CN108375876A

CN108375876A - Photosensitive composition, colour filter and image display device

Info

Publication number: CN108375876A
Application number: CN201810049683.8A
Authority: CN
Inventors: 柳在范; 金韩善; 李商范
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2017-02-01
Filing date: 2018-01-18
Publication date: 2018-08-07
Anticipated expiration: 2038-01-18
Also published as: CN108375876B; KR20180089738A; KR102510668B1

Abstract

The present invention provides photosensitive composition, utilizes the colour filter and image display device of its manufacture.Above-mentioned photosensitive composition is characterized in that, including：Photoepolymerizationinitiater initiater containing oxime ester fluorenes based compound；The colorant of rhodamine based dye containing particle shape；With the dispersant containing triazine based compound.The photosensitive composition of the present invention has the advantages that dispersion stabilization is excellent.In addition, the colour filter and image display device of the present invention be by comprising above-mentioned photosensitive composition, to have the advantages that heat resistance and excellent solvent resistance and prevent the generation of line peeling.

Description

Photosensitive composition, colour filter and image display device

Technical field

The present invention relates to photosensitive composition, utilize the colour filter and image display device of its manufacture.

Background technology

Colour filter is widely used in the various display devices such as photographing element, liquid crystal display device (LCD), and application range is just It is expanding rapidly.Above-mentioned colour filter is by red (Red), the colored pattern shape of green (Green) and blue (Blue) this 3 kinds of colors At, or formed by the colored pattern of yellow (Yellow), magenta (Magenta) and cyan (Cyan) this 3 kinds of colors.

The above-mentioned colour filter for being widely used in display device is generally as follows manufacture：Lead on the substrate for being formed with black matrix pattern Cross spin coating or slit coating be equably coated with containing be equivalent to each pattern color pigment dispensing composition color sensation Photosensitive resin composition, then heat drying, it is exposed and developed to be formed by film, is further heating and curing as needed, Aforesaid operations are repeated to each color, assorted pixel are formed, in addition, in the ink-jet method and print of not above-mentioned coating method Brush method etc. is without in the process of developing procedure, also utilizing the coloring phototonus that above-mentioned pigment dispensing composition is used as to coloured material Resin combination manufactures colour filter.

It is required the objects such as high brightness, high contrast using the colour filter of photosensitive composition as described above Property, in addition, being required the high pixel of color reproduction in recent years.Therefore, the coloring material used in above-mentioned colored resin composition The pigment of material and the content of carbon black gradually increase.But the content of coloured material in improving colored resin composition the case where Under, in order to show excellent optical characteristics, it has to make pigment particle, especially in manufacture high concentration pigment dispensing composition When, viscosity is got higher or pigment dispensing composition storage stabilities such as gelation in preservation are deteriorated, therefore there is also brightness and The problem of optical characteristics such as contrast reduce.

Japanese Laid-Open Patent Publication the 2013-61619th is related to colour filter blue colorant composition and utilizes the filter The filter substrate of color device blue colorant composition, and disclose the following contents：Colour filter blue colorant composition It is characterized in that, is colour filter at least containing colorant, adhesive resin, macromolecule dispersing agent and solvent with blue-colored Agent composition, above-mentioned colorant include pigment and rhodamine based dye, and in above-mentioned blue colorant composition, above-mentioned rhodamine Based dye exists with particle shape, but that there are dispersion stabilizations is bad, heat resistance and the insufficient problem of solvent resistance.

Therefore, actual conditions are to need and heat resistance excellent for various dispersion stabilizations and solvent resistance also excellent Photosensitive composition research.

Existing technical literature

Patent document

Japanese Laid-Open Patent Publication the 2013-61619th (2013.04.04)

Invention content

Project to be solved

Excellent, heat resistance that the object of the present invention is to provide dispersion stabilizations and solvent resistance are enhanced and line peels off To improved photosensitive composition.

It is further an object that providing the colour filter manufactured using above-mentioned photosensitive composition Device and image display device.

The method to solve the problem

For achieving the above object the present invention photosensitive composition be characterized in that, including：Under containing State the Photoepolymerizationinitiater initiater of the oxime ester fluorenes based compound of chemical formula 1；The colorant of rhodamine based dye containing particle shape；With Dispersant containing triazine based compound,

[chemical formula 1]

(in above-mentioned chemical formula 1,

R₁~R₅And R₇~R₁₀It is same or different to each other, is each independently selected from by the alkane of hydrogen, halogen, carbon atom number 1~20 Base, the aryl of carbon atom number 6~20, the alkoxy of carbon atom number 1~20, the aryl alkyl of carbon atom number 7~40, carbon atom number The group of the naphthenic base composition of 1~20 hydroxy alkyl, the hydroxy alkoxy alkyl of carbon atom number 2~40 and carbon atom number 3~20,

R₆Selected from by hydrogen, halogen, the alkyl of carbon atom number 1~20, the aryl of carbon atom number 6~20, carbon atom number 1~20 Alkoxy, the aryl alkyl of carbon atom number 7~40, the hydroxy alkyl of carbon atom number 1~20, carbon atom number 2~40 hydroxyl The group of alkoxyalkyl, the naphthenic base of carbon atom number 3~20, amino, nitro, cyano and hydroxyl composition,

The integer that p is 0~1).

In addition, the colour filter and image display device of the present invention are characterized in that, including above-mentioned coloring phototonus resin Composition.

Invention effect

The photosensitive composition of the present invention has the advantages that dispersion stabilization is excellent.

In addition, the colour filter and image display device of the present invention be by comprising above-mentioned photosensitive composition, To the generation for having the advantages that heat resistance and excellent solvent resistance and preventing line from peeling off.

Specific implementation mode

Include not only a certain component and another structure when pointing out that a certain component is located at another component "upper" in the present invention The case where part contacts further includes the case where there are other components between two components.

In the present invention, when pointing out a certain inscape of certain a part of "comprising", mean, as long as no especially opposite Record, then can further include other inscapes, rather than other inscapes are excluded.

Hereinafter, the present invention is described in more detail.

The photosensitive composition of the mode of the present invention includes the oxime ester fluorenes system chemical combination containing following chemical formula 1 The Photoepolymerizationinitiater initiater of object, the colorant of rhodamine based dye containing particle shape and the dispersion containing triazine based compound Agent, to have heat resistance and excellent solvent resistance, and the advantages of can prevent line from peeling off.

[chemical formula 1]

(in above-mentioned chemical formula 1,

The integer that p is 0~1).

In above-mentioned chemical formula 1, R₁~R₅And R₆~R₁₀Can specifically enumerate hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-propyl, Isopropyl, normal-butyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, phenyl, naphthalene, xenyl, three Phenyl, anthryl, indenyl, phenanthryl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tertiary fourth oxygen Base, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxyl n-pentyl, hydroxyl isopentyl, Hydroxyl n-hexyl, hydroxyl isohesyl, hydroxymethoxy methyl, hydroxymethoxy ethyl, hydroxymethoxy propyl, hydroxymethoxy Butyl, hydroxyethoxymethyl, hydroxyl ethoxy ethyl, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, hydroxyl-oxethyl penta Base, hydroxyl-oxethyl hexyl etc..

In above-mentioned chemical formula 1, R₆Hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-propyl, isopropyl, positive fourth can specifically be enumerated Base, isobutyl group, tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, phenyl, naphthalene, xenyl, terphenyl, anthryl, Indenyl, phenanthryl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxyl first Base, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxyl n-pentyl, hydroxyl isopentyl, hydroxyl just oneself Base, hydroxyl isohesyl, hydroxymethoxy methyl, hydroxymethoxy ethyl, hydroxymethoxy propyl, hydroxymethoxy butyl, hydroxyl Base oxethyl methyl, hydroxyl ethoxy ethyl, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, hydroxyethoxypentyl, hydroxyl Ethoxyhexyl, amino, nitro, cyano, hydroxyl etc..

In this specification " alkyl " refer to only be made of carbon and hydrogen atom, without degree of unsaturation, by singly-bound and molecule The hydrocarbon chain radical for the linear chain or branched chain type that remainder combines.Specifically, abovementioned alkyl can be carbon atom number 1~20 More specifically straight chain type or branch chain type alkyl can be the straight chain type or branch chain type alkyl of carbon atom number 1~10, more specifically For, can be the straight chain type or branch chain type alkyl of carbon atom number 1~6.It, can be with as the example of such non-substituted alkyl Enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, amyl, isopentyl, hexyl etc..On Stating more than one hydrogen atom contained in alkyl can be by halogen atom, hydroxyl, mercapto (- SH), nitro, cyano, substitution Or non-substituted amino, amidino groups, diazanyl, hydrazone group, carboxyl, sulfonic group, phosphate, C₁~C₂₀Alkyl, C₁~C₂₀Alkyl halide Base, C₂~C₂₀Alkenyl, C₂~C₂₀Alkynyl, C₁~C₂₀Miscellaneous alkyl, C₆~C₂₀Aryl, C₆~C₂₀Aryl alkyl, C₆ ~C₂₀Heteroaryl or C₆~C₂₀Heteroaryl alkyl substitution.

