KR20160038279A - Photosensitive resin composition for pixel - Google Patents
Photosensitive resin composition for pixel Download PDFInfo
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- KR20160038279A KR20160038279A KR1020140130851A KR20140130851A KR20160038279A KR 20160038279 A KR20160038279 A KR 20160038279A KR 1020140130851 A KR1020140130851 A KR 1020140130851A KR 20140130851 A KR20140130851 A KR 20140130851A KR 20160038279 A KR20160038279 A KR 20160038279A
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- photosensitive resin
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
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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
-
- 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
-
- 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
-
- 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
Abstract
The present invention relates to a photosensitive resin composition excellent in storage stability, reactivity and chemical resistance by including an alkali-soluble resin containing a monomer derived from a compound having a carboxyl group and having an aliphatic polycyclic epoxy group, And a liquid crystal display device.
Description
The present invention relates to a photosensitive resin composition for forming a pixel which is excellent in transparency and excellent in curability and chemical resistance, a color filter manufactured using the composition, and a liquid crystal display device.
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. Such a liquid crystal display (LCD) is widely used in all industrial fields such as portable equipment, industrial machinery, military, and medical applications.
2. Description of the Related Art Devices such as liquid crystal display devices and solid-state image pickup devices include members such as a color filter substrate on which colored pixels are formed on a substrate such as a glass substrate or a silicon wafer, or an array substrate on which driving elements and wirings are formed. These members may be subjected to severe treatment such as being immersed in an acid or an alkali solution in the manufacturing process, exposed to a high temperature locally by sputtering when the driving element or wiring is formed, or the like. For this reason, a protective film may be formed on the surface of the member in order to prevent damage to the member from the manufacturing process. This protective film is required to have characteristics capable of withstanding the above-mentioned severe treatment. Specifically, the protective film is required to have high adhesiveness to a substrate or a base material, high surface hardness, high transparency, excellent solvent resistance and heat resistance Is required. Examples of the thermosetting resin composition usable for such a protective film include a binder resin composed of an acrylic copolymer having an epoxy group represented by a carboxyl group and a glycidyl ether group, a thermosetting composition containing a polymerizable compound having an ethylenic unsaturated bond and a heat radical generating compound (Patent Document 1).
There is also known a thermosetting resin composition capable of forming a coating film (coating film) excellent in transparency and surface hardness through thermal curing. However, the photosensitive resin composition containing a carboxyl group and a glycidyl ether group at the same time has a disadvantage that storage stability at room temperature is poor, and when a glycidyl ether group is added to a carboxylic acid and a hydroxyl group to give a reactor, There is a disadvantage in that the molecular weight is increased due to the reaction of the glycidyl ether group.
SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art,
Soluble resin, which is excellent in storage stability, reactivity and transparency by shortening a carboxyl group in an alkali-soluble resin.
In addition,
An object of the present invention is to provide a transparent insulating film and a column spacer which are excellent in transparency and solvent resistance produced by using the above photosensitive resin composition and have no residue /
Also,
And a color filter and a liquid crystal display including the column spacer.
According to the present invention,
(A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D)
The alkali-soluble resin (A)
A monomer derived from a compound represented by the following formula (1); And
Monomers having an aliphatic polycyclic epoxy group; The present invention provides a photosensitive resin composition.
[Chemical Formula 1]
In Formula 1,
R is a C2-C6 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,
R 'is hydrogen or methyl (-CH 3),
Y is a group selected from the groups represented by the following formulas (Y1 to Y4).
(Y1)
[Y2]
[Y3]
[Y4]
In addition,
There is provided a color filter formed using the photosensitive resin composition for forming a pixel.
The photosensitive resin composition of the present invention can provide an advantage of excellent storage stability and reactivity by containing an alkali-soluble resin having a long carboxyl group and an aliphatic polycyclic epoxy group. In addition, the photosensitive resin composition of the present invention can provide the advantages of excellent hardness and chemical resistance reliability by enhancing the curing degree of the photosensitive resin due to the simultaneous presence of the photo-curing component and the thermosetting component in the photosensitive resin, And a column spacer can be formed at the same time, and a liquid crystal display device including the same.
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)
A monomer derived from a compound represented by the following formula (1); And
Monomers having an aliphatic polycyclic epoxy group; The present invention provides a photosensitive resin composition.
[Chemical Formula 1]
In Formula 1,
R is a C2-C6 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,
R 'is hydrogen or methyl (-CH 3),
Y is a group selected from the groups represented by the following formulas (Y1 to Y4).
(Y1)
[Y2]
[Y3]
[Y4]
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.
In the prior art, an alkali-soluble resin containing a carboxyl group and a glycidyl ether group, a photopolymerization initiator and an alkali-soluble resin having a reactive group for UV irradiation were polymerized and mixed. In this case, there is a disadvantage in that heat resistance and chemical resistance are poor due to no bonding between the two resins.
