CN109991808A

CN109991808A - Green photonasty resin composition, colored filter and image display device

Info

Publication number: CN109991808A
Application number: CN201811602415.0A
Authority: CN
Inventors: 尹贞玉; 申泳璨; 安大熙; 柳廷昊; 池仁爱; 崔世华
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2018-01-02
Filing date: 2018-12-26
Publication date: 2019-07-09

Abstract

The present invention provides green photonasty resin composition, colored filter and image display device.The green photonasty resin composition includes colorant, alkali soluble resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent, wherein, the colorant includes having 80% or the bigger and transmissivity less than 99% in the wave-length coverage of 450nm to 500nm, and there is 40% or bigger and the transmissivity less than 99% pigment in the wave-length coverage of 760nm to 780nm, and the alkali soluble resin includes being selected from one of repetitive unit indicated by chemical formula 1 to chemical formula 3 or a variety of, therefore, the green photonasty resin composition has excellent transmissivity and excellent contrast to show the color reprodubility of enhancing, and show the developing rate of excellent adhesiveness or chemical resistance and raising.

Description

Green photonasty resin composition, colored filter and image display device

Technical field

The present invention relates to green photonasty resin composition, include the colored filter of the green photonasty resin composition And image display device.

Background technique

Display industry is thoroughly changed into plasma display panel (PDP) from cathode-ray tube (CRT), is had Machine light emitting diode (OLED), liquid crystal display (LCD) etc. are the flat-panel monitor (FPD) of representative.Wherein, LCD is due to its example As thin, light-weight, resolution capability is excellent, the characteristics such as low in energy consumption and be widely used as image used in nearly all industrial circle Display device, and their application is constantly extending always.

In an lcd, transmissivity is adjusted while the white light generated from light source passes through liquid crystal cells, and is mixed by red Color, the three primary colors of green and blue (RGB) colored filter transmitting are panchromatic to realize.

It is known that, conventionally, the colored filter used in an lcd can pass through decoration method, print process, electrodeposition process and pigment Dispersion method manufactures.Past, it has been contemplated that using the method for dyestuff manufacture colored filter, but it is color when using dyestuff to manufacture When colo(u)r filter, which shows all these below pigment manufactures such as heat resistance, light resistance, chemical resistance Colored filter, thus be not easy to apply.Moreover, because the complexity of the technique, decoration method are not economically feasible. In recent years, most-often used pigment dispersion method.

Although pigment is not so good as dyes transparent, the fineness of pigment and the progress of dispersion technology have overcome this point. The colored filter manufactured by pigment dispersion method is worked as logical since the pigment used is stable to light, heat, solvent etc. Cross photoetching carry out patterning process when, the colored filter for large screen and high-precision color monitor be it is easily fabricated, Therefore it is most widely applied in recent years.

According to the method for manufacturing colored filter by pigment dispersion method, colored filter solution coating is arrived with spinner It is on substrate and dry to form film.Then, film is exposed to pattern and developed to obtain colored pixels, and at high temperature Temper tiniting pixel is to obtain the first colored pattern.Repeat the process according to chromaticity coordinates to manufacture colored filter.

In recent years, being widely used with liquid crystal display (LCD) equipment, application field has been expanded to various types of Display and television set (TV), it is desirable that color reprodubility further increases.

In this respect, the uncensored patent disclosure of South Korea the 10-2013-0134494th discloses printing ink composition, packet Include in 480nm or smaller and 600nm or more it is big have 10% or smaller spectral-transmission favtor, in 520nm to 540nm with 70% Or smaller spectral-transmission favtor and include a) C.I. pigment Green 7 and C.I. pigment yellow 185 colorant；With include b) adhesive The compound of resin and c) blocked isocyanate groups, wherein with relative to C.I. pigment Green 7 be 10 weight % to 40 weight % Amount include C.I. pigment yellow 185.

In addition, the uncensored patent disclosure of South Korea the 10-2016-0097261st discloses for colored filter Green composite, including green colourant, near infrared ray (NIR) absorbent and polymerizability compound, wherein when green combines When the coloring film that object is used to form with a thickness of 0.8 μm, which has 5% or smaller max transmissive in 400nm to 450nm Rate, has 70% or bigger maximum transmission rate in 500nm to 600nm, has 20% or smaller in 650nm to less than 700nm Minimum transmittance, 700nm to 900nm have 30% or smaller minimum transmittance, with by the quality of green colourant/ The quality of NIR absorbent and 0.1 to 0.4 mass ratio that calculates includes green colourant and NIR absorbent.

However, these routine techniques are not able to satisfy the requirement to color reprodubility level in recent years.

(existing technical literature)

(patent document)

The uncensored patent disclosure of (patent document 1) South Korea the 10-2013-0134494th (on December 10th, 2013)

The uncensored patent disclosure of (patent document 2) South Korea the 10-2016-0097261st (on August 17th, 2016)

Summary of the invention

1. technical problem

Present invention design is to solve the above problems, and be intended to provide green photonasty resin composition and green including this The colored filter and image display device of color sensation photosensitive resin composition, the green photonasty resin composition have excellent Transmissivity and excellent contrast can be realized high color reprodubility, and show excellent adhesiveness or chemical resistance and The developing rate of raising.

2. solution

In order to realize the above target, green photonasty resin composition according to the present invention includes colorant, alkali-soluble Resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent, wherein the colorant includes the wave in 450nm to 500nm Transmissivity in long range with 80% or bigger and less than 99%, in the wave-length coverage of 760nm to 780nm with 40% or Bigger and the transmissivity less than 99% pigment, and the alkali soluble resin includes selected from by following formula 1 to chemical formula 3 One of repetitive unit of expression is a variety of.

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

In chemical formula 1 into chemical formula 3,

R^aTo R^cEach independently represent hydrogen or methyl group.

In addition, colored filter according to the present invention includes the cured product of above-mentioned green photonasty resin composition.

In addition, image display device according to the present invention includes above-mentioned colored filter.

3. beneficial effect

Green photonasty resin composition according to the present invention can have excellent transmissivity and excellent contrast with It can be realized high color reprodubility, and the developing rate of excellent adhesiveness or chemical resistance and raising can be shown.

In addition, colored filter according to the present invention includes the cured product of the green photonasty resin composition, therefore It can have advantage same as described above.

In addition, image display device according to the present invention includes the cured product of the green photonasty resin composition, because This can have advantage same as described above.

Detailed description of the invention

Fig. 1 shows the composition of embodiment according to the present invention and comparative example according to the Optical transmission spectrum of wavelength.

Fig. 2 shows the compositions of embodiment according to the present invention and comparative example in the wave-length coverage of 450nm to 500nm Transmissivity.

Fig. 3 shows the composition of embodiment according to the present invention and comparative example in the wave-length coverage of 760nm to 780nm Transmissivity.

Specific embodiment

When describing the present invention, when component is referred to as at another component "upper", this not only includes two of them component The case where being in contact with each other, but also include the case where that there is third component between two of them component.

When describing the present invention, when component is referred to as " containing ", "comprising", " comprising " or " having " another group of timesharing, answer It is understood as the component to be not excluded for other components but also may include other components, unless otherwise clearly stating.

Hereinafter, the present invention will be described in further detail.

According to an aspect of the present invention, green photonasty resin composition includes that colorant, alkali soluble resin, light can Polymerizable compound, Photoepolymerizationinitiater initiater and solvent, wherein the colorant includes having in the wave-length coverage of 450nm to 500nm Have 80% or the bigger and transmissivity less than 99%, has 40% or bigger in the wave-length coverage of 760nm to 780nm and be less than The pigment of 99% transmissivity, and the alkali soluble resin includes selected from the repetition indicated by following formula 1 to chemical formula 3 One of unit is a variety of, and therefore, which has excellent transmissivity and excellent contrast To show the color reprodubility of enhancing, and show the developing rate of excellent adhesiveness or chemical resistance and raising.

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

In chemical formula 1 into chemical formula 3,

R^aTo R^cEach independently represent hydrogen or methyl group.

Alkali soluble resin

Alkali soluble resin usually has reactivity to light or heat and dissolves in alkali, and the dispersion for being used as colorant is situated between Matter.Green photonasty resin composition according to an aspect of the present invention can show the developing rate of raising and adhere to Property or chemical resistance in terms of show excellent reliability, and can be by including selected from being indicated by chemical formula 1 to chemical formula 3 One of repetitive unit or a variety of residue is inhibited to occur.

According to an embodiment of the invention, total repetitive unit of the alkali soluble resin relative to 100 moles of %, can wrap Containing 10 moles of % to 90 moles of % selected from one of repetitive unit indicated by chemical formula 1 to chemical formula 3 or a variety of.

