CN110018614A - Self-luminous photosensitive polymer combination, color conversion layer and display device - Google Patents
Self-luminous photosensitive polymer combination, color conversion layer and display device Download PDFInfo
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- CN110018614A CN110018614A CN201910015519.XA CN201910015519A CN110018614A CN 110018614 A CN110018614 A CN 110018614A CN 201910015519 A CN201910015519 A CN 201910015519A CN 110018614 A CN110018614 A CN 110018614A
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
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- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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Abstract
The present invention provides self-luminous photosensitive polymer combination, by the color conversion layer and display device of self-luminous photosensitive polymer combination manufacture.Above-mentioned self-luminous photosensitive polymer combination is characterized in that, includes dyestuff and tetraazatetradecane porphyrin (tetraazaporphyrin) based compound with metal centered on aluminium (Al) or silicon (Si).Self-luminous photosensitive polymer combination of the invention has the effect of to ensure excellent optical density (OD), fluorescence efficiency and luminous intensity characteristic.
Description
Technical field
The present invention relates to self-luminous photosensitive polymer combinations, the face manufactured using the self-luminous photosensitive polymer combination
Color converting layer and display device.
Background technique
In recent years, display industry is from cathode-ray tube (cathode-ray tube, CRT) to plasma display
Show panel (plasma display panel, PDP), Organic Light Emitting Diode (organic light-emitting diode,
OLED), liquid crystal display (liquid-crystal display, LCD) etc. is that the flat-panel monitor of representative occurs quickly to become
Change.Wherein, LCD is widely used as display device used in substantially all industries, and application range is continuing
Expand.
LCD adjusts transmitance by the white light generated by back light unit while passing through liquid crystal cells, and mixes saturating
Cross red (Red), green (Green), blue (Blue) colour filter and 3 primary colors that come out are full-color to realize.
The light source of back light unit uses cold-cathode fluorescence lamp (Cold Cathode Fluorescent Lamp, CCFL), but
In this case, back light unit often needs to apply power supply to CCFL, therefore the problem of consuming electricity can be caused.Furthermore, it is indicated that with
Previous CRT is compared, and is existed and is lacked as about 70% horizontal color reproduction rate, the problem of environmental pollution with the addition of mercury
It falls into.
As the substitute for solving the above problems, so far, actively carry out about using light emitting diode
The research of the back light unit of (Light Emitting diode, LED).In the case where LED is used as back light unit, 100%
More than (U.S.) National Television Standards Committee (National Television System Committee, NTSC), color is again
Show the index of range and distincter image quality can be provided the consumer with.
Therefore, in order to improve light efficiency by the material for changing colour filter and LCD panel (panel) and structure etc. to mention
The efficiency of high back light, similar industrial circle just carries out effort, but is difficult to due to the limitation through characteristic of coloured material
Meet colorrendering quality and light characteristic simultaneously, there is a problem of that certain level can not be surmounted.
The problem of low colorrendering quality, can be solved by increasing the light efficiency of colour filter, it is proposed to this end that increasing filter
The thickness of color device, or the scheme of color conversion layer (or light conversion layer) is laminated or imported in a manner of to it.
Fig. 1 is the schematic diagram for showing the effect of the color conversion layer in display device, as shown in Figure 1, being produced by back light unit
Raw light source can be such that light efficiency directly increases via color conversion layer and colour filter.
KR published patent the 10-2012-0048218th discloses a kind of display, and it includes have blue or purple
The incident light of outside line wavelength band is converted into the light converter section of at least one fluorescent material of the light of predetermined wavelength band.But still
Have the shortcomings that the fluorescence efficiency of light converter section is low such.
KR published patent the 10-2010-0056437th disclose can be desired not being additionally formed next door
Position forms color conversion layer, color conversion filter device using ink-jet method manufacturing method, but in this case, in the presence of only with
Dyestuff autofluorescence low efficiency due to using organic EL Material is insoluble problem in common solvent.
Existing technical literature
Patent document
Patent document 1: KR published patent the 10-2012-0048218th
Patent document 2: KR published patent the 10-2010-0056437th
Summary of the invention
Problems to be solved by the invention
The present invention is for solving above-mentioned problem of the prior art, it is intended that by the inclusion of specific four azepines porphin
Quinoline based compound, so that the self-luminous photosensitive polymer combination of excellent fluorescence efficiency characteristic can be ensured, use this by providing
The color conversion layer and display device of self-luminous photosensitive polymer combination manufacture.
The method used for solving the problem
The present invention provides a kind of self-luminous photosensitive polymer combination, which is characterized in that comprising dyestuff and has aluminium
(Al) tetraazatetradecane porphyrin (tetraazaporphyrin) based compound of metal or centered on silicon (Si).
In addition, the present invention provides a kind of color conversion layer, which is characterized in that by above-mentioned self-luminous photosensitive polymer combination
Manufacture.
Further, the present invention provides a kind of display device, which is characterized in that includes above-mentioned color conversion layer.
Invention effect
Self-luminous photosensitive polymer combination of the invention, the color for using the self-luminous photosensitive polymer combination to manufacture
Conversion layer and display device include the tetraazatetradecane porphyrin based compound with metal centered on aluminium (Al) or silicon (Si), thus
With can ensure excellent optical density (OD) (Optical Density, O.D.), fluorescence efficiency (fluorescence
) and the effect of luminous intensity (luminous intensity) characteristic efficiency.
