KR100849360B1 - A colored photosensitive resin composition, patterning method thereof, color filter, liquid crystal display device and imaging device having the same - Google Patents
A colored photosensitive resin composition, patterning method thereof, color filter, liquid crystal display device and imaging device having the same Download PDFInfo
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- KR100849360B1 KR100849360B1 KR1020070014852A KR20070014852A KR100849360B1 KR 100849360 B1 KR100849360 B1 KR 100849360B1 KR 1020070014852 A KR1020070014852 A KR 1020070014852A KR 20070014852 A KR20070014852 A KR 20070014852A KR 100849360 B1 KR100849360 B1 KR 100849360B1
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
The present invention relates to a colored photosensitive resin composition, a pattern forming method thereof, a color filter, a liquid crystal display device and an imaging device including the same.
Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device, an image pick-up element, etc. spin-coats the colored photosensitive resin composition containing the pigment corresponding to each color of red, green, and blue normally on the board | substrate with a black matrix patterned. After coating uniformly, an operation of exposing and developing a coating film formed by heating and drying (hereinafter sometimes referred to as preliminary firing) and further curing by heat (hereinafter sometimes referred to as postfiring) as necessary is performed for each color. It is manufactured by repeatedly forming pixels of each color. Subsequently, a process of forming an ITO electrode on the surface of the color filter for a liquid crystal display device is essential, and in this process, it is exposed to a high temperature of about 200 ° C or more. In addition, at the time of forming a culture film, it is exposed to high temperature 200 degreeC or more.
As such colored photosensitive resin composition, the composition containing a photopolymerizable compound and a photoinitiator with pigment and binder resin is used a lot. Moreover, the photosensitive resin composition containing a black pigment is used for formation in a black matrix. As such a photosensitive coloring composition, acrylic resin which has a carboxyl group in a side chain is used as resin excellent in light resistance and few color changes. For example, the colored resin composition obtained through the composition of the acrylic resin containing a carboxyl group in a side chain, a pigment, and a polyfunctional acrylate is disclosed. Also disclosed is a photosensitive resin composition using a reactive acrylic resin obtained by adding an unsaturated carboxylic acid to a polymer containing a monomer having an epoxy group and an unsaturated double bond in order to increase the sensitivity, followed by addition of a basic acid anhydride.
However, when the pixel is formed using a conventional composition, the colored layer formed on the base is poor in heat resistance after high-temperature process when the photosensitive resin composition having low heat resistance is deteriorated, resulting in deterioration in luminance and color properties or decomposition of the photosensitive resin composition. There is a problem in that image and color purity are lowered, such as afterimages generated by outgass.
An object of the present invention is to solve the afterimage problem caused by the outgas caused by lack of surface resistance and the like in the pixel portion due to the development residue does not occur on the substrate when the pixel is formed, the heat resistance after high-temperature process To provide a colored photosensitive resin composition in which the luminance and color characteristics are not deteriorated.
Further, another object of the present invention is to provide a colored photosensitive resin composition that can be suitably used in a liquid crystal display device, a color filter of an image pickup device, and the like.
The present invention for achieving the above object,
A colored photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a coloring material (D), and a solvent (E), wherein the binder resin (A) is represented by the following (A1) It is a copolymer obtained by the copolymerization reaction included, The coloring photosensitive resin composition is provided.
(A1): a compound represented by the following formula (1),
<Formula 1>
Wherein n is 0 or 1,
R 1 and R 2 are each independently an aliphatic or aromatic hydrocarbon containing or not containing hydrogen, a hetero atom having 1 to 12 carbon atoms,
R3, R4, R5, and R6 are each independently hydrogen or an aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 1 to 30 carbon atoms, and two or more selected from R3, R4, R5, and R6 are linked or Branches are not connected.)
In addition, the compound represented by Formula 1 provides a colored photosensitive resin composition, characterized in that at least one selected from the compounds represented by the following formula.
In addition, the said binder resin (A) is a copolymer obtained by copolymerization reaction containing the said (A1) and following (A2), (A3), or unsaturated group containing resin obtained by making the following (A4) further react. It provides the coloring photosensitive resin composition.
(A2): a compound having an unsaturated bond copolymerizable with (A1) and (A3),
(A3): unsaturated carboxylic acid,
(A4): A compound having an unsaturated bond and an epoxy group in one molecule.
Moreover, the ratio of the structural component guide | induced from each of said (A1)-(A3) is with respect to the total mole number of the said copolymer structural component,
Structural unit derived from (A1): 2 to 30 mol%,
Structural unit derived from (A2): 2 to 95 mol%,
Structural unit derived from (A3): 2 to 70 mol%,
It is a range and when it reacts (A4) further, it provides the coloring photosensitive resin composition characterized by reacting (A4) with 5 to 80 mol% with respect to the component derived from (A3).
The binder resin (A) is a copolymer obtained by copolymerizing the above-mentioned (A1) with the following (A2) and (A4), or after reacting the following (A3) with the copolymer, It is an unsaturated group containing resin obtained by making A5) react further, The coloring photosensitive resin composition characterized by the above-mentioned is provided.
(A2): a compound having an unsaturated bond copolymerizable with (A1) and (A4),
(A3): unsaturated carboxylic acid,
(A4): Compound which has an unsaturated bond and an epoxy group in 1 molecule
(A5): Polybasic acid anhydride.
In addition, the ratio of the component derived from each of said (A1), (A2), and (A4) is with respect to the total number of moles of the said copolymer component,
Structural unit derived from (A1): 2 to 30 mol%,
Structural unit derived from (A2): 2 to 95 mol%,
Structural unit derived from (A4): 2 to 85 mol%,
(A3) is 10-100 mol% reaction with respect to the component derived from (A4), and 5-100 mol% of (A5) is reacted with the hydroxyl group of the material obtained after reaction, The coloring photosensitive property characterized by the above-mentioned. It provides a resin composition.