" aryl " refers to the aromatic monocyclic or multicyclic hydrocarbon ring system being only made of hydrogen and carbon in this specification, at this time ring body System can partially or completely be saturated.At least one hydrogen atom can be by the substituent group as in abovementioned alkyl in above-mentioned aryl Substitution.Above-mentioned aryl be by removing a hydrogen derived from aromatic hydrocarbon organic free radical, may include containing 4 in each ring ~7, monocycle or condensed ring system specifically containing 5 or 6 annular atoms can also pass through singly linked shape including multiple aryl State.Above-mentioned aryl can include 6~20 carbon atoms, can include specifically 6~18 carbon atoms.

In this specification " alkoxy " can be respectively with carbon atom number 1~20 moieties oxygen-containing straight chain type or Branched chain type alkoxy.It is specifically as follows the alkoxy with 1~10 carbon atom, more specifically can is with 1~4 carbon atom Alkoxy.Above-mentioned alkoxy is for example, methoxyl group, ethyoxyl, propoxyl group, butoxy and tert-butoxy.Above-mentioned alcoxyl Base can also be further substituted with by more than one the halogen atom such as fluorine, chlorine or bromine and form halogenated alkoxy.As such Example can enumerate fluorine methoxyl group, chloromethane epoxide, trifluoromethoxy, trifluoro ethoxy, fluorine ethyoxyl and fluorine propoxyl group etc.. More than one hydrogen atom in above-mentioned alkoxy can be replaced by the substituent group as in abovementioned alkyl.

" aryl alkyl " refers to that the more than one hydrogen atom of abovementioned alkyl is replaced by above-mentioned aryl in this specification Group.The carbon atom number of above-mentioned aryl alkyl can be 7~40, specifically, carbon atom number can be 7~28, more Specifically, can be 7~24.

" hydroxy alkyl " refers to the OH- alkyl that hydroxyl is combined on alkyl defined above, above-mentioned hydroxyl in this specification Alkoxyalkyl refers to the hydroxy alkyl-O- alkyl that above-mentioned hydroxy alkyl is formed by connecting with alkyl by oxygen.Above-mentioned hydroxy alkyl Carbon atom number can be 1~20, specifically, carbon atom number can be 1~10, more specifically, carbon atom number can Think 1~6.The carbon atom number of above-mentioned hydroxy alkoxy alkyl can be 2~40, specifically, carbon atom number can be 2 ~20, more specifically, carbon atom number can be 2~9.

" naphthenic base " includes not only monocycle system hydrocarbon in this specification, also includes polycyclic system hydrocarbon, in above-mentioned naphthenic base at least One hydrogen atom can be replaced by the substituent group as in abovementioned alkyl.The carbon atom number of above-mentioned naphthenic base can be 3~ 20, specifically, carbon atom number can be 3~10, more specifically, carbon atom number can be 3~8.

Photoepolymerizationinitiater initiater

Photoepolymerizationinitiater initiater is the compound for causing aftermentioned photopolymerizable compound, a mode of the invention Color sensation photosensitive resin composition includes the oxime ester fluorenes based compound of above-mentioned chemical formula 1, to have the following advantages that：Make to include it The sensitivity of photosensitive composition improves, and the time for exposure is made to shorten, and thus, it is possible to prevent line from peeling off, improves and differentiates Rate.

The photosensitive composition of the present invention can be wrapped further in the range of not hindering the purpose of the present invention Draw containing the common photopolymerization that can make aftermentioned photopolymerizable compound polymerization other than above-mentioned Photoepolymerizationinitiater initiater Agent is sent out, common photopolymerization initiator used in the art can be further included furthermore according to needs.

In addition to it is above-mentioned containing the Photoepolymerizationinitiater initiater of oxime ester fluorenes based compound other than the photopolymerization that can further include draw Hair agent is not particularly limited as long as the substance for being used as Photoepolymerizationinitiater initiater in this field, can specifically enumerate triazine system chemical combination Object, acetophenone based compound, bisglyoxaline based compound, oxime compound, benzoin based compound, benzophenone based compound, thiophene Ton ketone based compound, anthracene based compound etc..

As above-mentioned triazine based compound, for example, bis- (the trichloromethyl) -6- (4- methoxyphenyls)-of 2,4- can be enumerated Bis- (the trichloromethyl) -6- of 1,3,5- triazines, 2,4- bis- (trichloromethyl) -6- (4- methoxyl groups naphthalene) -1,3,5- triazines, 2,4- are recklessly Bis- (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of green pepper base -1,3,5- triazines, 2,4-, the bis- (trichlorines of 2,4- Methyl) -6- [2- (5- methylfuran -2- bases) vinyl] -1,3,5- triazines, bis- (trichloromethyl) -6- [2- (furans -2- of 2,4- Base) vinyl] -1,3,5- triazines, bis- (the trichloromethyl) -6- of 2,4- [2- (4- diethylamino -2- aminomethyl phenyls) vinyl] - Bis- (the trichloromethyl) -6- of 1,3,5- triazines, 2,4- [2- (3,4- Dimethoxyphenyls) vinyl] -1,3,5- triazines etc..

As above-mentioned acetophenone based compound, for example, diethoxy acetophenone, 2- hydroxy-2-methyl -1- benzene can be enumerated Base propane -1- ketone, benzil dimethyl ketal, 2- hydroxyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -2- methylpropane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- methyl-1s-(4- methylthiophenyis) -2- morpholino propane -1- ketone, 2- benzyl -2- diformazans Base amino -1- (4- morphlinophenyls) butane -1- ketone, 2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) phenyl] propane - The oligomer etc. of 1- ketone.

As above-mentioned united imidazole, for example, 2 can be enumerated, 2 '-bis- (2- chlorphenyls) -4,4,5,5 '-tetraphenyl connection Imidazoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5, 5 '-four (alkoxyl phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline, 4, The imidazolium compounds etc. that the phenyl of 4 ', 5,5 ' positions is replaced by alkoxy carbonyl group.Wherein, it is preferable to use 2,2 '-bis- (2- chlorphenyls)- 4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines.

As above-mentioned benzoin based compound, for example, can enumerate benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin isobutyl ether etc..

As above-mentioned benzophenone based compound, for example, benzophenone, methyl o-benzoylbenzoate, 4- can be enumerated Phenyl benzophenone, 4- benzoyls -4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6- tri-methyl benzophenones, 4,4'- bis- (N, N'- dimethylamino)-benzophenone etc..

As above-mentioned thioxanthones based compound, for example, can enumerate 2-isopropylthioxanthone, 2,4- diethyl thioxanthones, Chloro- 4- propoxythioxanthones of bis- clopenthixal ketones of 2,4-, 1- etc..

As above-mentioned anthracene based compound, for example, 9,10- dimethoxys anthracene, 2- ethyl -9,10- dimethoxys can be enumerated Anthracene, 9,10- diethoxies anthracene, 2- ethyl -9,10- diethoxy anthracenes etc..

In addition to this, can use 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10- butyl -2- chloro-acridines ketone, 2- ethyl hydrazine, benzil, 9,10- phenanthrenequione, camphorquinone, phenylglyoxalates methyl esters, titanocenes compound etc., but be not limited to This.

If photopolymerization initiator and above-mentioned Photoepolymerizationinitiater initiater are used in combination, contain their coloring phototonus tree Oil/fat composition can more high-sensitivity, can improve productivity when manufacturing colour filter using it.

As long as above-mentioned photopolymerization initiator substance used in the art can use without particular limitation, tool Body can enumerate amine compounds, carboxylic acid compound etc..

As the concrete example of above-mentioned amine compounds, triethanolamine, methyl diethanolamine, triisopropanolamine can be specifically enumerated Equal aliphatic amine compounds；4- dimethylaminobenzoic acids methyl esters, ethyl 4-dimethylaminobenzoate, 4- dimethylamino benzene Isoamyl formate, 4- dimethylaminobenzoic acid 2- ethylhexyls, benzoic acid 2- dimethylamino ethyl esters, N, N- dimethyl is to first Aniline, 4,4 '-bis- (dimethylamino) benzophenone (common names：Michler's keton), the virtues such as 4,4 '-bis- (diethylamino) benzophenone More specifically fragrant race's amine compounds can preferably use aromatic amines compound.

It is thio that above-mentioned carboxylic acid compound can specifically enumerate phenyl acetic acid, aminomethyl phenyl thioacetic acid, ethylphenyl Acetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyphenylthio acetic acid, Dimethoxyphenyl Thioacetic acid, chlorophenylthio acetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio second Miscellaneous acetic acid class of aromatic series such as acid, N- naphthalenes glycine, naphthoxy acetic acid etc..