Detailed description of the invention
Fig. 1 is the schematic diagram for showing the effect of the color conversion layer in display device.
Specific embodiment
The present invention relates to the self-luminous photosensitive polymer combinations for the color conversion layer that can be used in display device.
Color conversion layer is used to improve the light efficiency reduced occurred by the use of colour filter, is located at and above-mentioned colour filter
The adjacent position of device (referring to Fig.1), by fine pattern structure in a manner of corresponding to the red (R) of colour filter, green (G) pattern
At.At this point, self-luminous photosensitive polymer combination can be used to be formed in above-mentioned fine pattern.
In particular, self-luminous photosensitive polymer combination of the invention can with comprising dyestuff and have aluminium (Al) or
Tetraazatetradecane porphyrin (tetraazaporphyrin) based compound of metal is characterized as essential component centered on silicon (Si).
In addition, self-luminous photosensitive polymer combination of the invention can further include bonding agent resin, optical polymerism
Compound, Photoepolymerizationinitiater initiater and solvent.
Hereinafter, being illustrated to each composition.
Tetraazatetradecane porphyrin based compound
Self-luminous photosensitive polymer combination of the invention is by the inclusion of four azepines with metal centered on aluminium or silicon
Porphyrin based compound, so as to ensure excellent optical density (OD) (Optical Density, O.D.), fluorescence efficiency
(fluorescence efficiency) and luminous intensity (luminous intensity) characteristic.
According to an embodiment of the present invention, above-mentioned tetraazatetradecane porphyrin based compound can be for represented by following chemical formula 1
Compound.
[chemical formula 1]
(in above-mentioned chemical formula 1, R26~R33Be each independently hydrogen, non-substituted phenyl, carbon atom number 1~8 alkyl,
The alkoxy of carbon atom number 1~8, nitro, halogen atom, cyano, the alkyl amino of carbon atom number 1~8, carbon atom number 1~8
Aminoalkyl or be selected from the alkoxy of carbon atom number 1~8, the alkyl of carbon atom number 1~8, nitro, halogen atom, carbon
The phenyl of the alkyl amino of atomicity 1~8, the aminoalkyl of carbon atom number 1~8 and the more than one substituent group in cyano,
M is with the more than one ligand in ammonia, the water and halogen atom or not no Al or Si of ligand.)
The content of tetraazatetradecane porphyrin based compound in self-luminous photosensitive polymer combination of the invention is relative to spontaneous
The total weight of light sensation photosensitive resin composition is preferably 0.001~15 weight %, more preferably 0.1~10 weight %.Above-mentioned
In the case that the content of tetraazatetradecane porphyrin based compound is within above range, excellent fluorescence efficiency can be shown and excellent
Choosing is reduced there are fluorescence and is made to process in the case where the content of tetraazatetradecane porphyrin based compound is more than above range
The problem of at detrimental effect.
In this specification, " substituted or non-substituted " is meant, be chosen free halogen base, itrile group, nitro, hydroxyl, alkyl,
Naphthenic base, alkenyl, alkoxy, aryloxy group, mercapto, alkylthio group, arylthio, sulfonyloxy, alkylsulfonyloxy, arylsulfonyl
Oxygroup, silicyl, boryl, arylamino, aryl alkyl amino, alkyl amino, aryl, aryl alkyl, aryl alkenyl, heterocycle
Replace with the more than one substituent group in the group of acetenyl composition, or without any substituent group.
In this specification, " halogen radical " means-F ,-Cl ,-Br or-I.
Dyestuff
Dyestuff contained by self-luminous photosensitive polymer combination of the invention can be used commonly used in color conversion layer
Dyestuff.
In addition, above-mentioned dyestuff can be characterized by being fluorescent dye, it preferably can be characterized by being red fluorescence dyestuff, more
It is preferred that can be characterized by being imidodicarbonic diamide (perylene bis-imide) based compound.
According to an embodiment of the present invention, above-mentioned imidodicarbonic diamide based compound can be for represented by following chemical formula 2
Compound.
[chemical formula 2]
(in above-mentioned chemical formula 2, R1 and R2 are each independently substituted or non-substituted aryl, substituted or non-substituted miscellaneous
Ring group or substituted or non-substituted linear or branched alkyl group,
R3, R4, R5 and R6 are each independently hydrogen atom, halogen atom, hydroxyl, substituted or non-substituted carbon atom number 1
3~10 alkoxy, substituted or non-substituted phenoxy group, substituted or non-substituted thio phenoxy group or following chemical formula tables
The substituent group shown, and R3, R4, R5 and R6 are all different.)
[chemical formula 3]
(in above-mentioned chemical formula 3, X1 and X5 are hydrogen atom,
X2, X3 and X4 are each independently hydrogen atom or halogen atom, and at least one of X2, X3 and X4 the above are
Halogen atom,
Y is oxygen atom or sulphur atom.)
In addition, compound represented by above-mentioned chemical formula 2 can be to be replaced the aryloxy group for having halogen by least more than one
Or compound made of thio phenoxy group substitution.