The present invention also includes the steps of applying the above-described colored photosensitive resin composition, selectively exposing a portion of the colored photosensitive resin composition and removing the exposed or non-exposed areas of the colored photosensitive resin composition; Provided is a method of forming a pattern of the colored photosensitive resin composition.
The present invention further provides a color filter comprising a color layer formed by exposing and developing a colored photosensitive resin composition in a predetermined pattern, wherein the colored photosensitive resin composition is the colored photosensitive resin composition described above. To provide.
The present invention also provides a liquid crystal display device having the above-described color filter.
The present invention also provides an imaging device having the above-described color filter.
EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
The colored photosensitive resin composition of one Embodiment which concerns on this invention contains binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), a coloring material (D), and a solvent (E). As said binder resin (A), it is characterized by being a copolymer obtained by the copolymerization reaction containing following (A1). Moreover, it is preferable that the other additive (F) is melt | dissolved or disperse | distributed in the solvent (E) arbitrarily.
(A1): a compound represented by the following formula (1),
<Formula 1>
N is 0 or 1,
R 1 and R 2 are each independently an aliphatic or aromatic hydrocarbon containing or not containing hydrogen, a hetero atom having 1 to 12 carbon atoms,
R3, R4, R5 and R6 are each independently hydrogen, an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 30 carbon atoms,
Two of R 3, R 4, R 5, and R 6 are selected to be linked or unbranched.
The hetero atom may be present in the main skeleton or in a branch, and may exist in the form of a carbonyl group, an ether group, an alcohol group, an amine group, a heterocycle, and the like, and is not limited.
The binder resin (A) usually has reactivity and alkali solubility due to the action of light or heat, and acts as a dispersion medium of the coloring material.
Binder resin (A) contained in the coloring photosensitive resin composition of this invention is an unsaturated group containing resin containing the structural unit which can be obtained by superposition | polymerization (this is also a concept including copolymerization) of the compound of the said General formula (1). That is, the compound of Formula 1 is polymerized alone or together with other compounds to form the binder resin. There is no restriction on the conditions of the other compound polymerized with the compound of Formula 1, and all are included in the present invention.
Preferably, the binder resin of one embodiment according to the present invention is a copolymer obtained by a copolymerization reaction containing the compound of Formula 1 (A1), a compound having an unsaturated bond (A2), and an unsaturated carboxylic acid compound (A3). It is preferable that it is an unsaturated group containing resin obtained by making the said obtained copolymer further react with the compound (A4) which has an unsaturated bond and an epoxy group in 1 molecule.
Also preferably, the binder resin (A) of another embodiment according to the present invention is a compound (A1) of the general formula (1), a compound (A2) having an unsaturated bond, and a compound (A4) having an unsaturated bond and an epoxy group in one molecule. It is a coloring photosensitive resin which is an unsaturated group containing resin obtained by making copolymerize and making the obtained copolymer or unsaturated carboxylic acid compound (A3) react, and then making a polybasic acid anhydride compound (A5) react further.
In one embodiment of the present invention, as an example of the compound (A1) of the general formula (1), a more specific structural formula is as follows, at least one of these may be selected and included.
The present invention is not limited to the structure of the above formula, and all derivatives or all derivatives of the compound of Formula 1 including the norbornene skeleton are included in the present invention. These can be used individually or in combination of 2 types or more, respectively.
In addition, the (meth) acrylate recorded in this specification means an acrylate and / or a methacrylate.
In one embodiment of the present invention, the compound (A2) having an unsaturated bond is not limited as long as it is a compound having an unsaturated double bond which can be polymerized. Specific examples thereof include methyl (meth) acrylate and ethyl (meth). Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate, and cyclopentyl (meth) acryl Rate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate , Cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, these Unsaturation containing alicyclic substituents, such as bornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate Substituent which has aromatic rings, such as monosaturated carboxylic acid ester compound of glycols, such as a carboxylic acid ester compound and oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, and phenoxy (meth) acrylate Carboxylic acid vinyl esters such as unsaturated carboxylic acid ester compounds, styrene, aromatic vinyl compounds such as α-methylstyrene and vinyltoluene, vinyl acetate and vinyl propionate, (meth) acrylonitrile and α-chloroacrylo And maleimide compounds such as vinyl cyanide compounds such as nitrile, N-cyclohexyl maleimide, and N-phenylmaleimide. These can be used individually or in combination of 2 types or more, respectively.
In one embodiment of the present invention, the unsaturated carboxylic acid (A3) is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized, and specific examples thereof include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used individually or in combination of 2 types or more, respectively. In addition to these acrylic acid and methacrylic acid, one or more other acids may be used. As another acid, it is also possible to specifically use together the carboxylic acid chosen from 1 type or more of other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid.
In one embodiment of the present invention, in the copolymer obtained by copolymerizing (A1) to (A3) used in the present invention (even when monomers other than A1 to A3 are further included and copolymerized, they are included in the present invention). It is preferable that the ratio of the structural component guide | induced from each of (A1)-(A3) exists in the following ranges by mole fraction with respect to the total mole number of the structural component which comprises said copolymer.
Structural unit derived from (A1): 2 to 30 mol%,
Structural unit derived from (A2): 2 to 95 mol%,
Structural units derived from (A3): 2 to 70 mol%
That is, the copolymer obtained by the copolymerization reaction containing the compound (A1) of the general formula (1), the compound having an unsaturated bond (A2) and the unsaturated carboxylic acid compound (A3), is represented by the general formula Monomers, monomers having unsaturated bonds and unsaturated carboxylic acid monomers are not limited but are preferably included in the range of 2 to 30 mol%, 2 to 95 mol%, and 2 to 70 mol%, respectively.
