention can be prevented.
Specific examples of the filler include glass, silica, and alumina.
Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane .
The curing agent is used for increasing the hardness of the deep portion and the mechanical strength. Examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound and an oxetane compound.
Examples of the epoxy compound in the curing agent include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a Novolak epoxy resin, an aromatic epoxy resin, Based epoxy resins, glycidyl ester-based resins, glycidylamine-based resins, aliphatic, alicyclic or aromatic epoxy compounds other than the brominated derivatives, epoxy resins and brominated derivatives of such epoxy resins, butadiene (co) polymeric epoxides , Isoprene (co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.
Examples of the oxetane compound in the curing agent include carbonates such as carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like. have.
The curing agent may further comprise a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with a curing agent. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like. As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents can be used. As the epoxy resin curing agent, for example, there may be mentioned epoxy resin curing agents such as trade name (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade name (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). These curing agents may be used alone or in combination of two or more.
As the dispersing agent, a commercially available surfactant can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), And polyethyleneimine, (Manufactured by Asahi Glass Co., Ltd.), Surfon (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kasei Kogyo Co., Ltd., MEGAFAC (manufactured by Dainippon Ink and Chemicals Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.
These dispersants may be used alone or in combination of two or more, and may be contained in an amount of usually 0.01 to 15% by weight based on the solid content in the photosensitive resin composition.
Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. These adhesion promoters may be used alone or in combination of two or more, and may contain 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solid content in the photosensitive resin composition.
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.
Specific examples of the anti-flocculant include sodium polyacrylate and the like.
The photosensitive resin composition for forming a pixel of the present invention can be produced, for example, by the following method. (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a solvent in an appropriate ratio, and further adding other components as needed to obtain a desired photosensitive resin composition .
Hereinafter, a pattern forming method using the photosensitive resin composition according to the present invention will be described.
The method for forming a pattern of a photosensitive resin composition according to the present invention comprises the steps of applying the above-mentioned photosensitive resin composition onto a substrate, selectively exposing a part of the photosensitive resin composition, and exposing the photosensitive resin composition to an exposure area or a non- And removing the exposure area.
As an example, it is coated on a substrate as follows to form a pattern by photo-curing and development, and can be used for the production of a black matrix or a transparent pixel.
More specifically, the composition is first applied on a substrate (not limited to glass or silicon wafer in general) or a layer containing a solid content of a previously formed photosensitive resin composition and preliminarily dried to remove volatile components such as a solvent, . The thickness of the coating film at this time is usually about 1 to 3 mu m. Ultraviolet rays are applied to a specific region through a mask to obtain a desired pattern on the thus obtained coating film. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel rays, and the mask and the substrate are accurately positioned. Thereafter, the coated film after curing is brought into contact with the aqueous alkaline solution to dissolve and expose the non-exposed region, thereby making it possible to produce a desired pattern. After development, if necessary, post-drying may be performed at about 150 to 230 DEG C for about 10 to 60 minutes.
On the other hand, the developer used for development after patterned exposure may be an aqueous solution containing an alkaline compound and a surfactant.
The alkaline compound may be either an inorganic or an organic alkaline compound.
Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.
Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoiso Propylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more.
The preferred concentration of the alkaline compound in the alkaline developer may be in the range of 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.
The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant or a cationic surfactant.
Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.
Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.
Each of these surfactants may be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.
The present invention also provides a color filter formed using the photosensitive resin composition of the present invention and a liquid crystal display device including the color filter.
Hereinafter, a color filter according to the present invention will be described.
The color filter according to the present invention is characterized by including a pixel formed by forming the above-mentioned photosensitive resin composition in a predetermined pattern, followed by exposure and development.
The pattern forming method of the photosensitive resin composition is described above, and a detailed description thereof will be omitted.
As described above, a pixel or a black matrix corresponding to the photosensitive resin composition is obtained through the application of the photosensitive resin composition solution, the drying, the patterned exposure to the dry film obtained, and the development, By repeating the number of required unit pixels, a color filter can be obtained.
The construction and manufacturing method of the color filter are well known in the art, and a detailed description thereof will be omitted.
The color filter produced by using the colorless photosensitive resin composition for pixel formation of the present invention has a small difference in the inter-pixel film thickness in the plane, for example, a film thickness of 1 to 4 mu m and an in-plane film thickness difference of 0.15 mu m or less, Mu m or less. Therefore, the color filter thus obtained has excellent smoothness, and by incorporating it into a color liquid crystal display device, a liquid crystal display device of excellent quality can be manufactured with high yield. In addition, by using the color filter described above, it is possible to manufacture an image pickup device of good quality.
Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to the following examples, and "%" and "parts" in the following examples and comparative examples are based on weight unless otherwise specified.
< Synthetic example >
Synthesis Example 1 : Alkali-soluble resin ( a1 ) Synthesis of
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, and 15 parts by weight of acetoacetoxymethyl methacrylate, 15 parts by weight of hydroxy methacrylate, 45 parts by weight, methacrylic acid 15 parts by weight, tricyclodecyl methacrylate 10 parts by weight, t-butylperoxy-2-ethylhexanoate 4 parts by weight, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA" 40 parts by weight) was added thereto, followed by stirring and mixing to prepare a monomer dropping tank. 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and stirred to prepare a chain transfer agent dropwise.
Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was raised to 90 DEG C while stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was heated to 110 DEG C for 1 h and held at this temperature for 3 hours. Thereafter, the mixture was cooled to room temperature to obtain an alkali having a solid content of 29.1 wt% and a weight average molecular weight of 25,000 and an acid value of 140 mgKOH / g To obtain a soluble resin a1.
Synthetic example 2: Alkali-soluble resin ( a2 ) Synthesis of
An alkali-soluble resin was synthesized in the same manner as in Synthesis Example 1, and the temperature was maintained at 90 占 폚 for 2 hours, and the temperature was elevated to 110 占 폚 for 1 hour and maintained for 3 hours. Then, Bubbling of 5/95 (v / v) mixed gas was started. Then, 10 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part by weight of triethylamine were charged into a flask, The reaction was continued and then cooled to room temperature to obtain an alkali-soluble resin a2 having a solid content of 29.1 wt% and a weight average molecular weight of 30,000 and an acid value of 114 mgKOH / g.
Synthetic example 3: Alkali-soluble resin ( a3 ) Synthesis of
An alkali-soluble photosensitive resin was synthesized in the same manner as in Synthesis Example 1, except that 30 parts by weight of hydroxy methacrylate was added instead of 15 parts by weight of acetoacetoxy methyl methacrylate. An alkali-soluble resin a3 having a solid content of 29.1% by weight and a weight-average molecular weight of 29,000 and an acid value of 120 mgKOH / g was obtained.
Synthetic example 4: Alkali-soluble resin ( a4 ) Synthesis of
An alkali-soluble resin was synthesized in the same manner as in Synthesis Example 3, and glycidyl methacrylate was added in the same manner as in Synthesis Example 2 to synthesize an alkali-soluble photosensitive resin. An alkali-soluble resin a4 having a solid content of 29.1% by weight and a weight-average molecular weight of 30,000 and an acid value of 100 mgKOH / g was obtained.
Molecular weight evaluation
The weight average molecular weight (M w ) of the alkali-soluble resin (A) was measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)
Column temperature: 40 DEG C
Mobile phase solvent: tetrahydrofuran
Flow rate: 1.0 ml / min
Injection amount: 50 μl
Detector: RI
Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)
Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)
Solids
The polymer solution was weighed in an amount of about 1 g into an aluminum cup, and about 3 g of acetone was added to dissolve it, followed by natural drying at room temperature. Then, it was dried in a vacuum at 160 ° C for 3 hours using a hot-air drier (trade name: PHH-101, manufactured by Espec Co., Ltd.), then cooled in a desiccator and weighed. The solid content of the polymer solution was calculated from the weight reduction amount.
Acid value
3 g of the resin solution was subjected to crystallization and dissolved in a mixed solvent of 90 g of acetone and 10 g of water. Using an automatic titration apparatus (manufactured by Hiranuma Industrial Co., Ltd., trade name: COM- 555), and the acid value per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.
< Example And Comparative Example >
Example 1 to 9 and Comparative Example 1 to 4: Preparation of Photosensitive Resin Composition for Pixel Forming
Each of the components was mixed as shown in Table 1, diluted with propylene glycol monomethyl ether acetate (solvent) so that the total solid content was 18% by weight, and sufficiently stirred to obtain a photosensitive resin composition.