Comprising it is above-mentioned replace the aryloxy group for having halogen or thio phenoxy group to replace by least more than one made of two acyls
The self-luminous photosensitive polymer combination of imines based compound can be such that the fluorescence of color conversion layer increases.In addition, pass through to
Imidodicarbonic diamide based compound imports the substituent group of asymmetric form and causes structural distortion, can make the solubility for solvent
Increase, can show excellent chemistry, heat and optical stability as a result, there is very favorable effect for being applicable in for process
Fruit.
Another embodiment according to the present invention, above-mentioned imidodicarbonic diamide based compound can be 4 tables of following chemical formula
The compound shown.
[chemical formula 4]
(in above-mentioned chemical formula 4, R1 and R2 are each independently substituted or non-substituted aryl, substituted or non-substituted miscellaneous
Ring group, substituted or non-substituted straight chained alkyl or substituted or non-substituted branched alkyl,
R11, R12, R13 and R14 are each independently the linear chain or branched chain alkane selected from halogen atom, carbon atom number 1~10
Base, the halogenated alkyl of carbon atom number 1~10, hydroxyl, the alkoxy of carbon atom number 1~10, carbon atom number 1~10 ester group and
Substituent group in amino, and the type of at least one of R11, R12, R13 and R14 and remaining substituent group or substituent group
Position is different,
Y1、Y2、Y3And Y4It is each independently oxygen (O) atom or sulphur (S) atom,
A, b, c and d are each independently 1~5 integer.)
In addition, in compound represented by above-mentioned chemical formula 4, any of above-mentioned R11, R12, R13 and R14 can be
The position (para) or the position (meta) are substituted.Above-mentioned R1, R2 may be substituent group represented by following chemical formula 5.
[chemical formula 5]
(in above-mentioned chemical formula 5, R21~R25 is each independently former selected from hydrogen atom and substituted or non-substituted carbon
The substituent group of the linear or branched alkyl group of subnumber 1~5.)
Another embodiment according to the present invention, above-mentioned imidodicarbonic diamide based compound can for following chemical formula 4-1~
Any one of compound represented by 4-12.
[chemical formula 4-1]
[chemical formula 4-2]
[chemical formula 4-3]
[chemical formula 4-4]
[chemical formula 4-5]
[chemical formula 4-6]
[chemical formula 4-7]
[chemical formula 4-8]
[chemical formula 4-9]
[chemical formula 4-10]
[chemical formula 4-11]
[chemical formula 4-12]
The content of dyestuff in self-luminous photosensitive polymer combination of the invention is relative to self-luminous photoresist group
The total weight for closing object is preferably 0.001~30 weight %, more preferably 0.1~10 weight %.It is in the content of above-mentioned dyestuff
It is advantageous from the aspect of fluorescence efficiency and process in the case where within above range, if it exceeds above range, then exist because
The agglutination of dyestuff occurs and fluorescence efficiency reduces and the problem of adversely affect to process.
Bonding agent resin
Bonding agent resin contained by self-luminous photosensitive polymer combination of the invention usually has the work based on light, heat
Reactivity and alkali solubility, as coloured material decentralized medium and play a role.Self-luminous photonasty tree of the invention
As long as the bonding agent resin contained by oil/fat composition plays a role as the bonding agent resin for dyestuff, and for making
The bonding agent resin that can be dissolved in alkaline-based developer used in the development step of color conversion layer is made, then can be made
With.
Bonding agent resin is for example, carboxyl group-containing monomer and the monomer and the other monomers that can be copolymerized with it
Copolymer etc..
As above-mentioned carboxyl group-containing monomer, for example, unsaturated monocarboxylic or unsaturated dicarboxylic, unsaturation three can be enumerated
Unsaturated carboxylic acids such as the unsaturated polybasic carboxylic acid in the molecules such as carboxylic acid with more than one carboxyl etc..Here, as unsaturation
Monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid etc. can be enumerated.As unsaturation two
Carboxylic acid, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. can be enumerated.Unsaturated polybasic carboxylic acid can be acid
Acid anhydride can specifically enumerate maleic anhydride, itaconic anhydride, citraconic anhydride etc..In addition, unsaturated polybasic carboxylic acid can be its single (2-
Methacryloxyalkyl) ester, for example, mono succinate (2- acryloyl-oxyethyl) ester, mono succinate (2- first can be enumerated
Base acryloyl-oxyethyl) ester, phthalic acid list (2- acryloyl-oxyethyl) ester, phthalic acid list (2- metering system
Trimethylammonium) ester etc..Unsaturated polybasic carboxylic acid may be list (methyl) acrylate of its two ends dicarboxyl based polyalcohol,
For example, ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc. can be enumerated.These contain
Carboxylic monomer can respectively individually or be use mixing two or more.