In particular, it is more preferable that the ratio of said structural component is the following ranges.
Structural unit derived from (A1): 5-30 mol%,
Structural unit derived from (A2): 5 to 80 mol%,
Structural units derived from (A3): 5-65 mol%
If said composition ratio is in the said range, since the balance of developability, solubility, and heat resistance is favorable, a preferable copolymer can be obtained.
In one Embodiment of this invention, when obtaining by copolymerizing (A1)-(A3) as an example of the manufacturing method of the said copolymer, it can manufacture by copolymerizing by the following methods.
To a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot and a nitrogen inlet tube, 0.5 to 20 times the amount of solvent (E) was introduced together on a mass basis with respect to the total amount of (A1) and (A1) to (A3). The atmosphere in the flask is replaced with nitrogen in air. Then, after heating up the solvent (E) at 40-140 degreeC, 0-20 times the solvent (E) by mass basis with respect to the predetermined amount of (A2)-(A3) and the total amount of (A2)-(A3). ) And a solution obtained by adding 0.1 to 10 mol% of a polymerization initiator such as azobisisobutyronitrile or terbutyryl peroxy 2-ethylhexyl carbonate to the total number of moles of (A1), (A2) to (A3) ( Stirring at room temperature or under heating) is added dropwise to the flask over 0.1 to 8 hours from the dropping lot, and further stirred at 40 to 140 ° C for 1 to 10 hours.
In addition, a part or whole quantity of a polymerization initiator may be put in a flask at the said process, and a part or whole quantity of (A1), (A2)-(A3) may be put in a flask. Moreover, in order to control molecular weight and molecular weight distribution, (alpha) -methylstyrene dimer and a mercapto compound can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% by mass with respect to the total amount of (A1), (A2)-(A3). In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..
The binder resin (A) contained in the colored photosensitive resin composition of one embodiment of the present invention can be obtained by further reacting (A4) with a copolymer obtained by copolymerizing (A1) to (A3). By adding (A4) to the copolymer, light / thermosetting property can be imparted to the binder resin.
In one embodiment of the present invention, specific examples of the compound (A4) having an unsaturated bond and an epoxy group in one molecule are glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3 And 4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 types or more, respectively.
It is preferable to react 5 to 80 mol% with respect to the number of moles of unsaturated carboxylic compound (A3) contained in the said copolymer, and the compound which has the said unsaturated bond and an epoxy group is especially 10-80 mol%. If the composition ratio of (A4) is in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and since it is excellent in reliability, it is preferable.
In one Embodiment of this invention, binder resin (A) can be manufactured by making said copolymer and (A4) react by the following methods, for example.
The atmosphere in the flask is replaced with nitrogen from air, and is a reaction catalyst of 5 to 80 mol% of (A4), a carboxyl group and an epoxy group in a molar fraction with respect to the structural unit derived from the copolymer (A3), for example, trisdimethylamino 0.01-5% by weight of the total amount of methylphenol (A1) to (A4) and a polymerization inhibitor, for example, hydroquinone is 0.001-5% by mass based on the total amount of (A1) to (A4). The above copolymer and (A4) can be reacted by putting into a flask and reacting at 60 to 130 ° C. for 1 to 10 hours. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.
In one embodiment of the present invention, the binder resin (A) preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of binder resin (A) exists in the range of 3,000-100,000, film | membrane decrease hardly arises at the time of image development, and since the missing property of a non-pixel part at the time of image development tends to be favorable, it is preferable.
It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A), it is more preferable that it is 1.8-4.0. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.5 to 6.0 because it is excellent in developability.
In another embodiment of the present invention, the compound (A1) of the formula (1) may be the same as that described in one embodiment of the present invention.
In another embodiment of this invention, the compound (A2) which has said unsaturated bond can use the same thing as what was described in one Embodiment of this invention.
In another embodiment of this invention, the compound (A4) which has an unsaturated bond and an epoxy group in the said 1 molecule can use the thing similar to what was described in one Embodiment of this invention.
In another embodiment of the present invention, monomers other than the copolymers ((A1), (A2) and (A4) obtained by copolymerizing (A1), (A2) and (A4) used in the present invention are further included. In the case of copolymerization, the proportion of the constituents derived from each of (A1), (A2) and (A4) is in the molar fraction with respect to the total moles of the copolymer constituents in the following ranges. It is desirable to have.
Structural unit derived from (A1): 2 to 30 mol%,
Structural unit derived from (A2): 2 to 95 mol%,
Structural unit derived from (A4): 2 to 85 mol%,
That is, the copolymer obtained by the copolymerization reaction containing the compound (A1) of the said General formula (1), the compound (A2) which has an unsaturated bond, and the compound (A4) which has an unsaturated bond and an epoxy group in 1 molecule, with respect to the total number of moles of a component In addition, the monomer of Formula 1, a monomer having an unsaturated bond and a monomer having an unsaturated bond and an epoxy group in one molecule are not limited, but are included in the range of 2 to 30 mol%, 2 to 95 mol%, 2 to 85 mol%, respectively. desirable.
In particular, it is more preferable that the ratio of said structural component is the following ranges.
Structural unit derived from (A1): 5-30 mol%,
Structural unit derived from (A2): 5 to 80 mol%,
Structural units derived from (A4): 5-75 mol%
If said composition ratio is in the said range, since the balance of developability, solubility, and heat resistance is favorable, a preferable copolymer can be obtained.
In another embodiment of the present invention, as an example of the method for producing the copolymer, the copolymer can be produced by copolymerizing in the following manner when it is obtained by copolymerizing (A1), (A2) and (A4).