The content of above-mentioned photopolymerization initiator is relative to all solids in the photosensitive composition comprising it 100 weight % of ingredient can be 0.1~20 weight %, be specifically as follows 1~10 weight %.In above-mentioned photopolymerization initiator Content within the above range in the case of, then include the photopolymerization initiator photosensitive composition spirit Sensitivity efficiency more improves, and can improve the productivity of the colour filter formed using the composition.

According to an embodiment of the present invention, the content of above-mentioned Photoepolymerizationinitiater initiater is relative to including its coloring phototonus 100 weight % of all solids ingredient in resin combination can be 0.1~20 weight %, be specifically as follows 1~12 weight %. In the case where the content of above-mentioned Photoepolymerizationinitiater initiater is in above range, has the following advantages：Include its coloring phototonus The sensitivity of resin combination improves, and the time for exposure shortens, and productivity improves, and is able to maintain that high-resolution, the intensity of pixel portion Become good with the flatness on pixel portion surface.In addition, in the case where above-mentioned Photoepolymerizationinitiater initiater is containing less than above range, it may Curing degree is insufficient and pattern formation is made to go wrong.In the case where content is more than above range, in possible pattern formation process The generation of gas becomes more and reliability is made to go wrong.

Colorant

Rhodamine based dye

The photosensitive composition of the mode of the present invention includes containing with rhodamine system existing for particle shape The colorant of dyestuff, to have the advantages that the colour filter of high brightness can be made.

According to an embodiment of the present invention, above-mentioned rhodamine based dye can include selected from by C.I. acid reds 52,87, 91、92、94、289；C.I. Indian yellow 73；C.I. alkali red 1:1；C.I. alkaline purple 10,11；And the group of C.I. solvent red 49s composition One or more of.

While not wishing to be limited by theory, but in the filter substrate using general dyestuff, since dyestuff dissolves In the composition, it is thus possible to the reduction of contrast caused by drying when front baking is aggregated occur；It is ultraviolet when because of exposure The reduction of contrast caused by the oxidation of dye molecule caused by line；Decomposition, the distillation of dye molecule etc. when being dried because after Caused by contrast reduction etc..

However, in the present invention, since above-mentioned rhodamine based dye exists with particle shape, even if being coated and dried, exposing Light, development, it is rear dry after, above-mentioned rhodamine based dye also can steadily maintain particle shape, thus the pixel with colour filter, Especially the brightness raising of blue pixel and the excellent advantage of contrast.

Above-mentioned rhodamine based dye can be not in as the propylene glycol monomethyl ether of ester series solvent (PGMEA) Dissolubility.Above-mentioned PGMEA is widely used in since the dispersion stabilization of stability, coating, drying property, pigment is excellent Using the solvent of the photosensitive composition of pigment, above-mentioned rhodamine based dye is insoluble in above-mentioned PGMEA In the case of, above-mentioned characteristic is not damaged, and aftermentioned pigment and above-mentioned rhodamine based dye can be with particle shapes in above-mentioned PGMEA State steadily exists, therefore preferably.

Above-mentioned rhodamine based dye removes ionic miscellaneous included in above-mentioned rhodamine based dye preferably by refining Matter.For example, it is preferred that by Na included in above-mentioned rhodamine based dye⁺、Cl^-、SO₄ ^2-Etc the total of ionic impurity be set as 20,000ppm hereinafter, be more preferably set as 10,000ppm or less.Na included in above-mentioned rhodamine based dye⁺、Cl^-、SO₄ ^2-It Total satisfaction 20 of the ionic impurity of class, in the case of 000ppm is below, having can prevent from disperseing surely in above-mentioned PGMEA The advantages of qualitative the phenomenon that being reduced because of ionic impurity.

About the process for purification of above-mentioned rhodamine based dye, as long as method commonly used in the art is then not limited to This, for example, reprecipitation method, recrystallization, reverse osmosis membrane can be used or utilize ion exchange resin (cation exchange tree Fat, anion exchange resin) the methods of ion exchange.

In above-mentioned photosensitive composition whether it is to exist with particle shape about above-mentioned rhodamine based dye State, Particle Size Analyzer (Particle size analyzer, accusizer 780A) can be utilized to confirm.

In order to find out above-mentioned rhodamine based dye in the colour filter by the photosensitive composition manufacture of the present invention It is particle shape or molecular conformation, for example, can judge colour filter as follows by FIB-TEM analyses and EDX elemental analyses Blue pixel.The colour filter of above-mentioned manufacture is right since pigment particles and above-mentioned rhodamine based dye particle mix Implement analysis in 100 these particles.Since the grain size of above-mentioned pigment and above-mentioned rhodamine based dye is 10~500nm, The measurement diameter of FIB-TEM is set as 1~10nm.After FIB-TEM observations, elemental analysis is implemented to observation portion by EDX.Compare The EDX analysis results of the EDX analysis results of 100 above-mentioned particles and above-mentioned rhodamine based dye itself, if analysis result one The particle of cause is 1~100, then may determine that whether above-mentioned rhodamine based dye is deposited with particle shape in manufactured colour filter .

On the other hand, whether can such as lead to comprising above-mentioned rhodamine based dye in above-mentioned photosensitive composition Laser Raman spectroscopy is crossed to judge.That is, implementing the coating of above-mentioned photosensitive composition, solvent seasoning, exposure, showing Shadow dries and makes pixel afterwards.LR laser raman spectrophotometric spectra by comparing the pixel so manufactured and above-mentioned rhodamine based dye The LR laser raman spectrophotometric spectra of itself, if so as to whether judge in above-mentioned photosensitive composition comprising above-mentioned red Bright based dye.

The average grain diameter of above-mentioned rhodamine based dye and aftermentioned pigment is preferably 30~200nm, more preferably 30~ 100nm.In the case where the average grain diameter of above-mentioned rhodamine based dye and aftermentioned dyestuff is more than 200nm, transmitance and comparison Degree may be reduced because of the scattering of particle, in the case where the average grain diameter of above-mentioned rhodamine based dye is less than 30nm, not The alkali solubility of adhesive resin in exposure portion may be decreased, and pattern processability may be decreased.

Using dispersion machines such as sand mill, ball mills by zirconium dioxide bead to above-mentioned rhodamine based dye and aftermentioned face Material applies shear stress, so as to which the average grain diameter of above-mentioned rhodamine based dye and aftermentioned pigment is adjusted to above-mentioned model It encloses.

But it is likely difficult under the dispersion condition of previously known pigment by the average grain diameter of above-mentioned rhodamine based dye It is adjusted in above range.For example, above-mentioned powder pigment is 1 particle assembly of manufactured 30nm or so and formed several μm Powder particle.Interparticle cohesive force is small due to 1 time above-mentioned powder pigment, passes through smaller shear stress, short time Dispersion, can break up the agglutination of 1 particle, and average grain diameter is made to become 30~200nm.However, dyestuff powder is 1nm or so Elements collection and several μm of the oversize grain formed.Dyestuff powder is since intermolecular cohesive force is strong, and therefore, it is difficult to by smaller Shear stress makes average grain diameter be less than 200nm.In addition, in dyestuff be not present 1 particle, so if make shear stress increase or Jitter time is set to increase, then average grain diameter may be less than 30nm.

Therefore, in order to which the average grain diameter of above-mentioned rhodamine based dye and aftermentioned pigment is set as 30~200nm, preferably exist Respectively disperseed under different dispersion conditions.

It is small preferably by 0.3~2.0 μm of zirconium dioxide of the small ball's diameter as the dispersion condition of above-mentioned rhodamine based dye Ball is disperseed with larger shear stress and with the jitter time of 3~10 hours/kg, as the dispersion condition of above-mentioned pigment, Disperseed with the jitter time of 1~10 hour/kg preferably by 0.1~2.0 μm of zirconium dioxide bead of bead grain size.

In the present invention, preferably in the above-mentioned rhodamine based dye dispersion liquid and above-mentioned pigment that will undergo respective dispersion process point After dispersion liquid mixing, the additional process for implementing dispersion.It, can be by the flat of above-mentioned rhodamine based dye and above-mentioned pigment by the process Equal particle size adjustment and can make transmitance and brightness improve and further increase contrast to the range of 30~100nm.

For the addition dispersion condition of above-mentioned mixed dispersion liquid, preferably by 0.01~0.2 μm of zirconium dioxide of the small ball's diameter Bead is disperseed with smaller shear stress and with the jitter time of 0.1~3 hour/kg.

In addition, the photosensitive composition of the mode of the present invention is due to including to disperse in above-mentioned composition simultaneously Stabilized rhodamine based dye and the dispersant containing triazine based compound, thus with individually include the feelings of rhodamine based dye Condition is compared, and has the advantages that brightness can be made more to improve and prevent contrast from reducing.