As the above-mentioned other monomers that can be copolymerized with carboxyl group-containing monomer, for example, styrene, Alpha-Methyl benzene second can be enumerated
Alkene, adjacent vinyltoluene, vinyltoluene, to vinyltoluene, p-chlorostyrene, o-methoxystyrene, meta-methoxy
Styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, vinyl benzyl methyl ether, to vinyl benzyl ylmethyl
Ether, adjacent vinylbenzyl glycidyl base ether, vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base
The aromatic ethenyl compounds such as ether, indenes；Methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid second
Ester, n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate,
The secondary butyl ester of n-BMA, isobutyl acrylate, Isobutyl methacrylate, sec-butyl acrylate, methacrylic acid,
Tert-butyl acrylate, Tert-butyl Methacrylate, acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-
Hydroxy propyl ester, methacrylic acid 2- hydroxy propyl ester, acrylic acid 3- hydroxy propyl ester, methacrylic acid 3- hydroxy propyl ester, acrylic acid 2-
Hydroxybutyl, methacrylic acid 2- hydroxybutyl, acrylic acid 3- hydroxybutyl, methacrylic acid 3- hydroxybutyl, acrylic acid 4-
Hydroxybutyl, methacrylic acid 4- hydroxybutyl, allyl acrylate, allyl methacrylate, benzyl acrylate, methyl-prop
Olefin(e) acid benzyl ester, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid 2- methoxy
Base ethyl ester, methacrylic acid 2- methoxy acrylate, acrylic acid 2- phenoxy ethyl, methacrylic acid 2- phenoxy ethyl, methoxy
Base diethylene glycol acrylate, methoxyl group diethylene glycol methacrylate, methoxy triethylene acrylate, methoxyl group three
Glycolmethacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxyl group dipropyl two
Alcohol acrylate, methoxyl group dipropylene glycol methyl acrylate, isobornyl acrylate, isobornyl methacrylate, propylene
Ice drops in sour bicyclopentadiene ester, two ring of methacrylic acid, penta diethyl ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid
Piece ester, acrylic acid 2- hydroxyl -3- phenoxy-propyl, methacrylic acid 2- hydroxyl -3- phenoxy-propyl, glycerol mono-acrylate,
The unsaturated carboxylate types such as glycerin monomethyl acrylic ester；Acrylic acid 2- amino ethyl ester, methacrylic acid 2- amino ethyl ester, propylene
Sour 2- dimethylamino ethyl ester, methacrylic acid 2- dimethylamino ethyl ester, acrylic acid 2- amino propyl ester, methacrylic acid 2- ammonia
Base propyl ester, acrylic acid 2- dimethylamino propyl ester, methacrylic acid 2- dimethylamino propyl ester, acrylic acid 3- amino propyl ester, first
The unsaturations such as base acrylic acid 3- amino propyl ester, acrylic acid 3- dimethylamino propyl ester, methacrylic acid 3- dimethylamino propyl ester
Carboxylic acid amide's alkyl esters；The unsaturated carboxylic acids ethylene oxidic ester such as glycidyl acrylate, glycidyl methacrylate
Class；The generating vinyl carboxylates esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate；Vinyl methyl ether,
The unsaturated ethers such as vinyl ethyl ether, allyl glycidyl ether；Acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, sub- second
The vinyl cyanides based compound such as alkenyl dicyan；Acrylamide, Methacrylamide, α-chloroacrylamide, N-2- hydroxyethyl third
The unsaturated acyls amines such as acrylamide, N-2- hydroxyethyl methacrylamide；Maleimide, benzyl maleimide, N- benzene
The unsaturated acyls imines such as base maleimide, N- N-cyclohexylmaleimide；1,3- butadiene, isoprene, chlorobutadiene
Equal aliphatic conjugated dienes class；And polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid N-butyl,
Vinalac 5920, polysiloxanes the end of polymer molecular chain there is single acryloyl group or monomethacrylate acyl group
Polymeric monomer class etc..These monomers can respectively individually or be use mixing two or more.In particular, as it is above-mentioned can with contain
The other monomers of carboxylic monomer copolymerization, the monomer with norborneol skeleton, have rosin skeleton at the monomer with adamantane framework
The large volumes monomer such as monomer there is the tendency for reducing relative permittivity value, thus preferably.
The acid value of bonding agent resin of the invention is preferably the range of 20~200 (mgKOH/g).If acid value is in above-mentioned
Range, then the dissolubility in developer solution improves and non-exposed portion is easy dissolution, and sensitivity increases, and as a result the pattern of exposure portion is aobvious
It is remained when shadow and membrane left rate (film remaining ratio) can be improved, thus preferably.
Here, so-called acid value refers to, as the amount in potassium hydroxide required when acrylic acid series polymeric compounds 1g
(mg) value measured, in general, being titrated and being found out by using potassium hydroxide aqueous solution.
Furthermore it is preferred that by gel permeation chromatography (GPC；By tetrahydrofuran be used as eluting solvent) measurement polystyrene conversion
Weight average molecular weight (hreinafter referred to as " weight average molecular weight ") is 3,000~200,000, preferably 5,000~100,000 knot
Mixture resin.If molecular weight is in above range, the hardness with film is improved, and membrane left rate is high, the non-exposure in developer solution
The dissolubility in light portion is outstanding, the tendency that resolution ratio improves, thus preferably.
The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of bonding agent resin is preferably 1.5~6.0,
More preferably 1.8~4.0.If molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] is 1.5~6.0, show
Shadow is excellent, thus preferably.