0.5-20 times of solvent (E) by mass relative to the total amount of (A1) and (A1), (A2) to (A4) in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot and a nitrogen introduction tube. Are introduced together and the atmosphere in the flask is replaced with nitrogen in air. Then, after heating up the solvent (E) at 40-140 degreeC, 0-20 times the solvent (E) by mass basis with respect to the predetermined amount of (A2)-(A4) and the total amount of (A2)-(A4). ) And a solution obtained by adding 0.1 to 10 mol% of a polymerization initiator such as azobisisobutyronitrile or terbutyryl peroxy 2-ethylhexyl carbonate to the total number of moles of (A1), (A2) to (A4) ( Stirring at room temperature or under heating) is added dropwise to the flask over 0.1 to 8 hours from the dropping lot, and further stirred at 40 to 140 ° C for 1 to 10 hours.
In addition, a part or whole quantity of a polymerization initiator may be put in a flask at the said process, and a part or whole quantity of (A1), (A2), and (A4) may be put in a flask. Moreover, in order to control molecular weight and molecular weight distribution, (alpha) -methylstyrene dimer and a mercapto compound can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% by mass with respect to the total amount of (A1), (A2), and (A4). In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..
The binder resin (A) contained in the colored photosensitive resin composition of another embodiment of the present invention reacts the unsaturated carboxylic acid compound (A3) with a copolymer obtained by copolymerizing (A1), (A2) and (A4). And a copolymer (A-1) containing an unsaturated group or hydroxyl group of a side chain produced by the reaction [a hydroxyl group formed by reaction of a carboxyl group and an epoxy group or a hydroxyl group contained in the component (A1) from the beginning]]. have.
The unsaturated carboxylic acid compound (A3) preferably reacts (A3) 10 to 100% with respect to the number of moles of the compound (A4) having an unsaturated bond and an epoxy group in one molecule included in the copolymer, particularly 15 to 100%. Is preferable, especially 30-100 mol% is preferable.
In another embodiment of this invention, a copolymer (A-1) can be manufactured by making it react by the following methods, for example.
The atmosphere in the flask is replaced with nitrogen from air, and the molar fraction of 5 to 80 mole% of (A3) and carboxyl groups is derived from the copolymer obtained by copolymerizing the above (A1), (A2) and (A4). As the reaction catalyst of the epoxy group, for example, trisdimethylaminomethylphenol is 0.01 to 5% by mass relative to the total amount of (A1) to (A4) and as a polymerization inhibitor, for example, hydroquinone (A1) to (A4). Copolymer (A-1) by adding 0.001 to 5% in a flask on a mass basis and reacting for 1 to 10 hours at 60 to 150 ° C, more preferably for 1 to 10 hours at 80 to 130 ° C, based on the total amount of Can be obtained. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.
The binder resin (A) of this invention can be obtained by making the hydroxyl group of (A-1) obtained above react with the polybasic acid anhydride compound which is (A5) component.
The polybasic acid anhydride compound (A5) is not particularly limited, and specific examples thereof include coharic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hexahydro. Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned. Tetrahydrophthalic anhydride and coharic anhydride are preferable above, and these 1 type, or 2 or more types may be used together.
The polybasic acid anhydride compound (A5) is preferably reacted 5 to 100 mol% with respect to the number of moles of unsaturated carboxylic acid compound (A3) contained in the copolymer, particularly preferably 20 to 80 mol%.
In another embodiment of this invention, binder resin (A) can be manufactured by making said copolymer and (A5) react by the following methods, for example.
After making the unsaturated carboxylic acid compound (A3) react with the reactor of (A4) contained in the copolymer (A-1) obtained by the above, ie, a side chain, it can obtain by adding an appropriate amount (A5) component as it is. In general, the reaction temperature is 50 ° C to 150 ° C and is preferably heated to 80 ° C to 130 ° C for reaction. There is no need to add a catalyst in particular.
In another embodiment of the present invention, the binder resin (A) preferably has a weight average molecular weight in terms of polystyrene thereof in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of binder resin (A) exists in the range of 3,000-100,000, film | membrane decrease hardly arises at the time of image development, and since the missing property of a non-pixel part at the time of image development tends to be favorable, it is preferable.
It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A), it is more preferable that it is 1.8-4.0. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.5 to 6.0 because it is excellent in developability.
Content of binder resin (A) is 5-90 mass% normally with respect to the total solid in a coloring photosensitive resin composition, Preferably it is the range of 10-70 mass%. When the content of the binder resin (A) is 5 to 90% by mass based on the above criteria, the solubility in the developing solution is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion. Since it is hard to produce and the missing property of a non-pixel part tends to be favorable, it is preferable.
The photopolymerizable compound (B) contained in the colored photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. have.
Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc.
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) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, thipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.
Of these, bifunctional or higher polyfunctional monomers are preferably used.
The photopolymerizable compound (B) is usually used in the range of 1 to 60 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass in total of the binder resin (A) and the photopolymerizable compound (B). If the photopolymerizable compound (B) is in the range of 1 to 60 parts by mass based on the above criteria, the intensity and smoothness of the pixel portion tends to be good, and thus it is preferable.
Although the photoinitiator (C) contained in the coloring photosensitive resin composition of this invention is not restrict | limited, It is 1 or more types of compounds chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound. The coloring photosensitive resin composition containing said photoinitiator (C) is highly sensitive, and the film | membrane formed using this composition becomes favorable the intensity | strength and surface smoothness of the pixel part.
Moreover, when photopolymerization start adjuvant (C-1) is used together with a photoinitiator (C), since the coloring photosensitive resin composition containing these becomes more sensitive and the productivity at the time of forming a color filter using this composition is preferable, it is preferable. .
As said triazine type compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl), for example -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran- 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Romethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.
Moreover, as said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4, for example. -(2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) And oligomers of phenyl] propan-1-one. As an acetophenone type compound, the compound represented by following formula (2) is mentioned, for example.
<Formula 2>
In Formula 2, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, or The naphthyl group which may be substituted by the C1-C12 alkyl group is shown.