In order to solve such a problem,
A monomer derived from a compound represented by the following formula (1); And
Monomers having an aliphatic polycyclic epoxy group; An alkali-soluble resin.
[Chemical Formula 1]
In Formula 1,
R is a C2-C6 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,
R 'is hydrogen or methyl (-CH 3),
Y is a group selected from the groups represented by the following formulas (Y1 to Y4).
(Y1)
[Y2]
[Y3]
[Y4]
The alkali-soluble resin (A) may contain the reactive alkali-soluble resin (A ') and the non-reactive alkali-soluble resin (A "
(A ') is preferably in a weight ratio of 9: 1 to 1: 9, more preferably 7: 3 to 3: 7, in the weight ratio of the reactive alkali-soluble resin (A') to the non-reactive alkali- 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 ') may be a copolymer obtained by polymerization of a compound containing the compounds (A1), (A2), (A3) and (A4) ) With (A4) in the presence of a catalyst. It is also within the scope of the present invention that further monomers other than monomers derived from the above-mentioned compounds (A1) to (A4) are added and polymerized.
The compound (A1) contained in the reactive alkali-soluble resin (A ') may be a compound of the following formula (1) or a combination of a compound of the following formula (1) and one or more compounds containing an unsaturated bond and a carboxylic acid group in one molecule .
[Chemical Formula 1]
In Formula 1,
R is a C2-C6 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,
R 'is hydrogen or methyl (-CH 3),
Y is a group selected from the groups represented by the following formulas (Y1 to Y4).
(Y1)
[Y2]
[Y3]
[Y4]
Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-4), but are not limited thereto.
[Formula 1-1]
[Formula 1-2]
[Formula 1-3]
[Formula 1-4]
In the above formulas 1-1 to 1-4, R 'may be hydrogen or methyl (-CH 3 ), but is not limited thereto.
Specific examples of the compound containing an unsaturated bond and a carboxylic acid group within one molecule 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;
ω-carboxypolycaprolactone mono (meth) acrylate, and other mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals, but are not limited thereto.
The compound (A2) contained in the reactive alkali-soluble resin (A ') is preferably a compound having an unsaturated double bond capable of polymerization with an aliphatic polycyclic epoxy group, and is preferably at least one selected from the following formulas (I) to (II).
(I)
≪ RTI ID = 0.0 &
In the above general formulas (I) to (II)
R is independently hydrogen or a C1-C4 alkyl group, and the alkyl group may include a hydroxyl group,
X is a C1-C6 alkylene group which may contain at least one member selected from N, O, S and P in a single bond or a chain.
The (A3) contained in the reactive alkali-soluble resin (A ') is not limited as long as it is a compound having 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) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl 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;
Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;
Unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate, phenoxy (meth) acrylate and the like;
Aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as (meth) acrylonitrile and? -Chloroacrylonitrile;
Maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide.
These may be used alone or in combination of two or more. Of these, aromatic vinyl compounds are preferred for improvement of sensitivity and loss of outgas, and they 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 having an unsaturated bond and an epoxy group in one molecule, and specific examples thereof include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (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 the molecule has a molar ratio of 5 to 5 based on the number of moles of the compound (A1) contained in the copolymer by polymerization of the compounds containing (A1), (A2) To 80 mol%, and more preferably 10 mol% to 80 mol%. (A4) is within the above-mentioned range, it has an advantage of excellent exposure sensitivity and developability.
The reactive alkali-soluble resin (A ') is a copolymer obtained by reacting the above-mentioned compounds (A1) to (A4), and may include a monomer represented by the following formula (5).
[Chemical Formula 5]
In Formula 5,
R is a C2-C6 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,
R 'is hydrogen or methyl (-CH 3),
Y is a group selected from the groups represented by the following formulas (Y1 to Y4)
(Y1)
[Y2]
[Y3]
[Y4]
Z may be a C1-C60 alkyl group containing a reactive group, and the alkyl group may include a hydroxyl group and the like.
The reactive group is preferably an acrylate group, but is not limited thereto.
The monomer represented by the formula (5) may include monomers represented by the following formulas (6) to (9), but is not limited thereto.
[Chemical Formula 6]
(7)
[Chemical Formula 8]
[Chemical Formula 9]
In the present invention, the reactive alkali-soluble resin (A ') is obtained, for example, by copolymerizing the compounds (A1), (A2), (A3) and (A4) .
A solvent in an amount of 0.5 to 20 times the weight of (A1) to (A3) is introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, and the atmosphere in the flask is 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 weight 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, for example, (A) can be reacted with the above-mentioned copolymer by reacting at 60 to 130 ° C for 1 to 10 hours.