Comprising selected from one of repetitive unit indicated by chemical formula 1 to chemical formula 3 or a variety of alkali soluble resins It can be prepared for example, by being copolymerized one or more monomers selected from the following: 3,4- epoxycyclohexyl-methyl acrylate, 3, 4- epoxycyclohexyl-methyl methacrylate, 3,4- epoxy tricyclic [5.2.1.0^2,6] decyl- 8- base acrylate, 3,4- epoxy Tricyclic [5.2.1.0^2,6] decyl- 8- methyl acrylate, 3,4- epoxy tricyclic [5.2.1.0^2,6] decyl- 9- base acrylate and 3, 4- epoxy tricyclic [5.2.1.0^2,6] decyl- 9- methyl acrylate.

In addition to selected from one of repetitive unit for being indicated by chemical formula 1 to chemical formula 3 or it is a variety of other than, alkali-soluble tree Rouge can also include other repetitive units.The ethylenic bond with carboxylic group is originated from such a case, it is possible to preferably include The repetitive unit of unsaturated monomer ensures as other repetitive units can developability.

The specific example of ethylenically unsaturated monomers with carboxylic group includes monocarboxylic acid, such as acrylic acid, methyl Acrylic acid, crotonic acid etc.；Dicarboxylic acids, such as fumaric acid, mesaconic acid, itaconic acid etc.；The acid anhydrides of dicarboxylic acids；In polymer Two ends respectively have list (methyl) acrylate of the polymer of carboxylic group and hydroxyl group, such as ω-carboxyl gathers oneself Lactone list (methyl) acrylate etc..It among these compounds, can preferred acrylic or methacrylic acid.

In addition, alkali soluble resin can be by further adding in addition to the ethylenically unsaturated monomers with carboxylic group Except can be selected from one of repetitive unit for being indicated by chemical formula 1 to chemical formula 3 or a variety of repetitive units with for introducing Monomer copolymerization other one or more unsaturated monomers prepared by being copolymerized.

The specific example of other copolymerizable unsaturated monomers includes:

Aromatic ethenyl compound, such as styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, adjacent first Oxygroup styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, vinyl benzyl ylmethyl Ether, to vinyl benzyl methyl ether, adjacent vinylbenzyl glycidyl ether, vinylbenzyl glycidyl ether, to vinyl Benzyl glycidyl ether etc.；

Based on the compound of the N- maleimide replaced, such as N- N-cyclohexylmaleimide, N- benzyl maleimide Amine, N-phenylmaleimide, N- salicyl maleimide, N- resorcyl maleimide, N- p-hydroxyphenyl Malaysia Methylphenylmaleimide between acid imide, N- o-methyl-phenyl maleimide, N-, N- p-methylphenyl maleimide, N- o-methoxyphenyl maleimide, N- m-methoxyphenyl maleimide, N- p-methoxyphenyl maleimide etc.；

(methyl) alkyl acrylate, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid N-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid Secondary butyl ester, (methyl) tert-butyl acrylate etc.；

(methyl) acrylate cyclic ester, such as (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) third Olefin(e) acid -2- methyl cyclohexyl, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decyl- 8- ester, two ring of (methyl) acrylic acid -2-, penta oxygen Base ethyl ester, (methyl) isobornyl acrylate etc.；

(methyl) benzyl acrylate, such as (methyl) phenyl acrylate, (methyl) benzyl acrylate etc.；With

Unsaturated oxetane compound, such as 3- (methacryloxymethyl) oxetanes, 3- (methyl-prop Alkene pivaloyloxymethyl) -3- Ethyloxetane, 3- (methacryloxymethyl) -2- trifluoromethyl oxetanes, 3- (methacryloxymethyl) -2- phenyl oxetanes, 2- (methacryloxymethyl) oxetanes, 2- (first Base acryloyloxymethyl) -4- trifluoromethyl oxetanes etc..

But the invention is not limited thereto, and these monomers can be used alone or be made with the combination of two or more With.

The preparation of copolymer is not limited to specific method, and can be carried out by conventional known polymerization methods.? In the polymerization known, polymerisation in solution be can be preferably.In addition, class of the temperature and time of polymerization according to the monomer to be introduced The desired molecular weight and acid value of type and ratio and alkali soluble resin and change.For example, polymerization can be at 60 DEG C to 130 DEG C It is lower to carry out 1 hour to 10 hours.

When being polymerize using solvent, the solvent that solvent can be commonly used in free radical polymerization, the specific reality of solvent Example may include tetrahydrofuran, dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, 3- methoxybutyl acetic acid esters, methanol, Ethyl alcohol, propyl alcohol, n-butanol, glycol monoethyl ether, propylene glycol monomethyl ether, toluene, dimethylbenzene, ethylbenzene, chloroform, dimethyl sulfoxide etc.. These solvents can be used alone or being applied in combination with two or more.

Polymerization initiator for polymerization can be common polymerization initiator, but be not particularly limited.Polymer causes The specific example of agent includes organic peroxide, such as diisopropyl benzene hydroperoxides, di-tert-butyl peroxide, peroxidating Benzoyl, BPIC t butyl peroxy isopropyl carbonate, t-amyl peroxy -2 ethyl hexanoic acid ester, t-butyl peroxy -2 ethyl hexanoic acid ester Deng；And nitrogen compound, such as 2,2 '-azos bis- (isobutyronitriles), 2,2 '-azos bis- (2,4- methyl pentane nitriles), 2,2 '-azos Bis- (2 Methylpropionic acid) dimethyl esters etc..These compounds can be used alone or being applied in combination with two or more.

In the course of the polymerization process, chain-transferring agent can be used to control the molecular weight or molecular weight distribution of copolymer.Chain tra nsfer The example of agent includes sulfhydryl compound, such as n- dodecyl mereaptan, mercaptoacetate, methyl thioglycolate etc.；α-methylstyrene Dimer；Deng.

Alkali soluble resin can have the acid value of 30mgKOH/g to 200mgKOH/g.Terms used herein " acid value " Refer to the value of amount (mg) measurement as potassium hydroxide needed for neutralizing 1g polymer, and usually can be by using hydroxide The titration of aqueous solutions of potassium calculates.When the acid value of alkali soluble resin is less than 30mgKOH/g, green photonasty resin composition Enough developing rates are difficult to ensure, and when the acid value of alkali soluble resin is greater than 200mgKOH/g, when forming pattern The adhesiveness of itself and substrate reduces, therefore is easy to happen pattern disconnection.

In addition, passing through gel permeation chromatography (GPC；Use tetrahydrofuran as eluting solvent) measurement alkali-soluble tree The weight average molecular weight (hereinafter referred to as " weight average molecular weight ") that lipid phase converts for polystyrene standards can be 5000 to 50000, preferably 5000 to 30000.When the weight average molecular weight of alkali soluble resin is fallen in the range, coated film be can have The hardness of enhancing and high film retention rate, unexposed area can have excellent dissolubility in developing solution, and differentiate Rate can be improved.

Alkali soluble resin preferably has 1.5 to 6.0, more preferably 1.8 to 4.0 molecular weight distribution (Weight-average molecular It measures (Mw)/number-average molecular weight (Mn)).When the molecular weight distribution (Mw/Mn) of alkali soluble resin is 1.5 to 6.0, can be enhanced It can developability.

The total solids content of green photonasty resin composition relative to 100 weight %, can be with 10 weight % to 80 The amount of weight %, preferably 10 weight % to 70 weight % include alkali soluble resin.When the content of alkali soluble resin falls in this When in range, due to the abundant dissolubility in developing solution, it can be readily formed pattern, and because prevent exposure Film on the pixel region in light region is reduced during development, it is possible to satisfactorily remove non-pixel region.

Colorant

Green photonasty resin composition according to an aspect of the present invention is by including the wave in 450nm to 500nm Transmissivity in long range with 80% or bigger and less than 99%, in the wave-length coverage of 760nm to 780nm with 40% or Bigger and the transmissivity less than 99% pigment, can have excellent transmissivity and excellent contrast to show enhancing Color reprodubility.

Pigment

According to an embodiment of the invention, the pigment for meeting above-mentioned spectral signature may include phthalocyanine aluminium compound.

Specifically, phthalocyanine aluminium compound can be center and aluminium and the phthalocyanine for being located at phthalocyanine ring with wherein trivalent aluminium The compound for the structure that ring nitrogen combines.Other than phthalocyanine ring nitrogen, the aluminium of phthalocyanine aluminium compound may be used also In conjunction with other atoms.Furthermore, it is possible to which the phthalocyanine ring to phthalocyanine aluminium compound carries out various chemical modifications.In addition to monomer it Outside, phthalocyanine aluminium compound can polymerize to form dimer, tripolymer etc..

According to an embodiment of the invention, phthalocyanine aluminium compound may include being indicated by following formula 4 or chemical formula 5 Compound.