Specific examples of the compound represented by the formula (2) include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 2-ethyl-2-amino (4-morpholinophenyl) ethane-1- On, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2- Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl ) Propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. are mentioned.
As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3), for example -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) ratio Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4', 5,5 'position And imidazole compounds substituted with a boalkoxy group. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetra phenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.
As said oxime compound, 0-ethoxycarbonyl- (alpha)-oxyimino- 1-phenyl propane- 1-one of following formula (3) is mentioned, for example.
<Formula 3>
Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.
As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.
As a benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra (tert) -Butyl peroxy carbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.
As a thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.
As an anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene, etc. are mentioned, for example. Can be.
Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.
Moreover, the photoinitiator which has group which can cause chain transfer can also be used, As this photoinitiator, what is described in Unexamined-Japanese-Patent No. 2002-544205 is mentioned, for example.
As a photoinitiator which has group which can cause said chain transfer, the compound represented by following formula (4)-9 is mentioned, for example.
<Formula 4>
<Formula 5>
<Formula 6>
<Formula 7>
<Formula 8>
<Formula 9>
The photoinitiator which has group (for example, unsaturated double bond) which can cause said chain transfer can be used also as a structural component (A2) of the copolymer obtained by copolymerizing said (A1)-(A3). The copolymer obtained using the photoinitiator which has group which can cause chain transfer as a structural component (A2) can be used together with binder resin (A).
In addition, you may use combining a photoinitiator (C-1) with a photoinitiator (C).
As the photopolymerization initiation assistant (C-1), an amine compound and a carboxylic acid compound are preferably used. Specific examples of the amine compound in the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoic acid, and 4- 2-ethylhexyl dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively: Michler's Ketone), 4,4'- Aromatic amine compounds, such as bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.
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 usage-amount of a photoinitiator (C) is 0.1-40 mass parts normally with respect to a total of 100 mass parts of binder resin (A) and a photopolymerizable compound (B), Preferably it is 1-30 mass parts, A photoinitiator adjuvant (C) The usage-amount of -1) is 0.1-50 mass parts normally on the said reference | standard, Preferably it is 1-40 mass parts.
When the usage-amount of a photoinitiator (C) exists in the said range, since the coloring photosensitive resin composition becomes high sensitivity and the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part tend to become favorable, it is preferable. . Moreover, when the usage-amount of a photoinitiator auxiliary (C-1) exists in the said range, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.
It is preferable that the coloring material (D) used by this invention is an organic pigment or inorganic pigment normally used for a pigment dispersion resist as a pigment normally. If necessary, dyes may be used and are included in the present invention.
Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or complex metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Etc. can be mentioned.
Specific examples of the organic pigment and inorganic pigment include compounds classified as pigments in the Color Index (published by The society of Dyers and Colorists), and more specifically, pigments having the following color index (CI) numbers. Although these are mentioned, It is not necessarily limited to these.
C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185
C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71
C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264
C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38
C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76
C.I. Pigment Green 7, 10, 15, 25, 36 and 47
C.I Pigment Brown 28
C.I pigment black 1 and 7, etc.
These coloring materials (D) can be used individually or in combination of 2 or more types, respectively. Content of a coloring material (D) is 3-60 mass% normally on the basis of the total solid amount in a coloring photosensitive resin composition, Preferably it is the range of 5-55 mass%. If the content of the coloring material (D) is in the range of 5 to 60% by mass based on the above criteria, even when a thin film is formed, the color density of the pixel is sufficient, and residues are less likely to occur because the omission of the non-pixel portion during development is not lowered. It is preferable because it tends to.
The solvent (E) contained in the colored photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of colored photosensitive resin composition can be used.
Specific examples thereof 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 dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, alkylene glycol alkyl ether acetates, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, Me Ketones such as amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. And cyclic esters such as γ-butyrolactone.
Among the solvents described above, organic solvents having a boiling point of 100 ° C. to 200 ° C. in the coating properties and drying properties are preferable, and alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy are more preferable. Ester, such as ethyl propionate and the methyl 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3- Methyl methoxy propionate etc. are mentioned.
These solvents (E) can be used individually or in mixture of 2 or more types, respectively.
Content of the solvent (E) in the coloring photosensitive resin composition of this invention is 60-90 mass% normally with a mass fraction with respect to the coloring photosensitive resin composition whole quantity containing it, Preferably it is 70-85 mass%. If the content of the solvent (E) is in the range of 60 to 90% by mass based on the above criteria, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. It is preferable because the coating property tends to be good when used.
In the coloring photosensitive resin composition of this invention, it is also possible to add additives (F), such as a filler, another high molecular compound, a hardening | curing agent, a pigment dispersant, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.
Specific examples of the filler include glass, silica, alumina and the like.
Specific examples of other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. have.
A hardening | curing agent is used in order to raise a deep part hardening and mechanical strength, As a hardening | curing agent, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned.
Examples of the epoxy compound in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins, other aromatic epoxy resins, Alicyclic, alicyclic or aromatic epoxy compounds other than alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxy Cargo, isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.
Examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane and cyclohexane dicarboxylic acid bis oxetane.
The curing agent may include a curing aid compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound with the curing agent. As a hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.
As the carboxylic anhydrides, those commercially available as epoxy resin curing agents can be used. As this epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditsudo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Nippon Ewha Co., Ltd.). The said hardening | curing agent can be used individually or in mixture of 2 or more types.
Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethyleneimine, and the like, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Industries, Ltd.), Florard (manufactured by Sumitomo 3M), Asahi guard, Suflon (manufactured by Asahi Glass), SOLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.
As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.
These adhesion promoters can be used individually or in combination of 2 or more types, respectively.
The concentration relative to the resist solid content is usually 0.01 to 10% by mass, preferably 0.05 to 2% by mass.