The content of bonding agent resin of the invention is relative to the total of the solid component in self-luminous photosensitive polymer combination
Weight is usually the range of 5~85 weight %, preferably 10~70 weight %.Above range is in the content of bonding agent resin
Within in the case where, have for developer solution dissolubility sufficiently and non-pixel portion on substrate develop when be not likely to produce it is residual
Slag, the film that when development is not susceptible to the pixel portion of exposure portion are reduced, the good tendency of the deciduous of non-pixel portion, thus excellent
Choosing.
Photopolymerizable compound
Photopolymerizable compound contained by self-luminous photosensitive polymer combination of the invention is poly- by aftermentioned light
The compound that closes the effect of initiator and can polymerize can enumerate monofunctional monomer, two functional monomers, other multifunctional lists
Body etc..
As the concrete example of monofunctional monomer, nonyl phenyl carbitol acrylate, acrylic acid 2- hydroxyl -3- can be enumerated
Phenoxy-propyl, 2- ethylhexyl carbitol acrylate, acrylic acid 2- hydroxy methacrylate, n-vinyl pyrrolidone etc..
As the concrete example of two functional monomers, 1,6- hexylene glycol (methyl) acrylate, two (first of ethylene glycol can be enumerated
Base) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A bis- (propylene
Trimethylammonium) ether, 3- methyl pentanediol two (methyl) acrylate etc..
As the concrete example of other polyfunctional monomers, trimethylolpropane tris (methyl) acrylate, season can be enumerated
Penta tetrol three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two
Pentaerythrite six (methyl) acrylate etc..Wherein, it is preferable to use more than two functions polyfunctional monomer.
Total weight of the above-mentioned photopolymerizable compound relative to the solid component in self-luminous photosensitive polymer combination is led to
Often used with 5~50 weight %, preferably with the range of 7~45 weight %.Above-mentioned model is in the content of photopolymerizable compound
In the case where within enclosing, intensity, flatness with pixel portion become good tendency, thus preferably.
Photoepolymerizationinitiater initiater
Photoepolymerizationinitiater initiater used in the present invention preferably comprises acetophenone based compound.As acetophenone system chemical combination
Object, for example, diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzil dimethyl contracting can be enumerated
Ketone, 2- hydroxyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -2- methylpropane -1- ketone, 1- hydroxycyclohexylphenylketone, 2- methyl -
1- (4- methylthiophenyi) -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) fourth
Alkane -1- ketone, oligomer of 2- hydroxy-2-methyl [4- (1- methyl ethylene) phenyl] propane -1- ketone etc., can preferably enumerate 2-
Benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- ketone etc..Furthermore, it is possible to by the light other than above-mentioned acetophenone system
Polymerization initiator is applied in combination.Photoepolymerizationinitiater initiater other than acetophenone system can enumerate irradiation light and generate living radical
Living radical producing agent, sensitizer, acid agent etc..As living radical producing agent, for example, benzoin system can be enumerated
Close object, benzophenone based compound, thioxanthones based compound, triazine based compound etc..As benzoin based compound, for example,
Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether etc. can be enumerated.As
Benzophenone based compound, for example, benzophenone, methyl o-benzoylbenzoate, 4- phenyl benzophenone, 4- benzene can be enumerated
Formyl -4'- dimethyl diphenyl sulfide, 3,3', 4,4'- tetra- (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6- trimethyl two
Benzophenone etc..As thioxanthones based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- bis- can be enumerated
Ethyl thioxanthones, bis- clopenthixal ketone of 2,4-, the chloro- 4- propoxythioxanthone of 1- etc..As triazine based compound, for example, can lift
Bis- (trichloromethyl) -6- (4- the methoxyphenyl) -1,3,5- triazines of 2,4-, bis- (trichloromethyl) -6- (the 4- methoxynaphthalenes of 2,4- out
Base) -1,3,5- triazine, bis- (trichloromethyl) -6- (4- the methoxyl-styrene) -1,3,5- triazines of 2,4-, bis- (three chloromethanes of 2,4-
Base) -6- [2- (5- methylfuran -2- base) ethylidene] -1,3,5- triazine, bis- (trichloromethyl) -6- [2- (furans -2- of 2,4-
Base) ethylidene] -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (4- diethylamino -2- aminomethyl phenyl) ethylidene] -
Bis- (the trichloromethyl) -6- of 1,3,5- triazine, 2,4- [2- (3,4- Dimethoxyphenyl) ethylidene] -1,3,5- triazine etc..As
Sensitizer, for example, bis- (Chloro-O-Phenyl) -4,4' 2,4,6- trimethylbenzoyl diphenyl phosphine oxides, 2,2'- can be enumerated, 5,
5'- tetraphenyl -1,2'- bisglyoxaline, 10- butyl -2- chloro-acridine ketone, 2- ethyl hydrazine, benzil, 9,10- phenanthrenequione, camphorquinone,
Phenylglyoxalates methyl esters, titanocenes compound etc..As above-mentioned acid agent, for example, 4- hydroxy phenyl dimethyl disulfide can be enumeratedTosilate, 4- hydroxy phenyl dimethyl disulfideHexafluoro antimonate, 4- acetoxyl group phenyl dimethyl disulfideTo toluene
Sulfonate, 4- acetoxyl group phenyl methyl dibenzylsulfideHexafluoro antimonate, triphenyl sulphurTosilate, triphenyl sulphurHexafluoro antimonate, diphenyl iodineTosilate, diphenyl iodineHexafluoro antimonate etc.Salt, nitrobenzyl first
Benzene sulfonic acid esters, benzoin tosylate class etc..In addition, same as also having in the above compound of living radical producing agent
When generate living radical and acid compound, for example, triazine system Photoepolymerizationinitiater initiater is also used as acid agent.