[chemical formula 4]

In chemical formula 4,

R¹To R¹⁶Each independently represent hydrogen, halogen atom, nitryl group, substitutive phthalimide methyl base Group, substitutive sulfamoyl group, substitutive C₁To C₁₈Alkyl group, substitutive C₆To C₁₄Aryl group may replace C₅To C₁₀Group of naphthene base, heterocyclic group, substitutive C₁To C₁₈Alkoxy base, substitutive C₆To C₁₄Aryloxy group base Group, substitutive C₁To C₁₈Alkylthio radicals or substitutive C₆To C₁₄Arylthio group, and

Z expression-OP (=O) X₁X₂,

Wherein, X₁And X₂Each independently represent hydrogen, hydroxyl group, substitutive C₁To C₁₈Alkyl group, substitutive C₆ To C₁₄Aryl group, substitutive C₁To C₁₈Alkoxy base or substitutive C₆To C₁₄Aryloxy group, and

X₁And X₂It can be in conjunction with phosphorus atoms to form heterocycle.

Terms used herein " substitutive " are to refer to further include substituent group.In this case, replace Base can be the same or different from each other, and the specific example of substituent group includes halogen group (including fluorine, chlorine, bromine etc.), characteristic group (example Such as hydroxyl group, nitryl group, amino group), alkyl group, aryl group, group of naphthene base, aryloxy group, alkane sulphur Base group, arylthio group etc., however, the present invention is not limited thereto.

Halogen atom can be fluorine, chlorine, bromine etc..In instances, as the R in chemical formula 4¹To R¹⁶When including hydrogen, chlorine or bromine, There may be 1 to 6 hydrogen atom, 3 to 9 chlorine atoms or 2 to 7 bromine atoms or all R¹To R¹⁶It can be hydrogen, But the invention is not restricted to this.

Alkyl group refers to straight-chain hydrocarbons or branched-chain hydrocarbons, and e.g. methyl group, ethyl group, propyl group, isopropyl Base group, butyl group, isobutyl groups, tertiary butyl groups, neopentyl group, n-hexyl group, n-octyl group, stearoyl Base group, 2- ethylhexyl group etc..In addition, alkyl group may include substituent group, the example of the alkyl group includes trichlorine Methyl group, trifluoromethyl group, 2,2,2- trifluoroethyl group, 2,2- dibromoethyl group, tetra- fluoropropyl base of 2,2,3,3- Group, 2- ethoxyethyl group group, 2- butoxyethyl group group, 2- nitropropyl group, benzyl group, 4- methyl benzyl group, 4- t-butylbenzyl group, 4- methoxybenzoyl group, 4- nitrobenzyl group, 2,4- dichloro benzyl group etc..

Aryl group is, for example, phenyl group, naphthyl group, anthracyl radical etc..In addition, aryl group may include replacing Base, the example of the aryl group include p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, to methoxybenzene Base group, 2,4 dichloro benzene base group, pentafluorophenyl group group, 2- aminophenyl group, 2- methyl -4- chlorophenyl group, 4- hydroxyl Base -1- naphthyl group, 6- methyl -2- naphthyl group, the chloro- 2- naphthyl group of 4,5,8- tri-, anthraquinonyl group, 2- amino anthracene quinonyl Group etc..

Group of naphthene base is, for example, cyclopentyl group, cyclohexyl groups, adamantyl group etc..In addition, group of naphthene base It may include substituent group, the example of the group of naphthene base includes 2,5- dimethylcyclopentyl group, 4- tert-butylcyclohexyl group Deng.

Heterocyclic group be, for example, Pyridyl residues, pyrazinyl group, piperidinyl group, pyranyl groups, morpholinyl group, Acridinyl group etc..

Alkoxy base can be straight chain or branch, and e.g. methoxy group, ethoxy group, propoxyl group Group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyl oxygen group, 2,3- bis- Methyl -3- amoxy group, positive hexyloxy group, n-octyloxy group, stearoyl-oxy group, 2- ethyl hexyl oxy group Deng.In addition, alkoxy base may include substituent group, the example of the alkoxy base includes trichloromethoxy group, fluoroform Oxygroup group, 2,2,2- trifluoro ethoxy group, 2,2,3,3- tetrafluoro propoxy group, bis- trifluoromethyl propoxyl group base of 2,2- Group, 2- ethoxy ethoxy group, 2- Butoxyethoxy group, 2- nitro propoxy group, benzyloxy group etc..

Aryloxy group is, for example, phenyloxy groups, naphthyloxy group, anthracene oxygroup group etc..In addition, aryloxy group can To include substituent group, the example of the aryloxy group includes to methylphenoxy group, p-nitrophenyl oxygroup group, to methoxyl group Phenyloxy groups, 2,4 dichloro benzene oxygroup group, pentafluorophenyloxy radical, 2- methyl -4- chlorophenoxy group etc..

Alkylthio radicals are, for example, methyl mercapto group, ethylmercapto group group, the third thio groups, butylthio group, thiophenyl base Group, own thio groups, pungent thio groups, last of the ten Heavenly stems thio groups, dodecylthio group, octa-decylthio group etc..In addition, alkane sulphur Base group may include substituent group, and the example of the alkylthio radicals includes methoxyl group ethylmercapto group group, aminoethanethio group, benzyl Base aminoethanethio group, mentioned methylcarbonylamino ethylmercapto group group, benzylcarbonylamino ethylmercapto group group etc..

Arylthio group is, for example, thiophenyl group, 1- naphthalene thio groups, 2- naphthalene thio groups, 9- anthracene thio groups etc.. In addition, arylthio group may include substituent group, the example of the arylthio group includes chlorophenylsulfanyl group, trifluoromethylbenzene sulphur Base group, cyano thiophenyl group, nitrophenylsulfenyl group, 2- aminobenzene-thio group, 2- hydroxy benzenes thio groups etc..

[chemical formula 5]

In chemical formula 5,

R¹⁷To R³²Each independently represent hydrogen, halogen atom, nitryl group, substitutive phthalimide methyl Group, substitutive sulfamoyl group, substitutive C₁To C₁₈Alkyl group, substitutive C₆To C₁₄Aryl group can use The C in generation₅To C₁₀Group of naphthene base, heterocyclic group, substitutive C₁To C₁₈Alkoxy base, substitutive C₆To C₁₄Aryloxy group base Group, substitutive C₁To C₁₈Alkylthio radicals or substitutive C₆To C₁₄Arylthio group, and

L is indicated

Wherein, X₃To X₇Each independently represent substitutive C₁To C₁₈Alkyl group or substitutive C₆To C₁₄Aryl base Group.

Halogen atom is, for example, fluorine, chlorine, bromine etc..

According to an embodiment of the invention, phthalocyanine aluminium compound may include C.I. naphthol green 62 or C.I. naphthol green 63.

According to an embodiment of the invention, all coloring agent relative to 100 weight %, it can be with 30 weight % to 100 The amount of weight % includes phthalocyanine aluminium compound.When the content of phthalocyanine aluminium compound is fallen in the range, high color may be implemented Color reproducibility, and colourability and transmissivity can also be improved.

Pigment may further include the pigment other than above-mentioned phthalocyanine aluminium compound.

Various organic pigments or inorganic pigment commonly used in the art can be used and be used as the pigment for further comprising.

As organic pigment, can be used for printing the various pigment in ink, jetted ink etc., and the pigment Specific example includes water-soluble azo pigment, insoluble azo colour, phthalocyanine color, quinacridone pigment, isoindolinone face Material, isoindoline pigment, pigment, pyrene ketone pigment, dioxazines pigment, anthraquinone pigment, bi-anthraquinone pigment, anthrapyrimidine pigment, Anthanthrone pigment, indanthrone pigment, yellow anthrone pigment, pyranthrone pigments, pyrrolo-pyrrole-dione pigment etc..Inorganic pigment Example includes metallic compound (such as metal oxide, metal complex salt etc.), and the specific example of the metallic compound includes The oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. or its metal composite oxide.Particularly, in colour index It is classified as in the compound of pigment in (learning to publish by dyers and colourist), organic pigment or inorganic pigment are preferably C.I. Naphthol green or C.I. pigment yellow more particularly can be the pigment with following colour indexs (C.I.) numerical value, but the present invention is not It is necessarily limited to this.

Pigment can be viridine green, such as C.I. pigment Green 7,36,58,59 etc.；Yellow uitramarine, such as C.I. pigment yellow 129,138,139,231,150,185 etc..These pigment can be used alone or being applied in combination with two or more.

According to an embodiment of the invention, green photonasty resin composition can also include the C.I. face in above-mentioned pigment Expect 138 or C.I. of Huang pigment yellow 231.When the pigment is used together with above-mentioned phthalocyanine aluminium compound, color can be further improved Color reproducibility and brightness can also improve colourability to prevent display defect (such as visibility deterioration etc.), and can hold It changes places to form fine pattern.