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 40,000, more preferably 5,000 to 30,000. When the weight average molecular weight of the reactive alkali-soluble resin (A ') is in the range of 3,000 to 40,000, film reduction of the exposed portion is unlikely to occur during 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 150 mgKOH / g on the solid basis. If the acid value is less than 30 mgKOH / g, the solubility in the alkaline developer may be lowered and the residue may be left on the substrate. If the acid value exceeds 150 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 polymerizing (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 a photopolymerization initiator and non-reactivity to UV irradiation, and is obtained by polymerization of the compounds containing (A1) to (A3) But is a non-reactive alkali-soluble resin, which is a copolymer having no unsaturated double bond or triple bond polymerizable within the resin molecular chain after polymerization.
In other words, the above-mentioned non-reactive alkali-soluble resin (A ") also includes other monomers which, after polymerization, do not have an unsaturated bond polymerizable in the chain and are polymerized.
The (A ") non-reactive alkali-soluble resin used in the present invention can be produced in the same manner as the above-mentioned reactive alkali-soluble resin (A ') except that (A" (A4) included in the reactive alkali-soluble resin (A ') can not be included because the polymerization should be performed in the absence of an unsaturated double bond capable of causing photopolymerization by a radical photoinitiator. A2) and (A3). The method example is the same as the general synthesis example of the reactive alkali-soluble resin (A '). The above exemplified materials may be used for (A1), (A2) and (A3), respectively.
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 40,000, more preferably 5,000 to 30,000. When the weight average molecular weight of the non-reactive alkali-soluble resin (A ") is in the range of 3,000 to 40,000, 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.
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 is lower than 30 mgKOH / g, If the acid value exceeds 150 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.
The non-reactive alkali-soluble resin (A ") is a copolymer obtained by polymerization of compounds containing (A1), (A2) and (A3) And (A3) the total molar amount of the constituent components.
(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.
(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 formula (10) may be mentioned.
[Chemical formula 10]
In Formula 10,
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 10 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl- 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 chemical formulas (11), (12) and (13).
(11)
[Chemical Formula 12]
[Chemical Formula 13]
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 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 thereof, it is coated on a substrate as follows to form a pattern by photo-curing and development, and it becomes possible to use it for producing a black matrix or a colored and transparent pixel (colored image).
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 : Reactive alkali-soluble resin ( A ' ) Synthesis of
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was provided with 60 parts by weight of phthalic acid mono (2-acroyloxy) ethyl ether, 60 parts by weight of 3,4- 30 parts by weight of tricyclo [5.2.1.0 2,6] decane (EDCPA), 10 parts by weight of N-benzylmaleimide, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, (Hereinafter referred to as "PGMEA") were charged, stirred and mixed 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 replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The temperature was raised to 110 DEG C after 1 hour, and the temperature was maintained for 3 hours. Thereafter, a gas introduction tube was introduced, and a bubble of an oxygen / nitrogen gas mixture of 5/95 (v / v) I started the ring. Subsequently, 30 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 a reactive alkali-soluble resin having a solid content of 29.1 wt% and a weight average molecular weight of 23,000 and an acid value of 120 mgKOH / g.
Synthetic example 2 to 6: Reactive alkali-soluble resin ( A ' ) Synthesis of
A reactive alkali-soluble resin was obtained in the same manner as in Synthesis Example 1 except that each component and ratio were changed as shown in Table 1 below.
Synthetic example 7: Non-reactive Synthesis of alkali-soluble resin (A ")
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, and 300 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added and heated to 75 DEG C with stirring. 30 parts by weight of phthalic acid mono (2-acroyloxy) ethyl ether, 60 parts by weight of 3,4-epoxy-8- (acryloyloxy) tricyclo [5.2.1.02,6] decane (EDCPA) -Cyclohexylmaleimide in 170 parts by weight of PGMEA was added dropwise over 5 hours using a dropping funnel.
On the other hand, a solution prepared by dissolving 30 parts by weight of azobisisobutyronitrile as a polymerization initiator in 200 parts by weight of PGMEA was added dropwise over 5 hours using a separate dropping funnel. After the dropping of the polymerization initiator was completed, the temperature was maintained for about 4 hours. Thereafter, the mixture was cooled to room temperature to obtain a non-reactive alkali-soluble resin having a solid content of 37.6% by weight, a weight average molecular weight of 23,000, and an acid value of 130 mgKOH / g.
Synthetic example 8-11: Non-reactive Synthesis of alkali-soluble resin (A ")
A non-reactive alkali-soluble resin was obtained in the same manner as in Synthesis Example 7 except that each component and ratio were changed as shown in Table 1 below.