The content of Photoepolymerizationinitiater initiater used in self-luminous photosensitive polymer combination of the invention is relative to above-mentioned
The total weight of the solid component of bonding agent resin and photopolymerizable compound, usually 0.1~40 weight %, preferably 1~30
Weight %.In the case where the content of Photoepolymerizationinitiater initiater is within above range, there is self-luminous photosensitive resin composition
Object high-sensitivity, intensity, the flatness on the surface of the pixel portion of the pixel portion formed using the composition are become good and inclined
To, thus preferably.
Further, in the present invention, photopolymerization initiator can be used.Photopolymerization initiator causes with photopolymerization sometimes
Agent is applied in combination, and is the change used to promote the polymerization for the photopolymerizable compound for being photopolymerized initiator initiation polymerization
Close object.As photopolymerization initiator, amine compound, alkoxy anthracene based compound, thioxanthones based compound etc. can be enumerated.
As amine compound, for example, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylamino benzene first can be enumerated
Sour methyl esters, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, benzoic acid 2- dimethylaminoethyl
Ester, 4- dimethylaminobenzoic acid 2- ethylhexyl, N, bis- (dimethylamino) the hexichol first of N- dimethyl-p-toluidine, 4,4'-
Ketone (common name, Michler's keton), bis- (diethylamino) benzophenone of 4,4'-, bis- (ethylmethylamino) benzophenone of 4,4'- etc.,
Wherein, bis- (diethylamino) benzophenone of preferably 4,4'-.As alkoxy anthracene based compound, for example, 9 can be enumerated,
10- dimethoxy anthracene, 2- ethyl -9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene
Deng.As thioxanthones based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thiophene can be enumerated
Ton ketone, bis- clopenthixal ketone of 2,4-, the chloro- 4- propoxythioxanthone of 1- etc..Such photopolymerization initiator can individually or will be more
Kind is applied in combination.
In addition it is possible to use commercially available photopolymerization initiator, as commercially available photopolymerization initiator, for example, can be with
Enumerate " EAB-F " [trade name, manufacturer: Baotugu Chemical Industrial Co., Ltd] etc..
Using these photopolymerization initiators, usage amount is usual in terms of every 1 mole of Photoepolymerizationinitiater initiater
For 10.0 moles hereinafter, preferably 0.01~5.0 mole.In the usage amount feelings within the above range of photopolymerization initiator
Under condition, the sensitivity with self-luminous photosensitive polymer combination is further got higher, and the color formed using the composition is turned
The tendency that the productivity of layer improves is changed, thus preferably.
Solvent
Solvent contained by self-luminous photosensitive polymer combination of the invention is not particularly limited, and color sensation can be used
Various organic solvents used in the field of photosensitive resin composition.As its concrete example, ethylene glycol monomethyl can be enumerated
The ethylene glycol monoalkyl ethers class such as ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol two
The diethylene glycol dialkyl ethers such as methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether
Class, the ethylene glycol alkyl ethers acetate esters such as methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether
Ester, propylene glycol monoethyl acetic acid esters, propylene glycol monopropyl ether acetic acid esters, methoxybutyl acetic acid esters, methoxypentyl acetic acid
The aklylene glycols alkylether acetates class such as ester, benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon, methyl ethyl ketone,
The ketones such as acetone, methyl amyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol,
The alcohols such as glycerol, the esters such as 3- ethoxyl ethyl propionate, 3- methoxy propyl acid methyl, ring-type esters such as gamma-butyrolacton etc..
About above-mentioned solvent, from the aspect of coating and drying property, it is 100 that above-mentioned solvent mid-boiling point, which preferably can be used,
DEG C~200 DEG C of organic solvent, aklylene glycol alkylether acetates class, ketone, 3- ethoxy-propionic acid more preferably can be used
Propylene glycol monomethyl ether, propylene glycol list further preferably can be used in the esters such as ethyl ester or 3- methoxy methyl propionate
Monoethyl ether acetate, cyclohexanone, 3- ethoxy-propionic acid ethyl, 3- methoxy propyl acid methyl etc..These solvents can respectively individually
Or it two or more is used in mixed way.
The content of solvent in self-luminous photosensitive polymer combination of the invention is relative to self-luminous photoresist group
The total weight for closing object is usually 60~90 weight %, preferably 70~85 weight %.Solvent content within the above range
In the case where, utilize roll coater, spin coater, slit spin coater, slit coater (otherwise referred to as die coating machine), ink jet printer etc.
When apparatus for coating is coated, there is coating to become good tendency, thus preferably.
Other additives
Self-luminous photosensitive polymer combination of the invention can also include filler, other macromolecule chemical combination as needed
The additives such as object, pigment dispersing agent, closely sealed promotor, antioxidant, ultraviolet absorbing agent, anticoagulant.