The compound (B)
Initiator (C)
week)
(B): Photopolymerization compound
Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
(C): Photopolymerization initiator
1,2-octanediol 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] (IRGACURE OXE01, manufactured by Ciba Specialty Chemical)
(D): solvent
Propylene glycol monomethyl ether acetate (PGMEA)
< Glass Board Manufacturing example >
Color filters and transparent films were prepared using the photosensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 4. That is, the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were applied on a glass substrate by spin coating, and then placed on a heating plate and held at a temperature of 100 캜 for 3 minutes to form a thin film. Subsequently, a test photomask having a square pattern of width x 50um x 50um to 10um x 10um and a line / space pattern of 1 mu m to 100 mu m was placed on the thin film and the distance between the test photomask and the test photomask was set to 300 mu m, Respectively. At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 40, 50 and 60 mJ / cm 2 using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI Co., .
The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 80 seconds to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 25 minutes to prepare a color filter and a transparent film. The film thickness of the photosensitive resin composition prepared by the above method was 3.0 탆.
< Experimental Example >
The taper drag of the color filter manufactured in the above production example, the exposure / development residual film ratio and the like were measured and evaluated as follows, and the results are shown in Table 2 below.
Residual film ratio evaluation
Each of the photosensitive resin compositions was coated on a glass substrate by a spin coating method and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a thin film. Ultraviolet rays of 50 mJ / cm 2 Then, the film thickness of the pattern was measured using a film thickness measuring device (DEKTAK 6M; Veeco). After the thickness measurement was completed, the substrate was again dipped in a KOH aqueous solution of pH 10.5 for 80 seconds, and then the thickness was measured.
(%) = Thickness after development (占 퐉) / pre-development thickness (占 퐉)
When the residual film ratio was 85% or less, it was judged that the film hardness was weak and the process margin was greatly influenced.
Top / Bottom CD Size, adhesion Residue And Azure evaluation
A 13um column spacer of a photomask was formed on the substrate prepared in the above production example, the size of the column spacer CD was measured, and the residue and the remaining film were observed and then photographed. The CD size of the column spacer was measured by measuring the CD size (Top CD) at the 95% of the thickness of the column spacer formed by observing with a 3D microscope, calculating the CD size (bottom CD) at the thickness of 20% Respectively.
3D microscope equipment: Keynes VT-XXXX
[Residue evaluation criteria]
O: Taper free state
△: Taper drag of one side is 2um or less
X: Taper pull of one side is more than 3um
[Adhesion Evaluation Criteria]
5-20 μm (1um interval) on the mask indicates the minimum size of the reproduced column spacer remaining after development.
Evaluation of transmittance
The transmittance of a 10 mm X 10 mm front exposed part was measured using a Uv-vis spectrometer using a photomask of 40 mm x 40 m on the substrate prepared in the above-mentioned production example.
Reliability evaluation
The substrate prepared in this Preparation Example was immersed in NMP (N-methyl-2-pyrrolidone) and heated at 100 ° C for 30 minutes to measure the thickness change before and after the film.
[Evaluation criteria for NMP resistance]
O: Greater than 98%
?: 95% to 98%
X: less than 95%
of mine ITO Gender evaluation
ITO sputtering was performed on the substrate prepared in the above production example to a thickness of 1000 Å to measure changes in film wrinkles.
[My ITO Evaluation Criteria]
O: no wrinkles
X: state of film wrinkle
of mine Etchability evaluation
The substrate prepared as described above was immersed in an ITO etchant at 60 ° C for 10 minutes, and the change in film thickness before and after immersion was measured and expressed as a percentage.
[Etching property evaluation criteria]
O: Greater than 98%
?: 95% to 98%
X: less than 95%
(um)
(T% at 400 nm)
As can be seen from Table 2, when the photosensitive resin composition comprising the alkali-soluble resin containing the compound of Formula 1 of the present invention was used, the color filter or the transparent resin having excellent adhesion, adhesion and NMP reliability as in Examples 1 to 9 A film was obtained. However, when a photosensitive resin composition containing an alkali-soluble resin not containing the compound of the formula (1) is used, undesirable color filters such as residues, adhesiveness of 10um or more, / Or a transparent film was formed.
When a photosensitive resin composition containing an alkali-soluble resin containing the compound of Chemical Formula 1 is used, an excellent T / B ratio of 0.6 or more as in Examples 1 to 9 is obtained even when the molecular weight is 20,000 or more when forming a CS there was. However, when the alkali-soluble resin not containing the compound of the formula (1) was included, it was found that the molecular weight had a T / B ratio of 20,000 or more to 0.5 or less.