According to an embodiment of the invention, when green photonasty resin composition also include above-mentioned C.I. pigment yellow 13 8 or It C.I., can be with 10 weight % to 70 weight %, particularly 20 relative to all coloring agent of 100 weight % when pigment yellow 231 The amount of weight % to 70 weight %, more particularly 30 weight % to 70 weight % include C.I. pigment yellow 13 8 or C.I. pigment yellow 231.When its content is fallen within this range, color reprodubility and brightness can be further improved.

Pigment uses preferably in the form of the evenly dispersed pigment dispersion of wherein pigment particle size.In order to be uniformly dispersed The granularity of pigment can be used comprising pigment dispersing agent and the method for carrying out decentralized processing, and in this way, can obtain The wherein evenly dispersed pigment dispersion in the solution of pigment.

Dispersing agent

Dispersing agent is added to keep the depolymerization and stability of colorant, and dispersing agent can be it is commonly used in the art Any dispersing agent is without limiting.Commercial dispersants can be DisperBYK-101,103,107,108,110,111,112, 116、130、140、142、154、161、162、163、164、165、166、167、168、170、171、174、180、181、182、 183、184、185、190、2000、2001、2009、2010、2020、2025、2050、2070、2095、2150、2155、2163、 2164 (BYK Additives&Instruments), Solsperse-3000,9000,13000,13240,13650,13940, 16000、17000、18000、20000、21000、24000、26000、27000、28000、31845、32000、32500、 32550、33500、32600、34750、35100、36600、38500、41000、41090、53095、55000、56000、76500 (Lubrizol Corporation) etc., however, the present invention is not limited thereto.

These dispersing agents can be used alone or being applied in combination with two or more, and preferably have acid official The dispersing agent that can be rolled into a ball, such as DisperBYK-2000,2001 (BYK Additives&Instruments), Solsperse- 3000,21000,26000,36600,41000 (Lubrizol Corporation) etc., however, the present invention is not limited thereto.

The content of dispersing agent is not particularly limited in the present invention, relative to the colorant total solids content of 100 parts by weight, It can include dispersing agent with 5 parts by weight to 60 parts by weight, the amount of preferably 15 parts by weight to 50 parts by weight.When the content of dispersing agent is big When the range, viscosity be will increase, and when the content of dispersing agent is less than the range, the atomization of pigment can be difficult, or meeting Gelation after leading to dispersion.

Dyestuff

When necessary, green photonasty resin composition according to the present invention can further include dyestuff.

Dyestuff can be further used without limiting, as long as the dyestuff has dissolubility in organic solvent or can divide It dissipates in organic solvent.It is preferable to use the dissolubility that can ensure in alkali developing solution, heat resistance and solvent resistance can By property, there is deliquescent dyestuff in organic solvent simultaneously.Dyestuff can selected from acidic-group acid dyes (such as Sulfonic acid, carboxylic acid etc.), the salt of acid dyes and nitrogenous compound, acid dyes sulfonamide and its derivative.In addition, dyestuff can To be selected from acid dyes, the acid dyes based on xanthene, the acid dyes and its derivative based on phthalocyanine of azo-based. Preferably, dyestuff may include be classified as in colour index (learning to publish by dyers and colourist) dyestuff compound or Known dye described in coloring explanation (Color Dyeing Co.).

The specific example of dyestuff includes:

C.I. solvent dye, such as C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99,162 Deng green 1,3,4,5,7,28,29,32,33,34,35 etc. (green dyes) of (weld) and C.I. solvent；

C.I. acid dyes, for example, C.I. Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54, 65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、 150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、 203, (the yellow dye such as 204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251 Material) and C.I. acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109 etc. (green dye)；

C.I. direct dyes, for example, C.I. directly Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70, 71,86,93,94,95,98,102,108,109,129,136,138,141 etc. (welds) and C.I. direct green 25,27, 31,32,34,37,63,65,66,67,68,69,72,77,79,82 etc. (green dye)；With

C.I. mordant dye, for example, C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61, 62, (the green such as 65 etc. (welds) and C.I. viridon 1,3,4,5,10,15,19,26,29,33,34,35,41,43,53 Dyestuff), however, the present invention is not limited thereto.These dyestuffs can be used alone or being applied in combination with two or more.

According to an embodiment of the invention, the total solid of the green photonasty resin composition relative to 100 weight % contains Amount can include colorant with the amount of 5 weight % to 60 weight %, preferably 15 weight % to 50 weight %.When containing for colorant When amount is fallen in the range, pixel has enough color densities during forming film, satisfactorily removes during development Non-pixel region, therefore can prevent residue from occurring.

Terms used herein " solid content of green photonasty resin composition " refer in addition to being included in green light sensitive The pure solid content except all solvents in property resin combination.

Photopolymerizable compound

Green photonasty resin composition according to an aspect of the present invention includes photopolymerizable compound.

Photopolymerizable compound is without limitation to be appointed by what the effect of following Photoepolymerizationinitiater initiaters polymerize What compound, e.g. monofunctional monomer, bifunctional monomer or polyfunctional monomer.Preferably, which is At least bifunctional polyfunctional monomer.

The specific example of monofunctional monomer includes nonyl phenyl carbitol acrylate, 2- hydroxyl -3- phenoxy propyl third Olefin(e) acid ester, 2- ethylhexyl carbitol acrylate, 2- hydroxy ethyl methacrylate, n-vinyl pyrrolidone etc., but the present invention It is without being limited thereto.

The specific example of bifunctional monomer includes 1,6-hexylene glycols two (methyl) acrylate, ethylene glycol two (methyl) propylene Acid esters, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A are bis- (acryloyl-oxyethyl) Ether, 3- methyl pentanediol two (methyl) acrylate etc., however, the present invention is not limited thereto.

The specific example of polyfunctional monomer includes the three hydroxyl first of trimethylolpropane tris (methyl) acrylate, ethoxylation Base propane three (methyl) acrylate, propenoxylated trimethylolpropane tris (methyl) acrylate, three (first of pentaerythrite Base) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, ethoxylation two Pentaerythrite six (methyl) acrylate, propenoxylated dipentaerythritol six (methyl) acrylate, six (first of dipentaerythritol Base) acrylate etc., however, the present invention is not limited thereto.

The total solids content of green photonasty resin composition relative to 100 weight %, can be with 5 weight % to 45 weights The amount for measuring %, preferably 7 weight % to 45 weight % includes photopolymerizable compound.When the content of photopolymerizable compound is fallen When in the range, the pixel region with satisfactory intensity and smoothness can produce.

Photoepolymerizationinitiater initiater

Green photonasty resin composition according to an aspect of the present invention includes Photoepolymerizationinitiater initiater.According to the present invention Embodiment, the Photoepolymerizationinitiater initiater includes oxime ester compound, therefore the green photonasty resin composition obtains more So as to prevent pattern from removing, and fine pattern may be implemented in high sensitivity.

The example of oxime ester compound includes 1,2- acetyl caproyl, 1- [4- (thiophenyl) phenyl] -2- (O- benzoyl oximes), 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] ethyl ketone 1- (O- acetyl group oxime) and commercial product (such asOxe01、Oxe02 andOxe03(BASF SE)).Oxime ester compound is preferably with two Kind or more is applied in combination, because it has various absorbances and generates various Kinds of Free Radicals.

In addition, green photonasty resin composition according to the present invention may include other than above-mentioned oxime ester compound Photoepolymerizationinitiater initiater.Typically, it is preferable to use selected from by acetophenone compound, benzophenone cpd, triaizine compounds, connection One of group of imidazolium compounds and thioxanthone compounds composition or multiple compounds.

The specific example of acetophenone compound include diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl propyl- 1- ketone, Benzyl dimethyl ketal, 2- hydroxyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -2- methyl propyl- 1- ketone, 1- hydroxycyclohexylphenyl Ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholino propyl- 1- ketone, 2- benzyl-2- dimethylamino-1- (4- morphlinophenyl) Butyl- 1- ketone, 2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) phenyl] propyl- 1- ketone, 2- (4- methylbenzyl) -2- (diformazan Amino) -1- (4- morphlinophenyl) butyl- 1- ketone etc..

The example of benzophenone cpd include benzophenone, O- benzoyl methyl benzoate, 4- phenyl benzophenone, 4- benzoyl -4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6- front three Base benzophenone etc..