The concrete example of filler may be exemplified glass, silica, aluminium oxide etc..
As other high-molecular compounds, the curable resins such as epoxy resin, maleimide resin can be specifically enumerated,
The thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester, polyurethane
Deng.
As pigment dispersing agent, commercially available surfactant can be used, for example, organic silicon-type, fluorine system, ester can be enumerated
Surfactants such as system, cationic system, anionic system, nonionic system, both sexes etc..They can respectively individually or will be two or more
It is applied in combination.As above-mentioned surfactant, for example, having polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, poly- second
Diol diesters class, sorbitan fatty acid ester class, fatty acid modified polyesters, tertiary-amine modified polyurethanes, polyethylene acyl are sub-
Amine etc., in addition, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), POLYFLOW (common prosperity society chemistry (strain) can be enumerated with trade name
Manufacture), EFTOP (manufacture of Tohkem Products company), MEGAFAC (big Japanese ink chemical industry (strain) manufacture),
Flourad (Sumitomo 3M (strain) manufacture), Asahi guard, Surflon (more than, Asahi Glass (strain) manufacture), SOLSPERSE
(Zeneca (strain) manufacture), EFKA (manufacture of EFKA Chemicals company), PB821 (aginomoto (strain) manufacture) etc..
As above-mentioned closely sealed promotor, for example, vinyltrimethoxysilane, vinyl triethoxyl silicon can be enumerated
Alkane, vinyl three (2- methoxy ethoxy) silane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, N-
(2- amino-ethyl) -3- TSL 8330,3-aminopropyltriethoxysilane, 3- epoxypropoxy front three
Oxysilane, 3- glycidoxypropyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3-
Chloropropylmethyldimethoxysilane, 3- r-chloropropyl trimethoxyl silane, 3- methyl allyl acyloxypropyl trimethoxysilane, 3-
Mercaptopropyi trimethoxy silane etc..
As above-mentioned antioxidant, 2,2 '-thiobis (4- methyl-6-tert-butylphenol), 2,6- bis--can be specifically enumerated
Tert-butyl-4-methyl-Phenol etc..As ultraviolet absorbing agent, 2- (3- tert-butyl -2- hydroxy-5-methyl base benzene can be specifically enumerated
Base) -5- chlorobenzotriazole, alkoxy benzophenone etc..As anticoagulant, Sodium Polyacrylate etc. can be specifically enumerated.
Self-luminous photosensitive polymer combination of the invention can for example be manufactured by the following method.Keep dyestuff preparatory
It mixes and dissolves with solvent.At this point, pigment dispersing agent is optionally used, in addition, also cooperating part or all of bonding agent sometimes
Resin.It is further added in the way of becoming scheduled concentration in resulting dispersion liquid (hereinafter, otherwise referred to as mill base)
Remaining bonding agent resin, Photoepolymerizationinitiater initiater, the other compositions optionally used, optionally adds photopolymerizable compound
Solvent, so as to obtain the self-luminous photosensitive polymer combination of target.
Color conversion layer
In addition, the present invention provides the color conversion layer manufactured by above-mentioned self-luminous photosensitive polymer combination.
Color conversion layer of the invention be applied to display device in the case where, due to display device by the light of light source and
It shines, therefore can be realized superior light efficiency.Having coloured light further, since issuing, colorrendering quality is more excellent,
And light is issued in omnidirection because of luminescence generated by light, thus can also improve visual angle.
More specifically, in the common display device comprising color conversion layer, white light through color conversion layer and
Color is presented, but a part of light can be absorbed by color conversion layer during this, therefore there are problems that light efficiency decline.But
It is, in the case where the color conversion layer comprising being manufactured by self-luminous photosensitive polymer combination of the invention, color conversion layer
Self-luminous is carried out by the light of light source, therefore can be realized superior light efficiency.
Pattern layer of the color conversion layer comprising substrate and the top for being formed in aforesaid substrate.
Substrate can be color conversion layer itself substrate, or may be in display device etc. locating for color conversion layer
Position is not particularly limited.Aforesaid substrate can be glass, silicon (Si), Si oxide (SiOx) or polymeric substrate, it is above-mentioned
Polymeric substrate can be polyether sulfone (polyethersulfone, PES) or polycarbonate (polycarbonate, PC) etc..
Pattern layer is the layer comprising self-luminous photosensitive polymer combination of the invention, be can be above-mentioned spontaneous by being coated with
Light sensation photosensitive resin composition, and be exposed according to scheduled pattern, develop and heat cure and the layer that is formed.
Can be had by the pattern layer that above-mentioned self-luminous photosensitive polymer combination is formed containing red quantum dot particle
Red pattern layer, the green pattern layer containing green quantum dot particles and the blue color patterns layer containing blue quantum dot particles.Light
When irradiation, red pattern layer issues red light, and green pattern layer issues green light, and blue color patterns layer issues blue light.At this point,
When applied to display device, the sending light of light source is not particularly limited, and from the aspect of superior colorrendering quality, can be made
With the light source for issuing blue light.