Relative to whole 100 parts by weight of above-mentioned colorant dispersion, the content of above-mentioned rhodamine based dye can be 1~80 Parts by weight preferably can be 2~50 parts by weight.The content of above-mentioned rhodamine based dye within the above range in the case of, from It is preferred from the aspect of dispersion stabilization and transmitance.The content of above-mentioned rhodamine based dye is less than the case where above range Under, transmitance may be decreased, and in the case of being more than above range, dispersion stabilization may be reduced because of the agglutination of dyestuff.

Pigment

The photosensitive composition of one embodiment of the present invention can wrap together with above-mentioned rhodamine based dye Containing pigment.

Above-mentioned pigment can use the organic pigment or inorganic pigment used generally in the art.Above-mentioned pigment can use The various pigment used in ink, jetted ink etc. are printed, specifically, water-soluble azo pigment, insoluble can be enumerated Azo pigments, phthalocyanine color, quinacridone pigment, isoindolenone pigments, isoindoline pigment, pigment, pyrene ketone pigment, twoPiperazine pigment, anthraquinone pigment, bi-anthraquinone base pigment, anthracene pyrimidine pigment, anthanthrone (anthanthrone) pigment, indanthrone (indanthrone) pigment, flavanthrone pigment, pyranthrone (pyranthrone) pigment, diketopyrrolo-pyrrole pigment etc., But it is not limited to this.

As above-mentioned inorganic pigment, the metallic compounds such as metal oxide or metallic complex salt can be enumerated, specifically, can To enumerate the oxide or metal composite oxide of the metal of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black etc. Deng but it is not limited to this.

In particular, as above-mentioned organic pigment and inorganic pigment, specifically, colour index (association of dyeing man can be enumerated Will (The society of Dyers and Colourists) is published) in be classified as the compound of pigment, more specifically, The pigment that following colour index (C.I.) number can be enumerated, but is not necessarily limited to this, they can be respectively individually or by two Kind combination of the above uses.

C.I. pigment yellow 13,20,24,31,53,83,86,93,94,109,110,117,125,137,138,139,147, 148、150、153、154、166、173、180、185；

C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71；

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,215,216, 224、242、254、255、264；

C.I. pigment violet 14,19,23,29,32,33,36,37,38；

C.I. pigment blue 15 (15:3、15:4、15:6 etc.), 21,28,60,64,76；

C.I. pigment Green 7,10,15,25,36,47,58,59,62,63；

C.I. pigment brown 28；

C.I. pigment black 1,7；Deng

Above-mentioned pigment can respectively individually or be used in combination of two or more.

It can preferably be used selected from C.I. pigment oranges 38, C.I. pigment red 122s, C.I. face in foregoing illustrative C.I. pigment Expect red 166, C.I. paratoneres 177, C.I. paratoneres 208, C.I. paratoneres 242, C.I. paratoneres 254, C.I. paratoneres 255, C.I. pigment yellow 13s 8, C.I. pigment yellow 13s 9, C.I. pigment yellows 150, C.I. pigment yellows 185, C.I. pigment Green 7s, C.I. Pigment green 36, C.I. naphthol greens 58, C.I. pigment Violet 23s, C.I. pigment blue 15s:3, pigment blue 15:Pigment in 6.

It is preferable to use the colorant dispersions that its uniform particle sizes disperses for above-mentioned pigment.As the grain size for making above-mentioned pigment The example of evenly dispersed method can enumerate the method etc. for carrying out decentralized processing by adding pigment dispersing agent, according to this Method can obtain the colorant dispersion of pigment evenly dispersed state in the solution, therefore preferably.

Above-mentioned pigment dispersing agent can separately be added with the aftermentioned dispersant containing triazine based compound, such as can be lifted Go out surfactants such as cationic system, anionic system, nonionic system, amphoteric ion system, Polyester, polyamine system etc., they can be with Respectively individually or be used in combination of two or more, but not limited to this.

Relative to whole 100 parts by weight of above-mentioned colorant dispersion, the content of above-mentioned pigment is 1~50 parts by weight, preferably For the range of 5~40 parts by weight.If the content of above-mentioned pigment is calculated as the range of 1~50 parts by weight, viscosity with said reference It is low, preserve stablize excellent, dispersion efficiency it is high and contrast is risen it is effective, therefore preferably.

In addition, above-mentioned colorant dispersion can further include decentralized medium.

Above-mentioned decentralized medium is can unlimitedly to use this field in order to which the solution of pigment is solidifying and maintains stability and adds In the decentralized medium that generally uses.Preferably, contain and include butyl methacrylate (BMA) or methacrylic acid N, N- dimethyl The acrylic ester dispersant (hereinafter referred to as dispersant containing acrylic) of amino ethyl ester (DMAEMA) is preferred.At this point, above-mentioned propylene It is preferable to use the objects by active control method manufacture disclosed in KR published patent 2004-0014311 for acid system dispersant Matter can enumerate DISPER BYK- as the commercially available product of the acrylic ester dispersant by above-mentioned active control method manufacture 2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 etc..

Foregoing illustrative dispersant containing acrylic can respectively individually or be used in combination of two or more.

Above-mentioned decentralized medium can also use the pigment dispersing agent of other resin types other than above-mentioned dispersant containing acrylic. As the pigment dispersing agent of other above-mentioned resin types, can enumerate the pigment dispersing agent of well known resin type, especially polyurethane, Using polyacrylate as the polycarboxylate of representative, unsaturated polyamide, polycarboxylic acids, (part) amine salt of polycarboxylic acids, polycarboxylic acids Ammonium salt, the alkylamine salt of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate, hydroxyl polycarboxylic acids ester and they Modified product or with the freely polyester of (free) carboxyl and the amide for reacting and being formed of poly- (low-grade alkylidene imines) or Oily dispersant as their salt；(methyl) acrylic-styrene copolymer, (methyl) acrylic acid-(methyl) acrylic acid Water-soluble resin or water solubility as ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone Polymer compound；Polyester；Modified polyacrylate；The addition product of oxireme/propylene oxide；With phosphate etc..Make For the commercially available product of above-mentioned resin-bonded pigment dispersant, for cationic system pitch dispersant, for example, BYK (finishes Gram) trade name of chemical company：DISPER BYK-160、DISPER BYK-161、DISPER BYK-162、DISPER BYK- 163、DISPER BYK-164、DISPER BYK-166、DISPER BYK-171、DISPER BYK-182、DISPER BYK- 184；The trade name of BASF (BASF) company：EFKA-44、EFKA-46、EFKA-47、EFKA-48、EFKA-4010、EFKA- 4050、EFKA-4055、EFKA-4020、EFKA-4015、EFKA-4060、EFKA-4300、EFKA-4330、EFKA-4400、 EFKA-4406、EFKA-4510、EFKA-4800；The trade name of Lubirzol (Lu Borun) company：SOLSPERS-24000、 SOLSPERS-32550、NBZ-4204/10；Grind the trade name for the company of refining in river：HINOACT T-6000、HINOACT T- 7000、HINOACT T-8000；The trade name of aginomoto company：AJISPUR PB-821、AJISPUR PB-822、AJISPUR PB-823；The trade name of chemical company of common prosperity society：FLORENE DOPA-17HF、FLORENE DOPA-15BHF、FLORENE DOPA-33, FLORENE DOPA-44 etc..The pigment dispersing agent of other resin types other than above-mentioned dispersant containing acrylic can be with Respectively individually or be used in combination of two or more, can also be used in combination with dispersant containing acrylic.

Relative to above-mentioned 100 parts by weight of photosensitive composition all solids ingredient, above-mentioned pigment dispersing agent Content can be 0.1~30 parts by weight, preferably can be 0.1~15 parts by weight.Meet in the content of above-mentioned pigment dispersing agent In the case of stating range, contrast and stability can be made to improve.

Dispersant containing triazine based compound

The photosensitive composition of the mode of the present invention includes the dispersant containing triazine based compound.It is above-mentioned Triazine based compound is not limited to this as long as being used as substance known to dispersant in this field.For example, Japan can be utilized Triazine system dispersant described in publication special open 2008-214515, Japanese Laid-Open Patent special open 2011-032374.

According to an embodiment of the present invention, above-mentioned triazine based compound can be indicated by following chemical formula 2.

[chemical formula 2]

(in above-mentioned chemical formula 2,

R₁₁Selected from the alkane by hydrogen atom, the alkyl of carbon atom number 1~20, the straight-chain of carbon atom number 1~20 or branched Oxygroup and-NR₁₂R₁₃The group of base composition,

R₁₂And R₁₃It is each independently selected from the group being made of the alkyl of hydrogen atom and carbon atom number 1~20,

At this point, abovementioned alkyl and alkoxy are taken by the alkoxy of the straight-chain or branched of hydroxyl or carbon atom number 1~20 In generation, is non-substituted.)