The specific example of triaizine compounds include bis- (trichloromethyl) -6- (4- the methoxyphenyl) -1,3,5- triazines of 2,4-, 2,4- bis- (trichloromethyl) -6- (4- methoxyl group naphthalene) -1,3,5- triazine, bis- (the trichloromethyl) -6- piperonyl -1,3,5- of 2,4- Bis- (trichloromethyl) -6- (4- the methoxyl-styrene) -1,3,5- triazines of triazine, 2,4-, bis- (trichloromethyl) -6- [2- of 2,4- (5- methylfuran -2- base) vinyl] -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (furans -2- base) vinyl] - Bis- (the trichloromethyl) -6- of 1,3,5- triazine, 2,4- [2- (4- lignocaine -2- aminomethyl phenyl) vinyl] -1,3,5- triazine, 2, Bis- (the trichloromethyl) -6- of 4- [2- (3,4- Dimethoxyphenyl) vinyl] -1,3,5- triazine etc..

The example of united imidazole includes 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 ' - Bis- (2,3- dichlorophenyl) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-four (alkoxies Phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines, 2,2 '-bis- (2,6- bis- Chlorphenyl) -4,4 ', 5,5 '-tetraphenyls -1,2 '-bisglyoxaline, wherein 4,4 ', 5,5 ' positions phenyl group by alkoxycarbonyl group Substituted imidazolium compounds etc..In these compounds listed above, it is preferred to use 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 '-bis- (2,3- dichlorophenyl) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines or the bis- (2,6- of 2,2- Dichlorophenyl) -4,4 ', 5,5 '-tetraphenyls -1,2 '-bisglyoxaline.

The example of thioxanthone compounds include 2-isopropylthioxanthone, 2,4- diethyl thioxanthone, bis- clopenthixal ketone of 2,4-, Chloro- 4- propoxythioxanthone of 1- etc..

In addition, Photoepolymerizationinitiater initiater is also in order to improve the sensitivity of green photonasty resin composition according to the present invention It may include photopolymerization initiator.When green photonasty resin composition according to the present invention also includes that this photopolymerization causes When auxiliary agent, sensitivity be can be further improved, so as to improve productivity.

As photopolymerization initiator, can be preferably used selected from by amine compounds, carboxylic acid compound and multifunctional sulphur One of group of alcoholic compound composition or multiple compounds.

Amine compounds are preferably aromatic amine compound, and the specific example of amine compounds includes amine compound, example Such as triethanolamine, methyl diethanolamine and triisopropanolamine；And aromatic amine compound, such as 4- dimethylamino benzene Methyl formate, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, 4- dimethylaminobenzoic acid 2- Ethylhexyl, 2- dimethyl aminoethyl benzoic ether, N, N- dimethyl-p-toluidine, 4,4 '-bis- (dimethylamino) hexichol Ketone (also known as michaelis ketone), 4,4 '-bis- (diethylamino) benzophenone etc..

Carboxylic acid compound is preferably the miscellaneous acetic acid of aromatic series, specific example include thiophenyl acetic acid, methylphenyl-sulfanyl acetic acid, Ethylthiophenyl acetic acid, ethyl methyl benzene ethyl thioglycollic acid, dimethyl benzene ethyl thioglycollic acid, Methoxv-phenylsulfanvl acetic acid, dimethoxy Thiophenyl acetic acid, chlorophenylsulfanyl acetic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthalene ethyl thioglycollic acid, N- Naphthalene glycine, naphthoxy acetic acid etc..

The example of multi-functional thiol's compound includes three-[(3- mercaptopropionyl oxygroup)-ethyl]-isocyanuric acid esters, three hydroxyls Three -3-thiopropionate of methylpropane, four -3-thiopropionate of pentaerythrite, six -3-thiopropionate of dipentaerythritol etc..

It, can be with 0.1 relative to the alkali soluble resin of 100 parts by weight and the total solids content of photopolymerizable compound Parts by weight to 40 parts by weight, the amount of preferably 1 parts by weight to 30 parts by weight includes Photoepolymerizationinitiater initiater.When containing for Photoepolymerizationinitiater initiater When amount is fallen in the range, green photonasty resin composition obtains higher sensitivity, therefore the time for exposure shortens, and is mentioned High productivity, and keep high-resolution.In addition, green photonasty resin composition according to the present invention, which can be formed, to be had The pixel region of satisfactory intensity and surface smoothness.

In addition, when Photoepolymerizationinitiater initiater contains oxime ester compound, it, can be with 10 weights relative to whole Photoepolymerizationinitiater initiaters The amount for measuring % to 100 weight %, preferably 20 weight % to 100 weight % includes oxime ester compound.When the content of oxime ester compound When less than 10 weight %, then it can be difficult to solve the problems, such as sensitivity decrease, and the meeting in developing process by using colorant Pattern occurs to disconnect.

When also including photopolymerization initiator, alkali soluble resin and photopolymerizable relative to 100 parts by weight The total solids content of object is closed, it can be poly- comprising light with 0.1 parts by weight to 40 parts by weight, the amount of preferably 1 parts by weight to 30 parts by weight It closes and causes auxiliary agent.When the content of photopolymerization initiator is fallen in the range, green photonasty resin composition obtains higher Sensitivity, and when the composition for colored filter produce when, the productivity of colored filter can be improved.

Solvent

Green photonasty resin composition according to an aspect of the present invention includes solvent.

Solvent is preferably propylene glycol methyl ether acetate, and can be any solvent used in the art without spy It does not limit, as long as it effectively dissolves the other compositions for including in green photonasty resin composition.The example of solvent include ether, Aromatic hydrocarbon, ketone, alcohol, ester, amide etc..

The specific example of solvent includes ether, such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, second two Alcohol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, propylene glycol list Methyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dimethyl ether, dipropylene glycol diethyl ether, two Propylene glycol dipropyl ether, dipropylene glycol butyl oxide etc.；Aromatic hydrocarbon, such as benzene,toluene,xylene, mesitylene etc.；Ketone, such as first Base ethyl ketone, acetone, methyl amyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.；Alcohol, such as ethyl alcohol, propyl alcohol, butanol, hexanol, ring Hexanol, ethylene glycol, glycerol etc.；And ester, such as 3- ethoxyl ethyl propionate, 3- methoxy methyl propionate, methyl cellosolve second Acid esters, ethyl cellosolve acetate, ethyl acetate, butyl acetate, pentyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3- methoxybutyl acetic acid esters, 3- methyl -3- methoxyl group -1- butylacetic acid ester, methoxypentyl acetic acid esters, ethylene glycol list acetic acid Ester, ethylene acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monoacetate, diethyl Glycol diacetate, butyl carbitol acetate, Propylene glycol monoacetate, propylene-glycol diacetate, dihydroxypropane single-ether Acetic acid esters, ethylene carbonate, propylene carbonate, gamma-butyrolacton etc., however, the present invention is not limited thereto.These solvents can individually make It is applied in combination with or with two or more.

It, can be with 60 weight % to 90 weight %, preferably 70 relative to the green photonasty resin composition of 100 weight % The amount of weight % to 87 weight % includes solvent.When the content of solvent is fallen in the range, when using apparatus for coating (such as roller Painting machine, spin coater, slit spin coater, slit coater (sometimes referred to as molding coating machine) and ink-jet printer) coating composition When, coating can be satisfactory.

Additive

Other than the above component, in the range of not damaging target of the invention, according to the need of those skilled in the art It wants, green photonasty resin composition according to the present invention can also include additive, such as filler, other polymers, solidification Agent, adhesion promoter, ultraviolet absorber, coagulation inhibitor etc..

The specific example of filler includes glass, silica, aluminium oxide etc., however, the present invention is not limited thereto.

The specific example of other polymers includes curable resin (such as epoxy resin, maleimide resin etc.)；With Thermoplastic resin (such as polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester, poly- ammonia Ester etc.), however, the present invention is not limited thereto.

Curing agent for realizing deep solidify and improve mechanical strength, the specific example of curing agent include epoxide, Polyfunctional isocyanate compound, melamine compound, oxetane compound etc., however, the present invention is not limited thereto.Epoxy The specific example of compound includes bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, A Hydrogenated Bisphenol A F ring Oxygen resin, phenolic resin varnish type epoxy resin, other aromatic epoxy resins, cycloaliphatic epoxy resin, glycidyl ester resin, contracting The bromo derivative of water glycerol polyimide resin or these epoxy resin；Different from the aliphatic epoxy of epoxy resin listed above The bromo derivative of compound, alicyclic epoxide compound or aromatic epoxy compound and these epoxy resin；Epoxidation fourth Diene (co) polymer；Epoxidized isoprene (co) polymer；(methyl) glycidyl acrylate (co) polymer；Isocyanide Urea acid three-glycidyl ester etc., however, the present invention is not limited thereto.The specific example of oxetane compound includes carbonic ester dioxygen Azetidine, dimethylbenzene dioxygen azetidine, adipate ester dioxygen azetidine, terephthalate dioxygen azetidine, ring Hexane dicarboxylic acid's dioxygen azetidine etc., however, the present invention is not limited thereto.