Molecular weight evaluation
The weight average molecular weight (Mw) 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, the resultant was dried in a vacuum at 160 DEG C for 3 hours using a hot-air dryer (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.
ingredient
< Example And Comparative Example >
Example 1 to 10 and Comparative Example 1 to 6: Preparation of Photosensitive Resin Composition for Pixel Forming
Each of the components was mixed as shown in Table 2, diluted with propylene glycol monomethyl ether acetate (solvent) so that the total solid content became 20% by weight, and sufficiently stirred to obtain a photosensitive resin composition.
compound
Initiator
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)
<Color filter ( Glass Board) Manufacturing example >
A color filter was prepared using the photosensitive resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 6.
That is, the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were coated on a glass substrate by spin coating, and then placed on a heating plate and held at a temperature of 100 ° C 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. The film thickness of the color filter prepared above was 3.0 mu m.
< 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 3 below.
Storage stability evaluation
The initial viscosity of the photosensitive resin composition for pixel formation prepared in Examples 1 to 10 to Comparative Examples 1 to 6 was measured, and the elapsed time at the time when the rate of change of viscosity was observed at 3% or more was expressed in days.
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.
Remaining film ratio (%) = thickness after development (um) / pre-development thickness (um)
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.
OM equipment: manufactured by ECLIPSE LV100POL Nikon
[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.
B.P
A color filter was prepared using the photosensitive resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 6 as in the color filter production example. The time for developing the boundary between the exposed portion and the non-exposed portion was visually confirmed, and the time (second) was recorded and shown in Table 3 below.
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%
(탆)
(T%, 380 nm)
As in Table 2 or 3, when the photosensitive resin composition of the present invention was used, a photosensitive resin composition for pixel formation having storage stability of 30 days or more was obtained as in Examples 1 to 10. When the compound (A1) was not included, a reactive alkali-soluble resin having a high molecular weight was obtained as in Synthesis Example 6, and a photosensitive resin composition having a storage stability of 7 days or less was formed as in Comparative Examples 1 to 6 using the same .
When the alkali-soluble resin of the present invention is used, as in Examples 1 to 10, the combination of the unsaturated double bond as the photocurable component and the component (A2) as the thermosetting component results in excellent reliability, . In the case of Comparative Examples 1 to 6, the component (A2) as a thermosetting component was polymerized during the reaction of imparting an unsaturated double bond group, resulting in a less bonding portion at the time of thermosetting, resulting in poor solvent resistance.
Claims (7)
The alkali-soluble resin (A)
A monomer derived from a compound represented by the following formula (1); And
Monomers having an aliphatic polycyclic epoxy group; Wherein the photosensitive resin composition is a photosensitive resin composition.
[Chemical Formula 1]
In Formula 1,
R is a C2-C6 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,
R 'is hydrogen or methyl (-CH 3),
Y is a group selected from the groups represented by the following formulas (Y1 to Y4).
(Y1)
[Y2]
[Y3]
[Y4]
The monomer having an aliphatic polycyclic epoxy group comprises at least one selected from the group consisting of the following formulas (I) to (II).
(I)
≪ RTI ID = 0.0 &
In the above general formulas (I) to (II)
R is each independently hydrogen or C1-C4 alkyl, and the alkyl may include a hydroxyl group,
X is a C1-C6 alkylene group which may contain at least one member selected from N, O, S and P in a single bond or a chain.
Wherein the alkali-soluble resin is a copolymer comprising a monomer represented by the following formula (5).
[Chemical Formula 5]
In Formula 5,
R is a C2-C6 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,
R 'is hydrogen or methyl (-CH 3),
Y is a group selected from the groups represented by the following formulas (Y1 to Y4)
(Y1)
[Y2]
[Y3]
[Y4]
Z is a C1-C60 alkyl group containing a reactive group.
Wherein the compound of Formula 1 is at least one compound selected from the group consisting of Formulas 1-1 to 1-4 below.
[Formula 1-1]
[Formula 1-2]
[Formula 1-3]
[Formula 1-4]
In the above Chemical Formulas 1-1 to 1-4, R 'is hydrogen or methyl (-CH 3 ).
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; / RTI >
Based on the total weight% of the photosensitive resin composition,
And 60 to 90% by weight of a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140130851A KR20160038279A (en) | 2014-09-30 | 2014-09-30 | Photosensitive resin composition for pixel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140130851A KR20160038279A (en) | 2014-09-30 | 2014-09-30 | Photosensitive resin composition for pixel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20160038279A true KR20160038279A (en) | 2016-04-07 |
Family
ID=55789490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140130851A KR20160038279A (en) | 2014-09-30 | 2014-09-30 | Photosensitive resin composition for pixel |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20160038279A (en) |
-
2014
- 2014-09-30 KR KR1020140130851A patent/KR20160038279A/en not_active Application Discontinuation
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