In above-mentioned chemical formula 2, the alkyl of above-mentioned carbon atom number 1~20 can specifically enumerate methyl, ethyl, n-propyl, different The alkoxy of propyl, Zhong Bingji, normal-butyl, isobutyl group, sec-butyl, tertiary butyl etc., above-mentioned carbon atom number 1~20 can specifically be lifted Go out methoxyl group, ethyoxyl, positive propoxy, isopropoxy, secondary propoxyl group, n-butoxy, isobutoxy, sec-butoxy, tertiary fourth oxygen Base etc..

Comprising above-mentioned triazine based compound, pigment and above-mentioned rhodamine based dye can be made to be uniformly dispersed In various media.Therefore, the photosensitive composition of a mode of the invention is by comprising containing above-mentioned triazine system The dispersant of compound, to the rising being aggregated again with viscosity with the above-mentioned colorant containing rhodamine based dye of inhibition The good advantage of storage stability.

In addition, above-mentioned triazine based compound and resin type dispersant and in the case of using in dispersant, can make in raising It states the effect of the dispersibility of rhodamine based dye and pigment and the effect being aggregated again is inhibited to become particularly significant.

In addition, white is presented in above-mentioned triazine based compound in visibility region, therefore can utilize by comprising above-mentioned triazine The colour filter that the photosensitive composition of based compound is formed makes the image display device for capableing of high brightness colour developing. The photosensitive composition manufactured using above-mentioned triazine based compound inhibits pigment since initial viscosity is relatively low The effect that is aggregated again is high, therefore the excellent storage stability with dispersant, less excellent of the rising of the viscosity caused by preserving Point.

Relative to whole 100 parts by weight of above-mentioned colorant, the content of above-mentioned triazine based compound can be 0.1~60 weight Part.The content of above-mentioned triazine based compound within the above range in the case of, can inhibit above-mentioned rhodamine based dye and The crystal growth of above-mentioned pigment, therefore preferably.It, may in the case where the content of above-mentioned triazine based compound is less than above range There is a phenomenon where above-mentioned rhodamine based dyes to be aggregated, and in the case where content is more than above range, contrast may be decreased.

The photosensitive composition of one embodiment of the present invention can be further included selected from by alkali solubility tree One or more of the group of fat, Photoepolymerizationinitiater initiater, solvent and additive composition.

Alkali soluble resins

The photosensitive composition of one embodiment of the present invention can further include alkali soluble resins.

Above-mentioned alkali soluble resins includes the ethylene unsaturated monomer with carboxyl and polymerize, when being for forming pattern Development treatment process used in alkaline developer assign soluble ingredient.

The above-mentioned ethylene unsaturated monomer with carboxyl is not particularly limited, for example, acrylic acid, methyl-prop can be enumerated The monocarboxylic acids class such as olefin(e) acid, crotonic acid；The omega-dicarboxylic acids such as fumaric acid, mesaconic acid, itaconic acid and their acid anhydrides；ω-carboxyl gathers oneself Lactone list (methyl) acrylate etc. has list (methyl) esters of acrylic acid of polymer etc. of carboxyl and hydroxyl in two ends, excellent Choosing can be acrylic acid, methacrylic acid.They can be independent or be use mixing two or more.

Above-mentioned alkali soluble resins, which can further include, to be gathered at least one other monomers that above-mentioned monomer is copolymerized It closes.For example, styrene, vinyltoluene, methyl styrene, p-chlorostyrene, o-methoxystyrene, methoxy can be enumerated Base styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, vinyl benzyl methyl ether, to vinyl benzyl first Base ether, adjacent vinylbenzyl glycidyl base ether, vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base The aromatic ethenyl compounds such as ether；N- N-cyclohexylmaleimides, N- benzyl maleimides, N-phenylmaleimide, Hydroxyphenyl-maleimides, N- p-hydroxybenzenes maleimide, N- neighbour's methyl between N- o-hydroxy-phenyls maleimide, N- Methylphenylmaleimide, N- p-methylphenyls maleimide, N- o-methoxyphenyl horses between phenyl maleimide, N- Carry out the N- substituted maleimide amine such as acid imide, N- m-methoxyphenyls maleimide, N- p-methoxyphenyl maleimides Based compound；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid are different Propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) acrylic acid uncle Butyl ester etc. (methyl) alkyl-acrylates；(methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid Alicyclic (methyl) such as 2- methyl cyclohexyls, bis- cyclopentyloxy ethyl esters of (methyl) acrylic acid 2-, (methyl) isobornyl acrylates Esters of acrylic acid；(methyl) the benzyl acrylate classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate；3- (methyl-props Alkene acyloxymethyl) oxetanes, 3- (methacryloxymethyl) -3- Ethyloxetanes, 3- (methacryloxypropyl first Base) -2- trifluoromethyls oxetanes, 3- (methacryloxymethyl) -2- phenyl oxetanes, 2- (methacryls Oxygen methyl) the unsaturated oxetanes such as oxetanes, 2- (methacryloxymethyl) -4- trifluoromethyl oxetanes Compound etc..They can be independent or be use mixing two or more.

In this specification, (methyl) acrylate means acrylate or methacrylate.

The content of above-mentioned alkali soluble resins is not particularly limited, such as relative to whole in photosensitive composition 100 weight % of solid constituent, content are preferably 5~80 weight %, more preferably 10~70 weight %.Above-mentioned alkali soluble resins Content within the above range in the case of, dissolubility in developer solution fully is easy to form pattern, and prevents from exposing when development The film of the pixel portion in light portion reduces and the deciduous of non-pixel portion can be made to become good.

Photopolymerizable compound

The photosensitive composition of one embodiment of the present invention can further include photopolymerizable compound.

As long as the chemical combination that above-mentioned photopolymerizable compound can be polymerize by the effect of aftermentioned Photoepolymerizationinitiater initiater Object is just not particularly limited, but can preferably enumerate multifunctional photopolymerizable compound, two function photopolymerizable compounds or three Multifunctional photopolymerizable compound more than function etc..

As the concrete example of above-mentioned simple function photopolymerizable compound, can enumerate nonylphenol acrylate phenyl carbitol ester, Acrylic acid 2- hydroxyl -3- phenoxy-propyls, acrylic acid 2- ethylhexyls carbitol ester, acrylic acid 2- hydroxy methacrylates, N- vinyl Pyrrolidones etc. can enumerate Aronix M-101 (East Asia synthesis), KAYARAD TC-110S (Japanizations as commercially available product Medicine) or Viscoat 158 (Osaka Organic Chemical Industry) etc..

As the concrete example of above-mentioned two functions photopolymerizable compound, 1,6- hexylene glycols two (methyl) acrylic acid can be enumerated Ester, ethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, Bis- (acryloyl-oxyethyl) ethers of bisphenol-A, 3- methyl pentanediols two (methyl) acrylate etc., as commercially available product, Ke Yiju Go out Aronix M-210, M-1100,1200 (East Asia synthesis), KAYARAD HDDA (Japanese chemical drug), the 260 (Osaka Viscoat Organic Chemical Industry), AH-600, AT-600 or UA-306H (chemical company of common prosperity society) etc..

As the concrete example of multifunctional photopolymerizable compound more than above-mentioned trifunctional, there is trimethylolpropane tris (first Base) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) Acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) Acrylate, ethoxylated dipentaerythritol six (methyl) acrylate, propoxylated dipentaerythritol six (methyl) acrylic acid Ester, dipentaerythritol six (methyl) acrylate etc. can enumerate Aronix the M-309, (East Asia TO-1382 as commercially available product Synthesis), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Japanese chemical drug) etc..

It is excellent from polymerism and from the aspect of intensity capable of being improved in foregoing illustrative photopolymerizable compound, especially It is preferred that (methyl) esters of acrylic acid more than trifunctional and carbamate (methyl) acrylate.

Foregoing illustrative photopolymerizable compound can respectively individually or be used in combination of two or more.

Relative to 100 weight % of all solids ingredient in above-mentioned photosensitive composition, above-mentioned optical polymerism The content for closing object can be 5~70 weight %, preferably can be 10~60 weight %, more preferably can be 15~50 weight %. In the case where the content of above-mentioned photopolymerizable compound is in above range, intensity or flatness with pixel portion are good Advantage.

Solvent

The photosensitive composition of one embodiment of the present invention can further include solvent.

As long as above-mentioned solvent solvent used in the art can use without particular limitation, can use each Kind organic solvent.

Above-mentioned solvent can specifically enumerate ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, second two The ethylene glycol monoalkyl ethers class such as alcohol single-butyl ether；Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl The diethylene glycol dialkyl ethers class such as ether, diethylene glycol dibutyl ether；The second such as methylcellosolve acetate, ethyl cellosolve acetate Glycol alkyl ether acetate esters；Propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, propylene glycol monopropyl ether second The aklylene glycols alkylether acetates class such as acid esters；The alkoxyalkyls such as methoxybutyl acetic acid esters, methoxypentyl acetic acid esters Acetate esters；Benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon；Methyl ethyl ketone, acetone, methyl amyl ketone, methyl The ketones such as isobutyl ketone, cyclohexanone；The alcohols such as ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerine；3- ethoxy-cs The esters such as acetoacetic ester, 3- methoxy methyl propionates；Ring-type esters such as gamma-butyrolacton etc..