Curing agent can be with the oxetanes skeleton for the epoxy group or oxetane compound for allowing epoxide The auxiliary curing agent for carrying out ring-opening polymerisation is applied in combination.The specific example of auxiliary curing agent includes polyvalent carboxylic acid, polyvalent carboxylic acid's acid anhydride, acid production Raw agent etc..Carboxylic acid anhydrides can be the commercial product as epoxy curing agent.The example packet of commercially available epoxy curing agent Include ADEKA HARDENER(Adeka Corporation)、RIKACID(New Japan Chemical Co.,Ltd.)、(New Japan Chemical Co., Ltd.) etc..

Curing agent and auxiliary curing agent exemplified as above can be used alone respectively or being applied in combination with two or more.

The specific example of adhesion promoter includes vinyltrimethoxysilane, vinyltriethoxysilane, three (2- of vinyl Methoxy ethoxy) silane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, N- (2- amino-ethyl) -3- TSL 8330,3-aminopropyltriethoxysilane, 3- glycidoxypropyltrimewasxysilane, 3- Glycidoxypropyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- chloropropyl Methyl dimethoxysilane, 3- r-chloropropyl trimethoxyl silane, 3- methacryloxypropyl trimethoxy silane, 3- sulfydryl Propyl trimethoxy silicane, 3- isocyanate group propyl trimethoxy silicane and 3- isocyanate group propyl-triethoxysilicane Alkane.These compounds can be used alone or being applied in combination with two or more.

The total solids content of green photonasty resin composition according to the present invention relative to 100 weight %, can be with The amount of 0.01 weight % to 10 weight %, preferably 0.05 weight % to 2 weight % include adhesion promoter.

The specific example of ultraviolet absorber includes 2- (3- tert-butyl -2- hydroxy-5-methyl base phenyl) -5- chloro benzo three Azoles, alkoxy benzophenone etc., however, the present invention is not limited thereto.

The specific example of coagulation inhibitor includes Sodium Polyacrylate etc., however, the present invention is not limited thereto.

The preparation of above-mentioned green photonasty resin composition is not limited to specific method, and the side used according to this field Method carries out.In this example, green photonasty resin composition can be prepared as follows.

Firstly, then pigment is dispersed in by pigment and solvent or dispersant in colorant using ball mill etc. In the solvent or dispersing agent, until the average grain diameter of pigment reaches 0.2 μm or smaller.In this case, if it is desired, pigment It can be mixed together with solvent with pigment dispersing agent, all or part of alkali soluble resin, dyestuff etc., then dissolve or disperse In the solvent.

It, can be further by dyestuff, remaining alkali soluble resin, photopolymerizable chemical combination for obtained dispersion Object, Photoepolymerizationinitiater initiater, and if necessary, additive and solvent are added to scheduled concentration, to prepare according to this hair Bright green photonasty resin composition.

According to another aspect of the present invention, colored filter includes that the solidification of above-mentioned green photonasty resin composition produces Object.Specifically, the cured product of green photonasty resin composition refers to by green photonasty resin combination according to the present invention The colored pattern that object is formed on substrate.Substrate can be transparent material, and have the stability for colored filter For enough intensity and support force, and preferably with excellent chemical stability and high-intensitive glass.Moreover, color Colo(u)r filter can also include blue-light source as light source.

The detailed configuration and production method of colored filter can be arrangements and methods conventionally known in this field.It is logical Often, colored filter can be by including applying step；Light guide step；It is produced with the technique of removal step.

Specifically, by method appropriate (such as spin-coating method, slot coated method etc.) by green photonasty resin composition Applied on the glass substrate for not applying any substance on it with 2.0 μm to 3.4 μm of thickness and be applied with thereon with a thickness ofExtremelySiN_xOn the glass substrate of (protective film).Then, light irradiation is carried out to be formed needed for colored filter Pattern.After light irradiation, coating is handled to dissolve the part of the coating not being irradiated by light with alkali developing solution, thus Pattern needed for forming colored filter.It can R, G and B color according to needed for obtaining the colored filter with desired pattern Quantity repeat the technique.In addition, in the process, the picture pattern that is obtained by development can by reheating or Solidified with photochemical radiation exposure, to further enhance crack resistance, solvent resistance etc..

According to a further aspect of the invention, image display device includes above-mentioned colored filter.

Specifically, image display device may include the other assemblies that can be conventionally included in image display device, Such as light-emitting component (such as light source), light guide plate, liquid crystal display component including colored filter according to the present invention etc., but this It invents without being limited thereto.

In addition, image display device according to the present invention can also include such other than above-mentioned colored filter Colored filter: the colored filter includes the red pattern layer containing red quantum dot particle, containing green quantum dot particle Green pattern layer and blue color patterns layer containing blue quantum dot particle.In such case, it is contemplated that better color is again Existing property, light source are preferably to emit the light source of blue light, and but the invention is not restricted to this.

Other than above-mentioned colored filter, image display device according to the present invention can also include only comprising red figure The colored filter of pattern layer, green pattern layer and the two in blue color patterns layer.In this case, colored filter also includes Transparent pattern layer without containing quantum dot particle.When colored filter only includes two kinds of pattern layer, hair can be used Penetrate the light source of the light of the wavelength corresponding to the color excluded.For example, when including red pattern layer and green figure in colored filter When pattern layer, the light source of transmitting blue light can be used.In this case, red quantum dot particle emission feux rouges, green quantum dot Particle emission green light, and transparent pattern layer shows blue light since blue light directly passes through.

The specific example of image display device includes various image display devices, such as electroluminescent (EL) display device, Plasmia indicating panel (PDP) device, field emission display (FED) device, Organic Light Emitting Diode (OLED) etc. and liquid crystal Show device (LCD).

Hereinafter, the present invention will be described in detail by exemplary implementation scheme.However, according to the implementation of this specification Scheme can be modified in the form of various other, and the range of this specification should not be construed as limited to the implementation being provided below Scheme.The embodiment of this specification is provided to describe this specification to those skilled in the art more thorough and completely.In addition, Unless otherwise particularly illustrating, the term (such as " % " and " part ") for describing content of material is based on weight.

Prepare embodiment 1: the preparation of pigment dispersion composition

Prepare embodiment 1-1: the preparation of pigment dispersion composition M1

By the C.I. naphthol green 62 as 10.0 parts by weight of pigment, the LPN- of 5.0 parts by weight as pigment dispersing agent 6919 (BYK Additives&Instruments) and the propylene glycol methyl ether acetate of 85.0 parts by weight as solvent use pearl Grinding machine mixes and disperses 12 hours to prepare pigment dispersion composition M1.

Prepare embodiment 1-2: the preparation of pigment dispersion composition M2

By the C.I. naphthol green 63 as 10.0 parts by weight of pigment, the LPN- of 5.0 parts by weight as pigment dispersing agent 6919 (BYK Additives&Instruments) and the propylene glycol methyl ether acetate of 85.0 parts by weight as solvent use pearl Grinding machine mixes and disperses 12 hours to prepare pigment dispersion composition M2.

Prepare embodiment 1-3: the preparation of pigment dispersion composition M3

By the C.I. pigment Green 7 as 10.0 parts by weight of pigment, the LPN- of 5.0 parts by weight as pigment dispersing agent 6919 (BYK Additives&Instruments) and the propylene glycol methyl ether acetate of 85.0 parts by weight as solvent use pearl Grinding machine mixes and disperses 12 hours to prepare pigment dispersion composition M3.

Prepare embodiment 1-4: the preparation of pigment dispersion composition M4

By the C.I. naphthol green 58 as 10.0 parts by weight of pigment, the LPN- of 5.0 parts by weight as pigment dispersing agent 6919 (BYK Additives&Instruments) and the propylene glycol methyl ether acetate of 85.0 parts by weight as solvent use pearl Grinding machine mixes and disperses 12 hours to prepare pigment dispersion composition M4.

Prepare embodiment 1-5: the preparation of pigment dispersion composition M5

By the C.I. naphthol green 59 as 10.0 parts by weight of pigment, the LPN- of 5.0 parts by weight as pigment dispersing agent 6919 (BYK Additives&Instruments) and the propylene glycol methyl ether acetate of 85.0 parts by weight as solvent use pearl Grinding machine mixes and disperses 12 hours to prepare pigment dispersion composition M5.

Prepare embodiment 1-6: the preparation of pigment dispersion composition M6

By the C.I. pigment yellow 13 8 as 10.0 parts by weight of pigment, the LPN- of 5.0 parts by weight as pigment dispersing agent 6919 (BYK Additives&Instruments) and the propylene glycol methyl ether acetate of 85.0 parts by weight as solvent use pearl Grinding machine mixes and disperses 12 hours to prepare pigment dispersion composition M6.