Specific examples of the anti-inflammatory agent include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.
Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.
The coloring photosensitive resin composition of this invention can be manufactured by the following methods, for example. The coloring material (D) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. At this time, a pigment dispersant is used as needed, and some or all of binder resin (A) may be mix | blended. The remainder of binder resin (A), the photopolymerizable compound (B), the photoinitiator (C), the other components used as needed, and the additional solvent as needed in the obtained dispersion liquid (henceforth a mill base). Is further added to a predetermined concentration to obtain a desired colored photosensitive resin composition.
Hereinafter, the pattern formation method of the coloring photosensitive resin composition which concerns on this invention is demonstrated.
The pattern forming method of the colored photosensitive resin composition according to the present invention comprises the steps of applying the above-described colored photosensitive resin composition on a substrate, selectively exposing a portion of the colored photosensitive resin composition, and the colored photosensitive resin composition Removing the exposed or non-exposed areas.
As an example, it can apply | coat on a base material as follows, and perform a photocuring and image development to form a pattern, and can be used as a black matrix or a colored pixel (colored image).
First, the composition is applied onto a substrate (not limited, usually glass or silicon wafer) or a layer containing solids of the colored photosensitive resin composition formed first and preliminarily dried to remove volatile components such as solvents to obtain a smooth coating film. . The thickness of the coating film at this time is about 1-3 micrometers normally. In order to obtain the desired pattern to the coating film obtained in this way, an ultraviolet-ray is irradiated to a specific area | region through a mask. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate will be correctly aligned. In addition, a desired pattern can be produced by contacting the aqueous coating solution after completion of curing with an aqueous alkali solution to dissolve and develop the non-exposed areas. After image development, after-drying for about 10 to 60 minutes can be performed at 150-230 degreeC as needed.
The developing solution used for image development after patterned exposure is the aqueous solution containing an alkaline compound and surfactant normally.
The alkaline compound may be either an inorganic or organic alkaline compound.
Specific examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate And potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.
In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively.
Preferable concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.
Surfactant in alkaline developing solution can use all of a nonionic surfactant, anionic surfactant, or a cationic surfactant.
Specific examples of non-ionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, and poly Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.
Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, and quaternary ammonium salts.
These surfactant can be used individually or in combination of 2 or more types, respectively.
The concentration of the surfactant in the alkaline developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.
Hereinafter, the color filter according to the present invention will be described.
The color filter according to the present invention is characterized by comprising a color layer formed by exposing and developing the above-described colored photosensitive resin composition in a predetermined pattern.
The pattern formation method of a coloring photosensitive resin composition is based on the above-mentioned, and detailed description is abbreviate | omitted. As described above, a pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained by applying the colored photosensitive resin solution, drying, patterning exposure to the resulting dried coating film, and developing. The color filter can be obtained by repeating the operation by the number of colors required for the color filter. Since the configuration and manufacturing method of the color filter are well known in the art, detailed description thereof will be omitted.
The color filter is usually a black matrix and three primary color pixels of red, green and blue arranged on a substrate, but by performing the above operation using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color. The black matrix and the three primary color pixels are disposed on a substrate by obtaining the black matrix or the pixel of the color and performing the same operation using the colored photosensitive resin composition of the present invention containing the coloring material corresponding to the desired color for other colors. can do. Of course, the photosensitive resin composition of this invention can also be apply | coated only to one color, two colors, or three colors of a black matrix and three primary colors.
In addition, although the black matrix which is a light shielding layer can also use the coloring (colored black) photosensitive resin of this invention, since it is formed by the chromium layer etc., for example, the coloring photosensitive resin composition of this invention for formation of a black matrix. There is no need to use.
The color filter manufactured using the coloring photosensitive resin composition of this invention has little in-plane film thickness difference, For example, it can make in-plane film thickness difference 0.15 micrometer or less and further 0.05 micrometer or less with the film thickness of 1-3 micrometers. . Therefore, the color filter obtained in this way is excellent in smoothness, and it can manufacture a liquid crystal display device and an image pick-up element of outstanding quality by high yield by assembling this to a color liquid crystal display device and an image pick-up element.
The present invention also includes a liquid crystal display device and an image pickup device provided with the color filter described above.
The liquid crystal display of the present invention includes a configuration known in the art, except that the above-described color filter is provided. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is faced at predetermined intervals, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Can be. There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.
As another example, a liquid crystal display device including a TFT (Thin Film Transistor) substrate joined on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate includes an outer frame made of a light-proof resin surrounding a peripheral surface of a color filter, a liquid crystal layer made of a nematic liquid crystal imposed in the outer frame, and a plurality of pixel electrodes provided for each region of the liquid crystal layer. , A transparent glass substrate on which the pixel electrode is formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.
The polarizing plate has a polarizing direction that traverses vertically and is made of an organic material such as polyimide. A plurality of pixel electrodes are connected to a plurality of thin film transistors each formed on a glass substrate of a TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage is applied between the specific pixel electrode and the transparent electrode. Therefore, the electric field formed according to the voltage changes the orientation of the region corresponding to the specific pixel electrode of the liquid crystal layer.
The image pickup device of the present invention is characterized by including the above-described color filter, and in the case of other configurations, the configurations known in the art can be applied without limitation. That is, all the image pickup devices to which the above-described color filter can be applied are included in the present invention. Both a charge coupled device (CCD) and a Complementary Metal Oxide Silicon (CMOS) imaging device are included in the present invention, and both an active pixel sensor and a passive pixel sensor are included in the present invention. Included.
For example, a semiconductor substrate divided into a light receiving area and a light blocking area, a light blocking film formed on the light blocking area, a flattening layer formed over the entire substrate on the light blocking film, a color filter formed on the flattening layer, and a concave lens formed on the color filter. And an image pickup device having a color filter, wherein the color filter is the color filter described above.