From the aspect of coating and drying property, above-mentioned solvent can preferably enumerate above-mentioned solvent mid-boiling point be 100 DEG C~ 200 DEG C of organic solvent can more preferably enumerate aklylene glycol alkylether acetates class, ketone, 3- ethoxyl ethyl propionates Or the esters such as 3- methoxy methyl propionates, it can further preferably enumerate propylene glycol monomethyl ether, propylene glycol list ethyl Ether acetic acid ester, cyclohexanone, 3- ethoxyl ethyl propionates, 3- methoxy methyl propionates etc..These solvents can respectively individually or incite somebody to action It is two or more to be used in mixed way.

The content of above-mentioned solvent is relative to the whole 100 weight % of the photosensitive composition comprising it, preferably 60~90 weight %, more preferably 70~85 weight %.The content of above-mentioned solvent within the above range in the case of, use roller The apparatus for coating such as painting machine, spin coater, slit spin coater, slit coater (otherwise referred to as die coating machine), ink-jet printer into Coating can become good when row coating.

Additive

The photosensitive composition of one embodiment of the present invention can further include additive.

Above-mentioned additive can be added selectively as needed, for example, other high-molecular compounds, solidification Agent, surfactant, closely sealed accelerating agent, antioxidant, ultra-violet absorber, anticoagulant etc..

Other above-mentioned high-molecular compounds can specifically enumerate the curable resins such as epoxy resin, maleimide resin, The thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester, polyurethane Deng, but not limited to this.

Above-mentioned curing agent is used to realize deeply-curing and improve mechanical strength, and epoxy compound can be specifically enumerated Object, polyfunctional isocyanate compound, melamine compound and oxetane compound etc., but not limited to this.

Epoxide in above-mentioned curing agent can more specifically enumerate bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy Resin, bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F types epoxy resin, phenolic resin varnish type epoxy resin, other aromatic system epoxies Resin, alicyclic ring family epoxy resin, ethylene oxidic ester system resin, glycidol amine system resin, above-mentioned epoxy resin bromination spread out Aliphatic, alicyclic or aromatic epoxy compound other than biology, epoxy resin and its brominated derivative, butadiene are (total) poly- Close object epoxides, isoprene (co) polymer epoxides, (methyl) glycidyl acrylate (co) polymer and different Cyanurate three-glycidyl ester etc..

Oxetane compound in above-mentioned curing agent can more specifically enumerate carbonic ester dioxygen azetidine, dimethylbenzene Dioxygen azetidine, adipate ester dioxygen azetidine, terephthalate dioxygen azetidine and cyclohexane dicarboxylic acid dioxygen Azetidine etc..

Above-mentioned curing agent can also be used in combination with curing compound is helped, described to help curing compound that make together with curing agent The epoxy group of epoxide, the oxetanes scaffolds open polymerization of oxetane compound.

It is above-mentioned to help curing compound such as having polybasic carboxylic acid class, polybasic carboxylic acid anhydride and acid agent.Above-mentioned polybasic carboxylic acid Anhydride can utilize commercially available epoxy curing agent.As commercially available product, ADEKA HARDENER EH-700 (ADEKA can be enumerated Industrial (strain) manufacture), RIKACID HH (new Japan Chemical (strain) manufacture) and MH-700 (new Japan Chemical (strain) manufactures) etc..On The curing agent stated and help curing compound that can respectively individually or be use mixing two or more.

Above-mentioned surfactant can use to more improve the envelope formation of photosensitive composition, excellent Choosing can use silicon-type, fluorine system, ester system, cationic system, anionic system, nonionic system, amphoteric ion system surfactant Deng.

Above-mentioned silicone based surfactants for example can enumerate DOW CORNING Dong Li organosilicons company as commercially available product DC3PA, DC7PA, SH11PA, SH21PA and SH8400 etc., TSF-4440, TSF-4300, TSF- of organosilicon company of GE Toshiba 4445, TSF-4446, TSF-4460 and TSF-4452 etc..

Above-mentioned fluorine system surfactant for example can enumerate big Japanese ink chemical industrial company as commercially available product MEGAFAC F-470, F-471, F-475, F-482 and F-489 etc..

In addition, as other workable commercially available products, KP (SHIN-ETSU HANTOTAI's chemical industry (strain)), POLYFLOW can be enumerated (altogether Flourish society is chemical (strain)), EFTOP (Tokheim product companies), MEGAFAC (big Japanese ink chemical industry (strain)), Flourad (Sumitomo 3M (strain)), Asahi guard, Surflon (being made above for Asahi Glass glass (strain)), (roads SOLSPERSE Bo Run), EFKA (EFKA chemical companies), PB 821 (aginomoto (strain)) and Disperbyk series (Bi Ke chemistry) etc..

Above-mentioned cationic system surfactant is for example, stearyl amine hydrochloride and lauryl trimethyl ammonium chloride etc. Amine salt or quaternary ammonium salt etc..

Above-mentioned anionic surfactant is for example, laruyl alcohol sodium sulfovinate and oleyl sulfate sodium etc. are advanced The alkylsurfuric acids such as alcohol sulfuric ester salt, NaLS and Texapon Special salt, neopelex and 12 Alkylaryl sulfonates class such as Negel etc..

Above-mentioned nonionic surfactants are for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxy Vinyl alkyl aryl ether, polyoxyethylene deriv in addition, ethylene oxide/propylene oxide block copolymer, anhydrosorbitol Aliphatic ester, polyoxyethylene sorbitan aliphatic ester, polyoxyethylene sorbitol aliphatic ester, fatty acid glyceride, Polyoxyethylene fatty acid ester and polyoxyethylene alkyl amine etc..

Above-mentioned surfactant can respectively individually or be used in combination of two or more.

The type of above-mentioned closely sealed accelerating agent is not particularly limited, can be with as the concrete example of workable closely sealed accelerating agent Enumerate vinyltrimethoxysilane, vinyltriethoxysilane, vinyl three (2- methoxy ethoxies) silane, N- (2- Amino-ethyl) -3- aminopropylmethyldimethoxysilanes, N- (2- amino-ethyls) -3- TSL 8330s, 3- Aminopropyltriethoxywerene werene, 3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxypropyl dimethoxies Base silane, 2- (3,4- expoxycyclohexyls) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilanes, 3- chloropropyls Trimethoxy silane, 3- methacryloxypropyl trimethoxy silanes, 3-mercaptopropyi trimethoxy silane, 3- isocyanic acids Ester group propyl trimethoxy silicane and 3- isocyanate group propyl-triethoxysilicanes etc..

Above-mentioned closely sealed accelerating agent can respectively individually or be used in combination of two or more.Relative to coloring phototonus resin group The feline amount in object is closed, content typically 0.01~10 weight % of above-mentioned closely sealed accelerating agent preferably can be with For 0.05~2 weight %.

The type of above-mentioned antioxidant is not particularly limited, but can enumerate 2,2'- thiobis (4- methyl-6-tert butyl Phenol), 2,6 di tert butyl 4 methyl phenol etc..

The type of above-mentioned ultra-violet absorber is not particularly limited, and as workable concrete example, can enumerate 2- (uncles 3- Butyl-2-hydroxy -5- aminomethyl phenyls) -5- chlorobenzotriazoles, alkoxy benzophenone etc..

The type of above-mentioned anticoagulant is not particularly limited, and as workable concrete example, can enumerate Sodium Polyacrylate etc..

The another way of the present invention is related to colour filter, is manufactured using above-mentioned photosensitive composition, to Developability and excellent heat resistance, brightness improve, and when development does not generate residue.

Above-mentioned colour filter includes substrate and is formed in the pattern layer on the top of aforesaid substrate.

For aforesaid substrate, above-mentioned colour filter itself can be substrate, or may be colour filter in display device etc. Position residing for device, is not particularly limited.Aforesaid substrate can be glass, silicon (Si), Si oxide (SiOx) or polymer-based Plate, above-mentioned polymeric substrate can be polyether sulfone (polyethersulfone, PES) or makrolon (polycarbonate, PC) etc..

Layer of the above-mentioned pattern layer as the photosensitive composition comprising the present invention can be above-mentioned by being coated with It photosensitive composition and is exposed, develops and heat cure and the layer that is formed in a predetermined pattern.Above-mentioned pattern layer It can be formed by implementing method commonly known in the art.

Including substrate as described above and the colour filter of pattern layer can further include between being formed in each pattern every Wall can also further include black matrix, and but not limited to this.

Further, it is also possible to further include the protective film on the pattern layer top for being formed in above-mentioned colour filter.