Synthetic example: the synthesis of alkali soluble resin

The synthesis of 1. alkali soluble resin B-1 of synthetic example

By the propylene glycol methyl ether acetate of 120 parts by weight, the propylene glycol monomethyl ether of 80 parts by weight, 2 parts by weight AIBN, The acrylic acid of 13.0 parts by weight, the benzyl methacrylate of 10 parts by weight, the 4- methyl styrene of 57.0 parts by weight, 20 parts by weight Methyl methacrylate and 3 parts by weight n-dodecyl mercaptan introduce equipped with blender, thermometer, reflux condenser, In the flask of dropping funel and nitrogen introducing tube, with the atmosphere in nitrogen purification flask.Then, under stiring by reaction solution Temperature rises to 110 DEG C, makes substance reaction 6 hours.The solid acid value of resulting alkali soluble resin is 100.2mgKOH/g, through solidifying The weight average molecular weight (Mw) of glue penetration chromatography (GPC) measurement is about 15110.

The synthesis of 2. alkali soluble resin B-2 of synthetic example

By the propylene glycol methyl ether acetate of 120 parts by weight, the propylene glycol monomethyl ether of 80 parts by weight, 5 parts by weight AIBN, The 3,4- epoxy tricyclic [5.2.1.0 of the methacrylic acid of 10 parts by weight and 90 parts by weight^2.6] decyl- 8- base acrylate and 3,4- Epoxy tricyclic [5.2.1.0^2.6] mixture of decyl- 9- base acrylate (mixes with the molar ratio of 50:50；Trade name " E- DCPA " is purchased from Daicel Corporation) it introduces equipped with blender, thermometer, reflux condenser, dropping funel and nitrogen Gas is introduced into the flask of pipe, with the atmosphere in nitrogen purification flask.Then, the temperature of reaction solution is risen to 85 under stiring DEG C, make substance reaction 6 hours.

The solid acid value of resulting alkali soluble resin is 54mgKOH/g, and the weight average molecular weight (Mw) through gpc measurement is 8100。

The synthesis of 3. alkali soluble resin B-3 of synthetic example

By the propylene glycol methyl ether acetate of 120 parts by weight, the propylene glycol monomethyl ether of 80 parts by weight, 5 parts by weight AIBN, The methacrylic acid of 10 parts by weight, the vinyltoluene of 40 parts by weight, the methyl methacrylate of 40 parts by weight and 10 parts by weight 3,4- epoxy tricyclic [5.2.1.0^2.6] decyl- 8- base acrylate and 3,4- epoxy tricyclic [5.2.1.0^2.6] decyl- 9- base propylene The mixture of acid esters (is mixed with the molar ratio of 50:50；Trade name " E-DCPA ", purchased from commercially available from Daicel Corporation) draw Enter in the flask equipped with blender, thermometer, reflux condenser, dropping funel and nitrogen introducing tube, purifies flask with nitrogen In atmosphere.Then, the temperature of reaction solution is risen to 85 DEG C under stiring, makes substance reaction 6 hours.

The solid acid value of resulting alkali soluble resin is 54mgKOH/g, and the weight average molecular weight (Mw) through gpc measurement is 10000。

The synthesis of 4. alkali soluble resin B-4 of synthetic example

By the propylene glycol methyl ether acetate of 120 parts by weight, the propylene glycol monomethyl ether of 80 parts by weight, 5 parts by weight AIBN, The 3,4- epoxycyclohexyl-methyl acrylate (trade name " Cyclomer of the methacrylic acid of 10 parts by weight, 30 parts by weight M100 ", the styrene purchased from Daicel Corporation), the benzyl methacrylate of 10 parts by weight and 50 parts by weight introduce Equipped in the flask of blender, thermometer, reflux condenser, dropping funel and nitrogen introducing tube, purified in flask with nitrogen Atmosphere.Then, the temperature of reaction solution is risen to 85 DEG C under stiring, makes substance reaction 6 hours.

The solid acid value of resulting alkali soluble resin is 54mgKOH/g, and the weight average molecular weight (Mw) through gpc measurement is 12000。

The synthesis of 5. alkali soluble resin B-5 of synthetic example

By the propylene glycol methyl ether acetate of 120 parts by weight, the propylene glycol monomethyl ether of 80 parts by weight, 2 parts by weight AIBN, The acrylic acid of 13.0 parts by weight, the benzyl methacrylate of 10 parts by weight, the styrene of 57.0 parts by weight, 20 parts by weight methyl Methyl acrylate and the n-dodecyl mercaptan of 3 parts by weight are introduced to be leaked equipped with blender, thermometer, reflux condenser, dropping liquid In the flask of bucket and nitrogen introducing tube, with the atmosphere in nitrogen purification flask.Then, under stiring by the temperature liter of reaction solution To 110 DEG C, make substance reaction 6 hours.

The solid acid value of resulting alkali soluble resin is 100.2mgKOH/g, the weight average molecular weight (Mw) through gpc measurement It is about 15100.

Prepare embodiment 2: the preparation of green photonasty resin composition

Prepare embodiment 2-1:

By 52.5 parts by weight according to the pigment dispersion composition M1 of preparation embodiment 1-1, the basis of 9.55 parts by weight The resin of synthetic example 1, the KAYARAD DPHA (Nippon Kayaku Co., Ltd.) of 3.39 parts by weight, 0.34 parts by weight 'sThe mixing of (BASF SE) and the propylene glycol methyl ether acetate of 34.22 parts by weight prepares green sense Photosensitive resin composition.

Prepare embodiment 2-2:

By 52.5 parts by weight according to the pigment dispersion composition M2 of preparation embodiment 1-2, the basis of 9.55 parts by weight The resin of synthetic example 1, the KAYARAD DPHA (Nippon Kayaku Co., Ltd.) of 3.39 parts by weight, 0.34 parts by weight 'sThe mixing of (BASF SE) and the propylene glycol methyl ether acetate of 34.22 parts by weight prepares green sense Photosensitive resin composition.

Prepare embodiment 2-3:

By 52.5 parts by weight according to the pigment dispersion composition M3 of preparation embodiment 1-3, the basis of 9.55 parts by weight The resin of synthetic example 1, the KAYARAD DPHA (Nippon Kayaku Co., Ltd.) of 3.39 parts by weight, 0.34 parts by weight 'sThe mixing of (BASF SE) and the propylene glycol methyl ether acetate of 34.22 parts by weight prepares green sense Photosensitive resin composition.

Prepare embodiment 2-4:

By 52.5 parts by weight according to the pigment dispersion composition M4 of preparation embodiment 1-4, the basis of 9.55 parts by weight The resin of synthetic example 1, the KAYARAD DPHA (Nippon Kayaku Co., Ltd.) of 3.39 parts by weight, 0.34 parts by weight 'sThe mixing of (BASF SE) and the propylene glycol methyl ether acetate of 34.22 parts by weight prepares green sense Photosensitive resin composition.

Prepare embodiment 2-5:

By 52.5 parts by weight according to the pigment dispersion composition M5 of preparation embodiment 1-5, the basis of 9.55 parts by weight The resin of synthetic example 1, the KAYARAD DPHA (Nippon Kayaku Co., Ltd.) of 3.39 parts by weight, 0.34 parts by weight 'sThe mixing of (BASF SE) and the propylene glycol methyl ether acetate of 34.22 parts by weight prepares green sense Photosensitive resin composition.

Embodiment and comparative example: the preparation of green photonasty resin composition

Component is described in table 1 below mixing to prepare green photonasty resin composition.

[table 1]

Prepare embodiment 3: the manufacture of colored filter

Each of the green photonasty resin composition prepared in preparation embodiment 2, embodiment and comparative example is logical It crosses spin-coating method to be applied on 2 inches × 2 inches of glass substrate (" EAGLE XG " purchased from Corning Inc.), then by glass Glass substrate put on hot plate and 100 DEG C at a temperature of keep 3 minutes to form film.Then, there will be 1 μm to 100 μm Line/space pattern test photomask be placed on the film, and with ultraviolet light irradiation away from test photomask have 300 μm The film at interval.In this case, use the 1kW high-pressure sodium lamp including whole g ray, h ray and i ray as UV light Source, in 40mJ/cm²Exposure intensity under carry out UV irradiation, and do not use certain optical filter.By the film of UV irradiation in KOH Development 80 seconds in developing aqueous solution (pH 10.5).The glass substrate for being applied with film thereon is washed with distilled water, purging is passed through Nitrogen is dry, and heats 20 minutes in 230 DEG C of heating furnace to manufacture colored filter.In this case, so preparation Colored filter there is 2.0 μm of thickness.

EXPERIMENTAL EXAMPLE 1: chromaticity coordinates and transmissivity measurement

It is every using being prepared in colorimeter (OSP-200 purchased from Olympus Corporation) measurement preparation embodiment 3 Chromaticity coordinates, transmissivity and the spectral-transmission favtor of kind colored filter.