Claims (11)
The alkali-soluble resin (A)
A photosensitive resin composition comprising a monomer derived from a compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
X is a C1-C4 alkylene group;
R 'is hydrogen or a methyl group;
Y is hydrogen, an alkyl group of C20 or less, or an electron withdrawing group (EWG).
The alkali-soluble resin includes a photopolymerization initiator or a reactive alkali-soluble resin (A ') which shows reactivity to UV irradiation; And
A photopolymerization initiator, and a non-reactive alkali-soluble resin (A ") which exhibits non-reactivity against UV irradiation.
The alkali-soluble resin (A) is a compound (A1) containing one unsaturated bond and an acetoacetyl group in one molecule; A compound (A2) containing an unsaturated bond and a carboxylic acid group in one molecule; A compound (A3) comprising a polymerizable unsaturated bond with (A1) and (A2); And a compound (A4) containing a unsaturated bond and an epoxy group in one molecule.
Wherein the alkali-soluble resin (A) comprises a reactive alkali-soluble resin (A ') and a non-reactive alkali-soluble resin (A ") in a weight ratio of 8: 2 to 2: 8.
The compound (A1) containing an unsaturated bond and an acetoacetyl group in the above-
(Meth) acrylate, acetoacetyl (meth) acrylate, acetoacetyl (meth) acrylate, acetoacetyl ethyl (meth) acrylate, acetoacetyl (Meth) acrylate, isopropenyl acetoacetate, isopropenyl acetoacetate, hex-5-enyl acetone, One or two selected from the group consisting of hex-5-enyl acetoacetate, allyl acetoacetate, vinylacetoacetate, acetoacetoxyethyl crotonate and acetoacetoxypropyl crotonate. Type or more.
The compound (A2) containing an unsaturated bond and a carboxylic acid group in one molecule is a mono-carboxylic acid, a dicarboxylic acid, an anhydride of the dicarboxylic acid, and a mono ) Acrylates; and at least one member selected from the group consisting of
The compound (A3) containing a polymerizable unsaturated bond with the above-mentioned (A1) and (A2) can be obtained by reacting an unsubstituted or substituted alkyl ester compound of an unsaturated carboxylic acid; An unsaturated carboxylic acid ester compound containing an alicyclic substituent; An unsaturated carboxylic acid ester compound containing a thermosetting substituent; Mono-saturated carboxylic acid ester compounds of glycols; An unsaturated carboxylic acid ester compound having a substituted or unsubstituted aromatic ring; Aromatic vinyl compounds; Carboxylic acid vinyl ester compounds; And at least one member selected from the group consisting of vinyl cyanide compounds.
The compound (A4) having an unsaturated bond and an epoxy group in one molecule is preferably a compound selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (Meth) acrylate and methyl glycidyl (meth) acrylate.
With respect to the solid content in the photosensitive resin composition,
20 to 85% by weight of an alkali-soluble resin;
10 to 60% by weight of photopolymerizable compound; And
0.1 to 20% by weight of a photopolymerization initiator; And it includes a
Based on the total weight of the photosensitive resin composition,
And 60 to 90% by weight of a solvent.
Wherein the alkali-soluble resin has an acid value of 50 to 200 mgKOH / g and a weight-average molecular weight of 5,000 to 30,000.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140141456A KR20160046093A (en) | 2014-10-20 | 2014-10-20 | Photosensitive resin composition for pixel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140141456A KR20160046093A (en) | 2014-10-20 | 2014-10-20 | Photosensitive resin composition for pixel |
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| KR20160046093A true KR20160046093A (en) | 2016-04-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663262A (en) * | 2016-07-28 | 2018-02-06 | 住友化学株式会社 | Resin, hardening resin composition and cured film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140034956A (en) | 2012-09-10 | 2014-03-21 | 동우 화인켐 주식회사 | Alkali soluble polymer composition and method of manufacturing the same |
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2014
- 2014-10-20 KR KR1020140141456A patent/KR20160046093A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140034956A (en) | 2012-09-10 | 2014-03-21 | 동우 화인켐 주식회사 | Alkali soluble polymer composition and method of manufacturing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663262A (en) * | 2016-07-28 | 2018-02-06 | 住友化学株式会社 | Resin, hardening resin composition and cured film |
| JP2022010246A (en) * | 2016-07-28 | 2022-01-14 | 住友化学株式会社 | Resin, curable resin composition and cured film |
| JP7256247B2 (en) | 2016-07-28 | 2023-04-11 | 住友化学株式会社 | Resin, curable resin composition and cured film |
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