In addition, the another way again of the present invention is related to image display device, by developing comprising above-mentioned colour filter Property and excellent heat resistance, brightness improve, when development, does not generate residue.

The image display device of the present invention has above-mentioned colour filter, as concrete example, can enumerate liquid crystal display, OLED, flexible display etc., but not limited to this.

Hereinafter, in order to help to understand the present invention, open preferred embodiment, but following embodiments only illustrate the present invention, Diversified change and modification can be carried out within the scope of scope of the invention and technological thought, this is for those skilled in the art For be it will be apparent that it is such deformation and modification also would naturally fall within appended claims range.Embodiment below and In comparative example indicate content " % " and " part " as long as no it is specifically mentioned then be weight basis.

Synthesis example

Synthesis example 1：Triazine based compound 1

The chloro- 4,6- diaminostilbenes of 2-, 18.4 parts by weight of 3,5- triazines and 3- (2- ethyl hexyls are added in 100 parts by weight of water Oxygroup) 21 parts by weight of propylamine, it is reacted 1 hour at 10 DEG C.The reactant of gained is set to be reacted 5 hours at 85 DEG C.It will make the anti-of gained After answering object leaching and the washing residue that obtains, stands in 100 DEG C of thermostat and be dried the whole night, to obtain following chemistry The compound of formula 3.

[chemical formula 3]

Synthesis example 2：Triazine based compound 2

Chloro- 4,6- diamino-1,3,5-triazines, 18.4 parts by weight of 2-, 21 parts by weight of butylamine are added in 100 parts by weight of water, It is reacted 1 hour at 10 DEG C.The reactant of gained is set to be reacted 5 hours at 85 DEG C.It will make the reactant leaching of gained and obtain residual It after pulp water is washed, stands in 100 DEG C of thermostat and is dried the whole night, to obtain the compound of following chemical formula 4.

[chemical formula 4]

Synthesis example 3：Fluorenes based compound

Reactant 1.

Keep fluorenes 200g, potassium hydroxide 268.8g, potassium iodide 19.9g molten in anhydrous dimethyl sulfoxide 1L in a nitrogen atmosphere Solution, while reactant to be maintained to 15 DEG C through when be slowly added to bromoethane 283.3g within 2 hours after, by above-mentioned reactant 15 DEG C stirring 1 hour.Later, distilled water 2L is added to reactant, and after stirring 30 minutes, product is extracted with dichloromethane 2L, The organic layer of extraction is cleaned 2 times with distilled water 2L, then dries above-mentioned organic layer with anhydrous magnesium sulfate, vacuum distillation is molten The product obtained is fractionated by agent under reduced pressure, to obtain the liquid high as viscosity lurid reactant 1 (9, 9- diethyl -9H- fluorenes) 248.6g.

Reactant 2.

So that the above-mentioned reactants of 100.5g 1 is dissolved in dichloromethane 1L, after reactant is cooled to -5 DEG C, is slowly added to chlorine Change aluminium 72.3g, then while the temperature rise for preventing reactant through when be slowly added within 2 hours be diluted in dichloromethane 50ml In propionyl chloride 50.1g, and stirred 1 hour at -5 DEG C.Later, above-mentioned reactant is poured slowly into ice water 1L, stirs 30 points Clock and by after organic layer separation, cleaned with distilled water 500ml, be evaporated under reduced pressure the organic layer of recycling, by the product obtained use Silica gel column chromatography is (as developing solvent, ethyl acetate:N-hexane=1:4) it refines, to obtain as lurid solid Reactant 2 (1- (9,9- diethyl -9H- fluorenes -2- bases) -1,2- propanedione -2- oximes) 27.5g.

Reactant 3.

So that the above-mentioned reactants 2 of 44.5g is dissolved in tetrahydrofuran (THF) 900ml, sequentially adds 150ml and be dissolved in Isosorbide-5-Nitrae- TwoAfter 4N HCl and 24.7g isobutyl nitrites in alkane, reactant is stirred 6 hours at 25 DEG C.Later, molten to reaction Ethyl acetate 500ml is added in liquid, stirs after organic layer separation 30 minutes, is cleaned with distilled water 600ml, then by recycling Organic layer is dried with anhydrous magnesium sulfate, is evaporated under reduced pressure solvent, and the solid product obtained is utilized ethyl acetate:Hexane=1: It is dried again after 6 mixed solvent 300ml recrystallizations, to obtain (1- (9, the 9- diethyls of reactant 3 as light gray solid Base -9H- fluorenes -2- bases) -1,2- propanedione -2- oximes) 27.5g.

Reactant 4.

So that above-mentioned reactant 3 is dissolved in n-methyl-2-pyrrolidone (NMP) 1L in a nitrogen atmosphere, reactant is tieed up Hold after -5 DEG C addition triethylamine 35.4g, and after stirring 30 minutes, through when be slowly added within 30 minutes that chloroacetic chloride 27.5g is made to dissolve Solution in n-methyl-2-pyrrolidone 75ml stirs 30 minutes while preventing reactant from heating up.Later, it will distill Water 1L is slowly added in reactant, stirs after organic layer separation 30 minutes, the organic layer of recycling is done with anhydrous magnesium sulfate It is dry, and solvent under reduced pressure is distilled.By the solid product of acquisition using being dried again after ethyl alcohol 1L recrystallizations, to obtain conduct C-2 (1- (9,9- diethyl -9H- fluorenes -2- bases) -1,2- propanedione -2- oxime -0- acetic acid esters) 93.7g of grayish solid.

Synthesis example 4：Alkali soluble resins

Prepare the flask for having blender, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe, on the other hand, As monomer dropping funel, prepare input benzyl maleimide 74.8g (0.20 mole), acrylic acid 43.2g (0.30 mole), Vinyltoluene 118.0g (0.50 mole), peroxide -2-ethyl hexanoic acid tert-butyl 4g, propylene glycol monomethyl ether (PGMEA) substance being stirred after 40g as chain-transferring agent dropwise adding tank prepares that n-dodecane mercaptan 6g, PGMEA is added The substance being stirred after 24g.Later, PGMEA 395g are imported into flask, and the atmosphere in flask is made to be replaced as nitrogen from air After gas, the temperature of flask is warming up to 90 DEG C while stirring.Then, monomer and chain-transferring agent are dripped since dropping funel Add.It when dropwise addition, is respectively carried out 2 hours while maintaining 90 DEG C, 110 DEG C is warming up to after 1 hour and is maintained 3 hours, is then introduced into Gas introduction tube starts the bubbling of oxygen/nitrogen=5/95 (v/v) mixed gas.Then, by glycidyl methacrylate 28.4g [(0.10 mole), (carboxyl relative to the acrylic acid used in this reaction is 33 moles of %)], 2,2'- methylene In bis- (4- methyl-6-tert-butylphenols) 0.4g, triethylamine 0.8g input flasks, at 110 DEG C, the reaction was continued 8 hours, consolidate Body ingredient acid value is the alkali soluble resins of 70 ㎎ KOH/g.The weight average molecular weight of the polystyrene conversion measured by GPC is 16, 000, molecular weight distribution (Mw/Mn) is 2.3.

The measurement of weight average molecular weight (Mw) and number-average molecular weight (Mn) about above-mentioned resin, using GPC method with following Condition carries out.

Device：HLC-8120GPC (Tosoh (strain) manufacture)

Column：TSK-GELG4000HXL+TSK-GELG2000HXL (is connected in series with)

Column temperature：40℃

Mobile phase solvent：Tetrahydrofuran

Flow velocity：1.0ml/ minute

Injection rate：50μl

Detector：RI

Measure sample solution concentration：0.6 mass % (solvent=tetrahydrofuran)

Calibration standard substance：TSK standard polystyrens F-40, F-4, F-1, A-2500, A-500 (Tosoh (strain) manufacture)

The ratio between weight average molecular weight obtained above and number-average molecular weight are set as molecular weight distribution (Mw/Mn).

Production Example

Production Example 1：Colorant dispersion 1 (A-1)

By 20.48 parts by weight of compound, 9.12 weight of the chemical formula 3 synthesized in the synthesis example 1 as pyrrolotriazine derivatives Part C.I. pigment blue 15s:6,2.88 parts by weight C.I. acid reds 52, dispersant containing acrylic (DisperBYK-2000, Bi Kegong Department manufacture) 3.84 parts by weight, 2.88 parts by weight of resin of synthesis example 4, the propylene glycol monomethyl ether 55.04 as solvent 5.76 parts by weight of parts by weight and propylene glycol monomethyl ether, 360 parts by weight of zirconium dioxide bead of 0.2mm diameters input capacity are In the mayonnaise bottle of 140ml, it is kneaded 10 hours at 60 DEG C using paint regulator and carries out decentralized processing.Later, dioxy is removed Change zirconium bead, obtains dispersion liquid.By the above-mentioned dispersion liquid membrane filter of 1.0 μm of aperture (pore size), colorant is obtained Dispersion liquid 1.