Firstly, for the colored filter for using the green photonasty resin composition preparation according to preparation embodiment 2, really Whether the spectral characteristic (according to the transmissivity of wave-length coverage) of (a type of) pigment for including in fixed every kind of composition meets Requirement of the invention, the results are shown in Fig. 1 into Fig. 3 and the following table 2.Referring to Figures 1 and 2, it can be confirmed in implementation of the invention The C.I. naphthol green 62 (preparation embodiment 2-1) and C.I. naphthol green 63 (preparing embodiment 2-2) for including as pigment in example exist 80% or the bigger and transmissivity less than 99% are shown in the wave-length coverage of 450nm to 500nm, therefore meet of the invention want It asks, different from C.I. pigment Green 7 (preparation embodiment 2-3), the C.I. naphthol green 58 (preparation embodiment 2-4) for including in comparative example With C.I. naphthol green 59 (preparation embodiment 2-5).Referring to Figure 1 and Figure 3, it can be confirmed in an embodiment of the present invention as pigment The C.I. naphthol green 62 and C.I. naphthol green 63 for including shown in the wave-length coverage of 760nm to 780nm 40% or bigger and Transmissivity less than 99%, therefore meet requirement of the invention.

In addition, in order to comparatively evaluate the saturating of every kind of colorant as described above for identifying spectral signature under the same conditions Rate is penetrated, the ratio addition as shown in embodiment 1 to embodiment 6 and comparative example 1 to comparative example 6 with variation is according to preparation embodiment 1- 6 pigment dispersion composition comprising C.I. pigment yellow 13 8, to adjust chromaticity coordinates, so that Gx is 0.266 and Gy is 0.575 (1931 color model of CIE).The evaluation result of transmissivity is shown in the following table 3, and the evaluation criterion of transmissivity is as follows.

OK: relative to 60 standard transmissivity (GY), transmissivity increases by 2% or more

NG: relative to 60 standard transmissivity (GY), transmissivity increases less than 2%

EXPERIMENTAL EXAMPLE 2: adhesivity evaluation

The pattern formed in the colored filter prepared in preparation embodiment 3 is evaluated with optical microscopy.To figure The evaluation criterion of the extent of exfoliation of case is as follows, and the results are shown in the following table 3.

Zero: not removed on pattern

△: 1 to 4 entity is removed on pattern

×: 5 or more entities are removed on pattern

EXPERIMENTAL EXAMPLE 3: developing rate evaluation

In the preparation according to the colored filter of preparation embodiment 3, measurement is complete in developing solution in developing process Time (developing rate) needed for dissolving unexposed portion, the results are shown in the following table 3.

EXPERIMENTAL EXAMPLE 4: residue evaluation

For having carried out the colored filter of developing process using patterning BM glass in preparation embodiment 3, pass through mesh It whether there is development residue on substrate depending on observing.Evaluation criterion is as follows, and the results are shown in the following table 3.

Zero: there is no development residue on substrate

×: there is development residue on substrate

EXPERIMENTAL EXAMPLE 5: chemical resistance evaluation

Other than without using test photomask, prepared in a manner of identical with preparation embodiment 3 for evaluating resistance toization The colored filter for the property learned.The colored filter so prepared is immersed in 80 DEG C n-methyl-2-pyrrolidone (NMP) solution 30 minutes, chromaticity coordinates is then measured before dipping and after dipping, and color difference is calculated according to following equation 1.For chemical resistance Evaluation criterion is as follows, and the results are shown in the following table 3.

[equation 1]

In equation 1, L₁*、a₁And b *₁* the chromaticity coordinates before dipping, L are indicated₂*、a₂And b *₂* the chromaticity coordinates after dipping is indicated.

Zero: △ E*ab value is 3 or smaller

△: △ E*ab value is greater than 3 and less than 6

×: △ E*ab value is greater than 6

[table 2]

	450nm	500nm	760nm	780nm
					Prepare embodiment 2-1	82%	92%	78%	89%
Prepare embodiment 2-2	87%	97%	73%	93%
					Prepare embodiment 2-3	13%	84%	18%	23%
Prepare embodiment 2-4	18%	85%	12%	22%
					Prepare embodiment 2-5	14%	80%	14%	21%

It referring to table 2, can determine: (the preparation embodiment of the C.I. naphthol green 62 as pigment in an embodiment of the present invention 2-1) meet the spectral characteristic of colorant of the presently claimed invention with C.I. naphthol green 63 (preparation embodiment 2-2).

[table 3]

Referring to table 3, can determine: be unsatisfactory for the comparative example 1 of any of requirement of the invention to 6 phase of comparative example Than the implementation of colorant and the alkali soluble resin comprising specific repetitive unit including meeting the required spectral characteristic of the present invention Example 1 to embodiment 6 not only show excellent transmissivity and also show high developing rate, without development residue and preferably Chemical resistance.

Claims

1. a kind of green photonasty resin composition, the green photonasty resin composition includes colorant, alkali-soluble tree Rouge, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent,

Wherein, the colorant includes having 80% or bigger and saturating less than 99% in the wave-length coverage of 450nm to 500nm It penetrates rate and there is 40% or bigger and the transmissivity less than 99% pigment in the wave-length coverage of 760nm to 780nm, and

The alkali soluble resin includes being selected from one of repetitive unit indicated by following formula 1 to chemical formula 3 or more Kind:

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

Wherein, R^aTo R^cEach independently represent hydrogen or methyl group.

2. green photonasty resin composition according to claim 1, wherein the pigment includes phthalocyanine aluminium compound.

3. green photonasty resin composition according to claim 2, wherein the phthalocyanine aluminium compound includes by following The compound that chemical formula 4 or chemical formula 5 indicate:

[chemical formula 4]

Wherein, R¹To R¹⁶Each independently represent hydrogen, halogen atom, nitryl group, substitutive phthalimide methyl Group, substitutive sulfamoyl group, substitutive C₁To C₁₈Alkyl group, substitutive C₆To C₁₄Aryl group can use The C in generation₅To C₁₀Group of naphthene base, heterocyclic group, substitutive C₁To C₁₈Alkoxy base, substitutive C₆To C₁₄Aryloxy group base Group, substitutive C₁To C₁₈Alkylthio radicals or substitutive C₆To C₁₄Arylthio group, and

Z expression-OP (=O) X₁X₂,

Wherein, X₁And X₂Each independently represent hydrogen, hydroxyl group, substitutive C₁To C₁₈Alkyl group, substitutive C₆To C₁₄ Aryl group, substitutive C₁To C₁₈Alkoxy base or substitutive C₆To C₁₄Aryloxy group, and

X₁And X₂It can be in conjunction with phosphorus atoms to form heterocycle；And

[chemical formula 5]

Wherein, R¹⁷To R³²Each independently represent hydrogen, halogen atom, nitryl group, substitutive phthalimide methyl Group, substitutive sulfamoyl group, substitutive C₁To C₁₈Alkyl group, substitutive C₆To C₁₄Aryl group can use The C in generation₅To C₁₀Group of naphthene base, heterocyclic group, substitutive C₁To C₁₈Alkoxy base, substitutive C₆To C₁₄Aryloxy group base Group, substitutive C₁To C₁₈Alkylthio radicals or substitutive C₆To C₁₄Arylthio group, and

L is indicated

Wherein, X₃To X₇Each independently represent substitutive C₁To C₁₈Alkyl group or substitutive C₆To C₁₄Aryl group.

4. green photonasty resin composition according to claim 2, wherein the phthalocyanine aluminium compound includes C.I. face Expect green 62 or C.I. naphthol green 63.

5. green photonasty resin composition according to claim 1, wherein the alkali relative to 100 moles of % can Total repetitive unit of soluble resin, the alkali soluble resin include 10 moles of % to 90 moles of % selected from by chemical formula 1 to One of described repetitive unit that chemical formula 3 indicates is a variety of.

6. green photonasty resin composition according to claim 2, wherein relative to total colorant of 100 weight %, It include the phthalocyanine aluminium compound with the amount of 30 weight % to 100 weight %.

7. green photonasty resin composition according to claim 1, wherein the colorant further includes C.I. pigment yellow 138 or C.I. pigment yellow 231.

8. green photonasty resin composition according to claim 7, wherein relative to total colorant of 100 weight %, It include the C.I. pigment yellow 13 8 or C.I. pigment yellow 231 with the amount of 30 weight % to 70 weight %.

9. green photonasty resin composition according to claim 1, wherein the green relative to 100 weight % The total solids content of photosensitive polymer combination includes the colorant with the amount of 5 weight % to 60 weight %.

10. a kind of colored filter, the colored filter includes green photonasty described in any one of claims 1 to 9 The cured product of resin combination.

11. a kind of image display device, described image display device includes colored filter described in any one of claim 10.