The semiconductor substrate is divided into a light receiving region in which light passing through the lens is received and a light blocking region in which light is not received, and a photodiode may be formed in the semiconductor substrate of the light receiving region. An impurity layer may be formed. A charge transfer electrode may be formed on the impurity layer to transfer charges supplied from the photodiode. The light blocking film is made of a material capable of blocking light, and is formed over the entire light blocking area. The planarization layer may be formed to planarize the uneven portion by the elements (eg, the charge transfer electrode, the light shielding film, etc.) formed on the impurity layer, and protect the charge transfer electrode, the light shielding film, and the like. On the planarization layer, color filters are formed in respective colors corresponding to the respective light receiving regions. The pad supplies an external electrical signal to the solid-state image pickup device or transmits an internal electrical signal to the solid-state image pickup device. The lens is a concave lens, and is a hybrid polyamide-based polyimide layer having a refractive index of 0.1 or more lower than the transparent epoxy resin layer formed thereon. The transparent epoxy resin layer having a refractive index higher than 0.1 may be formed on the lens.
As another example, a plurality of photo diodes (PDs) for converting a signal of light into an electrical signal are arranged in a matrix form, and are formed between each of the vertical photo diodes arranged in the matrix form. A plurality of vertical charge coupled device (VCCD) for transferring charges generated in the vertical direction, and a horizontal charge transfer region for transferring charges transferred by each of the vertical charge transfer regions in a horizontal direction (Horizontal charge coupled device; HCCD) and a sense amplifier for outputting an electrical signal by sensing the charge transmitted in the horizontal direction (Sense Amplifier) and the above-described color filter formed on a vertical line of the photodiode and It may be configured to include a micro lens.
As another example, photodiodes (PDs) and MOS transistors, which are light-receiving elements disposed at predetermined intervals on a semiconductor substrate, may form an element layer constituting a pixel and an insulating layer separating each pixel. have. A metal wiring layer having a plurality of metal wires is formed on the semiconductor substrate, and then a color filter array is formed thereon, and a coating layer for adjusting the focal length is formed on the color filter array. The upper portion of the coating layer corresponds to each photodiode PD, and a microlens for concentrating external light to the photodiode PD is formed, and the upper portion of the microlens is supported by a CMOS image sensor module, An objective lens for condensing light can be formed. The color filter may be configured to be the above-described color filter.
<Example>
As follows, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and further includes all modifications within the meaning and range equivalent to those of the claims. Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.
<Synthesis of Resin A>
90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and 11.0 g of 2-norbornene were mixed and introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. After making the atmosphere into nitrogen in the air, the temperature was raised to 80 ° C., and then a tertiary portion was added to a mixture containing 70.5 g (0.4 mol) of benzyl methacrylate, 45.0 g (0.5 mol) of methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate. The solution to which 3.2 g of tyrperoxy 2-ethylhexyl carbonate was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g [0.2 mol of glycidyl methacrylate ((40 mol% based on the carboxyl groups of methacrylic acid used in this reaction)]], 0.9 g of trisdimethylaminomethylphenol and hydroquinone 0.145 g was thrown into the flask, and reaction was continued at 110 degreeC for 6 hours, and resin A with a solid acid value of 100 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 31,000, and molecular weight distribution (Mw / Mn) was 2.3.
<Synthesis of Resin B>
90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and 11.0 g of 2-norbornene were mixed and introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. After the atmosphere was nitrogen in the air, the temperature was raised to 80 ° C., and then terbutyrruff was added to a mixture containing 47.2 g (0.4 mol) of vinyltoluene, 45.0 g (0.5 mol) of methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate. The solution to which 3.2 g of hydroxy 2-ethylhexyl carbonate was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g [0.15 mol of glycidyl methacrylate ((50 mol% based on the carboxyl groups of methacrylic acid used in this reaction)]], 0.9 g of trisdimethylaminomethylphenol, 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC for 6 hours, and resin B with a solid acid value of 123.7 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 20,000, and molecular weight distribution (Mw / Mn) was 2.3.
<Synthesis of Resin C>
90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and 22.1 g of 2-norbornene were introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the flask was introduced. After raising the atmosphere to nitrogen in the air, the mixture was heated to 80 ° C., and then to a mixture containing 70.5 g (0.4 mol) of benzyl methacrylate, 30 g (0.5 mol) of glycidyl methacrylate, and 136 g of propylene glycol monomethyl ether acetate. The solution to which 3.2 g of terbutyryroxy 2-ethylhexyl carbonates was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 25.8 g (0.3 mol) of methacrylic acid, 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 120 DEG C., where the solid acid value was 0.8. When it became mgKOH / g, reaction was stopped and copolymer C-1 was obtained. Subsequently, 99.7 g (0.6 mol) of tetrahydro phthalic anhydrides were added, it was made to react at 115 degreeC for 2 hours, and the resin C of 77 mgKOH / g of solid content acid value was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 19,500, and molecular weight distribution (Mw / Mn) was 2.3.
<Synthesis of Resin D>
90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and 11.0 g of 2-norbornene were mixed and introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. After making the atmosphere into nitrogen in the air, the temperature was raised to 80 ° C., and then a tertiary portion was added to a mixture containing 105.7 g (0.6 mol) of benzyl methacrylate, 25.8 g (0.3 mol) of methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate. The solution to which 3.2 g of tyrperoxy 2-ethylhexyl carbonate was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Resin D whose solid acid value was 122 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 26,000, and molecular weight distribution (Mw / Mn) was 2.3.
.