Production Example 2：Colorant dispersion 2 (A-2)

The compound of the chemical formula 4 synthesized using in synthesis example 2 is as pyrrolotriazine derivatives, in addition to this, same with Production Example 1 Implement to sample.

Production Example 3：Colorant dispersion 3 (A-3)

Without using pyrrolotriazine derivatives, in addition to this, implement in the same manner as Production Example 1.

Production Example 4：Colorant dispersion 4 (A-4)

In addition to this implemented in the same manner as Production Example 1 instead of C.I. acid reds 52 using C.I. pigment Violet 23s.

Embodiment and comparative example

According to the composition described in following table 1, the photosensitive composition of embodiment and comparative example is manufactured.

[table 1]

Experimental example

Experimental example 1：Line peels off evaluation

The each photosensitive composition manufactured in above-described embodiment and comparative example is coated on to the glass of 5 × 5cm Glass substrate, and carry out rod coating in such a way that the final thickness after drying is 2.5 μm.Later, dry 3 in 100 DEG C of baking oven Minute and after solvent is removed, the interval with photoresist is set as 300 μm, and with Non-polarized lamp (Fusion Lamp) After the bright mode for reaching 40mJ of accumulation of 313nm wavelength exposes, taken after being impregnated 3 minutes in the KOH aqueous solutions of pH14 respectively Go out, taken out after being impregnated 1 minute in distilled water again, be allowed to cure 20 minutes in 230 DEG C of baking ovens, manufactures colour filter.

Pattern peeling phenomenon degree is measured for the colour filter of above-mentioned manufacture, benchmark judged as follows, and by result It is recorded in following table 2.

○：It is not peeled off on pattern

△：1~3 is peeled off on pattern

×：4 or more are peeled off on pattern

Experimental example 2：Brightness measuring

The coloring phototonus resin of Examples 1 to 5 and comparative example 1~4 is utilized by method identical with above-mentioned experimental example 1 Composition manufactures colour filter.Manufactured colour filter is set to spectral photometric colour measuring meter (CM-3700d, Konica Minolta sensing (strain) product), the transmission coloration of X, Y, Z coordinate axis when measuring 2 ° of illuminant-C, using Y value at this time as brightness.Result is remembered It is loaded in following table 2.

Filter of the brightness value will be manufactured using the photosensitive composition of comparative example 1 described in following table 2 The relative value when brightness of color device is as standard (100) indicates.

Experimental example 3：Heat-tolerance Determination

The coloring phototonus resin of Examples 1 to 5 and comparative example 1~4 is utilized by method identical with above-mentioned experimental example 1 Composition manufactures colour filter.Compare the colour filter of above-mentioned manufacture the aberration before and after 230 DEG C/2hr.Above-mentioned colour filter is set to Spectral photometric colour measuring meter (CM-3700d, Konica Minolta sense (strain) product) measures L*, a*, b* value when 2 ° of illuminant-C.By L*, Aberration in the three-dimensional colorimeter that a*, b* are defined is calculated according to [mathematical expression 1], and value of chromatism is smaller, it is meant that colour filter can It is higher by property.Record its result in following table 2.

[mathematical expression 1]

Δ Eab*=[(Δ L*)²+(Δa*)²+(Δb*)²]^1/2

Experimental example 4：Solvent resistance is evaluated

The coloring phototonus resin of Examples 1 to 5 and comparative example 1~4 is utilized by method identical with above-mentioned experimental example 1 Composition manufactures colour filter.So that the colour filter of above-mentioned manufacture is impregnated in N-Methyl pyrrolidone (NMP) solution after 30 minutes, utilizes Ultra-pure water is washed, and after carrying out drying in 2 minutes in the heating plate for being heated to 120 DEG C, measures the front and back aberration of dipping.

At this point, aberration is carried out by method identical with experimental example 3, and record the result in following table 2.Value of chromatism is got over It is small, it is meant that the reliability of colour filter is higher.

Experimental example 5：Speckle generates evaluation

The coloring phototonus resin of Examples 1 to 5 and comparative example 1~4 is utilized by method identical with above-mentioned experimental example 1 Composition manufactures colour filter.The colour filter of above-mentioned manufacture is taken out after the KOH aqueous solutions of pH10.5 impregnate 3 minutes respectively, then It is secondary impregnate 1 minute and take out in distilled water after, be allowed to cure 20 minutes in 230 DEG C of baking ovens.By the colour filter of above-mentioned manufacture A half part impregnated in distilled water after ten minutes, nitrogen blowing is allowed to drying.

The speckle of the part and untreated part that are impregnated in distilled water using Surface testing lamp (FR-100R) observation generates Whether, evaluation criteria is as follows, and records the result in following table 2.

○：The speckle caused by distilled water is not generated

×：Generate the speckle caused by distilled water

[table 2]

	Line peels off	Brightness	Heat resistance	Solvent resistance	Speckle
						Embodiment 1	○	1.13	1.21	1.01	○
Embodiment 2	○	1.09	1.31	1.03	○
						Embodiment 3	○	1.3	1.82	1.26	○
Embodiment 4	○	1.11	2.09	1.54	○
						Embodiment 5	○	1.07	1.56	1.34	○
Comparative example 1	△	1	4.74	5.74	×
						Comparative example 2	×	1.06	3.01	3.62	×
Comparative example 3	×	1.03	3.24	3.84	×
						Comparative example 4	○	0.63	1.23	1.34	○

With reference to above-mentioned table 2, can be confirmed at the same time to include the colorant of the rhodamine based dye containing particle shape, contains (implement in the case of the Photoepolymerizationinitiater initiater for having the dispersant of triazine based compound and the oxime ester fluorenes based compound containing the present invention Example 1~5), the case where with without triazine based compound (comparative example 1) and the case where without oxime ester fluorenes based compound (comparative example 2 and Comparative example 3) it compares, brightness, heat resistance and excellent solvent resistance, line peeling does not occur, when developing procedure does not generate by distilling yet Speckle caused by water, with without rhodamine based dye the case where compared with (comparative example 4), brightness is better.

Claims

1. a kind of photosensitive composition, which is characterized in that include：

The Photoepolymerizationinitiater initiater of oxime ester fluorenes based compound containing following chemical formula 1；

The colorant of rhodamine based dye containing particle shape；With

Dispersant containing triazine based compound,

Chemical formula 1

In the chemical formula 1,

R₁~R₅And R₇~R₁₀Be same or different to each other, be each independently selected from by hydrogen, halogen, carbon atom number 1~20 alkyl, The aryl of carbon atom number 6~20, the alkoxy of carbon atom number 1~20, the aryl alkyl of carbon atom number 7~40, carbon atom number 1~ The group of the naphthenic base composition of 20 hydroxy alkyl, the hydroxy alkoxy alkyl of carbon atom number 2~40 and carbon atom number 3~20,

R₆Selected from the alkane by hydrogen, halogen, the alkyl of carbon atom number 1~20, the aryl of carbon atom number 6~20, carbon atom number 1~20 The hydroxy alkoxy of oxygroup, the aryl alkyl of carbon atom number 7~40, the hydroxy alkyl of carbon atom number 1~20, carbon atom number 2~40 The group of base alkyl, the naphthenic base of carbon atom number 3~20, amino, nitro, cyano and hydroxyl composition,

The integer that p is 0~1.

2. photosensitive composition according to claim 1, which is characterized in that the coloring phototonus resin group Close one or more of the group that object further includes alkali soluble resins, photopolymerizable compound, solvent and additive composition.

3. photosensitive composition according to claim 1, which is characterized in that the triazine based compound is by changing The expression of formula 2,

Chemical formula 2

In the chemical formula 2,

R₁₁Selected from by hydrogen atom, the alkyl of carbon atom number 1~20, the straight-chain of carbon atom number 1~20 or branched alkoxy, With-NR₁₂R₁₃The group of base composition,

At this point, the alkyl and alkoxy replaced by the alkoxy of the straight-chain or branched of hydroxyl or carbon atom number 1~20 or It is non-substituted.

4. photosensitive composition according to claim 1, which is characterized in that oxime ester fluorenes system photopolymerization is drawn The content of hair agent is 0.1~20 weight % relative to the whole 100 weight % of the photosensitive composition comprising it.

5. photosensitive composition according to claim 1, which is characterized in that the colorant further includes Pigment.

6. photosensitive composition according to claim 1, which is characterized in that the rhodamine based dye includes Selected from by C.I. acid reds 52,87,91,92,94,289；C.I. Indian yellow 73；C.I. alkali red 1:1；C.I. alkaline purple 10,11； With one or more of the group of C.I. solvent red 49s composition.

7. a kind of colour filter, which is characterized in that include coloring phototonus resin combination according to any one of claims 1 to 6 The solidfied material of object.

8. a kind of image display device, it includes the colour filters described in claim 7.