<Synthesis of Resin E>
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. g (0.4 mol), 43.0 g (0.5 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 g (0.10 mol), and 136 g of propylene glycol monomethyl ether acetate The solution which added 3.6 g of azobisisobutyronitrile to the mixture containing was dripped at the flask over 2 hours from the dropping lot, and stirring was further continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate [0.2 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and hydroquinone 0.145 g was thrown into the flask, and reaction was continued at 110 degreeC for 6 hours, and resin E with 94 mgKOH / g of solid acid value was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 30,000, and molecular weight distribution (Mw / Mn) was 2.1.
<Synthesis of Resin F>
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. g (0.6 mole), 25.3 g (0.3 mole) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 g (0.10 mole), and 136 g of propylene glycol monomethyl ether acetate The solution to which 3.6 g of azobisisobutyronitrile was added to the mixture containing it was dripped at the flask over 2 hours from the dropping lot, and stirring was continued for further 5 hours at 100 degreeC, The resin whose solid acid value is 120 mgKOH / g. F was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 24,000, and molecular weight distribution (Mw / Mn) was 2.1.
About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said binder polymer, it carried out on condition of the following using GPC method.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)
Column temperature: 40 ℃
Mobile phase solvent: tetrahydrofuran
Flow rate: 1.0 ml / min
Injection volume: 50 μl
Detector: RI
Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)
Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).
<Example 1>
In each component of the following Table 1, it mixes so that the total amount of the pigment which is a coloring material (D), and the pigment dispersant which is an additive (F) may be 20 mass% with respect to the mixture of a pigment, a pigment dispersant, and a propylene glycol monomethyl ether acetate. After the pigment was sufficiently dispersed using the bead mill, the bead mill was separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a colored photosensitive resin composition.
Table 1
A 2 square inch glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The coated photosensitive resin composition (Table 1) was exposed on the glass substrate at an exposure amount (365 nm) of 100 mJ / cm 2 and spin-coated so that the film thickness after post-firing when the developing step was omitted was 1.9 µm. Preliminary drying was carried out at 100 ° C for 3 minutes in a clean oven. After cooling, the substrate to which the colored photosensitive resin composition was applied and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 μm to 50 μm) The space | interval was 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, and then dried at 220 ° C. for 30 minutes after washing with water. No surface roughness was found in the obtained pixel portion. In addition, in the non-pixel portion, no developing residue was generated on the substrate. And even if it develops, the minimum required exposure amount required in order to form the pattern without surface roughness was 30mJ / cm <2>.
<Example 2>
It carried out similarly to Example 1 except having changed resin A into resin B in Example 1. The evaluation results are shown in Table 2.
<Example 3>
It carried out similarly to Example 1 except having changed resin A into resin C in Example 1. The evaluation results are shown in Table 2.
<Example 4>
It carried out similarly to Example 1 except having changed resin A into resin D in Example 1. The evaluation results are shown in Table 2.
Comparative Example 1
It carried out similarly to Example 1 except having changed resin A into resin E in Example 1. The evaluation results are shown in Table 2.
Comparative Example 2
It carried out similarly to Example 1 except having changed resin A into resin F in Example 1. The evaluation results are shown in Table 2.
Table 2
* 1: It shows the minimum required exposure amount necessary to form a thin film free of pattern errors (line tearing) even when developed.
* 2: ○: No development residue on substrate, X: Development residue on substrate
* 3: The cross-sectional shape of the pixel edge part was observed using SEM.
○: Forward tapered, X X: Reverse tapered
* 4: The cured coating film was produced like Example except having not used a photomask. Measurement of the pencil hardness is in accordance with JIS K5600-5-4.
* 5: Outgas was analyzed by pyrolysis at 230 ° C. for 30 minutes through Py-GC / FID to analyze the collected compounds. The results were obtained as a percentage based on 100% of the value of Comparative Example 1.
* 6: The heat resistance measurement calculated | required the color change value before and after leaving to stand at 230 degreeC for 120 minutes.
The photosensitive resin compositions of Examples 1, 2, and 3 containing the unsaturated group-containing binder resin of the present invention from Table 2 have a high sensitivity, and outgas generation is very low in comparison with Comparative Examples 1 and 2, so that a color filter can solve an afterimage problem. It can be seen that is obtained. On the contrary, with the colored photosensitive resin compositions of Comparative Examples 1 and 2 which do not contain the unsaturated group-containing binder resin of the present invention, the amount of outgas is large, so that the quality of the color filter is lowered and a high quality color filter cannot be obtained.
According to the present invention, it is possible to provide a colored photosensitive resin composition having no development residue on the substrate or surface defects occurring in the pixel portion when forming pixels, and excellent in sensitivity, resolution and flatness of the base surface.
In particular, even after a high temperature manufacturing process, it is excellent in heat resistance and can provide the photosensitive resin composition with little change in brightness | luminance and a color characteristic.
In addition, the outgas is significantly reduced, thereby providing a photosensitive resin composition that solves the afterimage problem, thereby providing a high quality color filter.
Moreover, the coloring photosensitive resin composition of this invention can also be used for the liquid crystal display device of a color filter on array system (henceforth a COA system). The coloring photosensitive resin composition of this invention can be preferably used, in order to form the coloring pixel (color image) used for a color liquid crystal display device, an imaging element, etc.
Claims (10)
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KR20040029978A (en) * | 2001-05-11 | 2004-04-08 | 클래리언트 파이낸스(비브이아이)리미티드 | Polymer suitable for photoresist compositions |
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KR20070009419A (en) * | 2005-07-15 | 2007-01-18 | 스미또모 가가꾸 가부시키가이샤 | Colored photosensitive resin composition |
KR20070014998A (en) * | 2005-07-29 | 2007-02-01 | 스미또모 가가꾸 가부시끼가이샤 | Photosensitive resin composition |
KR20070014991A (en) * | 2005-07-29 | 2007-02-01 | 스미또모 가가꾸 가부시끼가이샤 | Photosensitive resin composition for photo spacer |
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