According to other embodiments of the present invention, above-mentioned pattern layer can also only have red pattern layer, green pattern layer,
And the pattern layer of two kinds of colors in blue color patterns layer.In this case, above-mentioned pattern layer is further equipped with without containing quantum dot grain
The transparent pattern layer of son.
In the case where only having the pattern layer of two kinds of colors, the wave for issuing and the remaining color not contained being presented can be used
The light source of long light.For example, the light for issuing blue light can be used comprising red pattern layer and in the case where green pattern layer
Source.In this case, red quantum dot particle issues red light, green quantum dot particles issue green light, and transparent pattern layer is direct
Blue is presented through blue light.
Color conversion layer comprising substrate as described above and pattern layer, which can further include, to be formed between each pattern
Next door, black matrix can also be further included.Further, it is also possible to further include the pattern layer for being formed in color conversion layer
The protective film on top.
Display device
In addition, the present invention provides the display device comprising above-mentioned color conversion layer.
Color conversion layer of the invention can be applied not only to common liquid crystal display device, and can be applied to electroluminescent
The various image display devices such as luminous display unit, plasm display device, field emission display device.
Display device of the invention can have comprising the red pattern layer containing red quantum dot particle, containing green amount
The son point green pattern layer of particle and the color conversion layer of the blue color patterns layer containing blue quantum dot particles.In this case,
When applied to display device, the sending light of light source is not particularly limited, and from the aspect of superior colorrendering quality, preferably may be used
To use the light source for issuing blue light.
According to other embodiments of the present invention, display device of the invention can also have only comprising red pattern layer,
The color conversion layer of the pattern layer of two kinds of colors in green pattern layer and blue color patterns layer.In this case, above-mentioned color conversion
Layer is further equipped with the transparent pattern layer without containing quantum dot particles.
In the case where only having the pattern layer of two kinds of colors, the wave for issuing and the remaining color not contained being presented can be used
The light source of long light.For example, the light for issuing blue light can be used comprising red pattern layer and in the case where green pattern layer
Source.In this case, red quantum dot particle issues red light, green quantum dot particles issue green light, and transparent pattern layer is direct
Blue is presented through blue light.
The light efficiency of display device of the invention is excellent and shows high brightness, and colorrendering quality is excellent, can have wide
Visual angle.
Hereinafter, the present invention is described in more detail using embodiment and comparative example.But following embodiments is for example
Show of the invention, the present invention is not limited by following embodiments, can varied ground modifications and changes.The scope of the present invention
It is determined by the technical idea of aftermentioned the scope of the claims.In addition, hereinafter, indicate content " % " and " part " as long as no
Specifically mentioned is then weight basis.
Synthesis example 1
It is following to synthesize represented by chemical formula 1-1 by well known method in document (J.Am.Soc., 4839 (1952))
Tetraazatetradecane porphyrin compound.
By no 50 parts by weight of metal octaphenyl tetraazatetradecane porphyrin and 1.5 parts by weight of aluminium oxide in 25 parts by weight of o-dichlorohenzene
It carries out flowing back for 1.5 hours under solvent.When the reaction is finished, above-mentioned reaction mixture is flowed back with the state of heat.Reaction knot
Shu Hou is cooled to room temperature and cleans the solid of generation with hot water and ethyl alcohol, then extracted using chlorobenzene.It then, will be upper
It states extract crystallization and obtains pure octaphenyl tetraazatetradecane porphyrin aluminium.
Synthesis example 2
Aluminium oxide is replaced according to method same as above-mentioned synthesis example 1, to obtain chemical formula 1-2 in addition to this using silicic acid
Represented pure octaphenyl tetraazatetradecane porphyrin silicon.
Compare synthesis example 1
Aluminium oxide is replaced according to method same as above-mentioned synthesis example 1, to obtain chemical formula 1-3 in addition to this using manganese trioxide
Represented pure octaphenyl tetraazatetradecane porphyrin manganese.
Compare synthesis example 2
Aluminium oxide is replaced according to method same as above-mentioned synthesis example 1, to obtain chemical formula in addition to this using copper nitrate
Pure octaphenyl tetraazatetradecane porphyrin copper represented by 1-4.
Synthesis example 3
Extremely by 1,6,7,12- tetrachloro tetracarboxylic dianhydride (0.11mol) and 2,6- diisopropyl aniline (0.44mol) investment
After in propionic acid 1L, heats up and maintain react within 5 hours at 140 DEG C.Then, reaction solution is cooled to room temperature and depressurized precipitate
Filter, is washed with methanol.After above-mentioned filtrate is dispersed in water and maintains 30 minutes, it is filtered under diminished pressure, is dispersed again
In methanol and after maintaining 30 minutes, it is filtered under diminished pressure.Above-mentioned filtrate is dry, intermediate is obtained with 80.5% yield
It closes object (INT).
For the midbody compound of above-mentioned formation, mass spectrum (Mass is measured using MALDI-TOF measurement device
Spectrometric, MS), as a result confirming molecular weight is 848.16.
Synthesis example 4: the synthesis of the compound of chemical formula 4-1
Midbody compound (0.04mol) and N-Methyl pyrrolidone (266.1g) synthesized by above-mentioned synthesis example 3 are molten
It solves after adding potassium carbonate (0.04mol) in liquid, is warming up to 120 DEG C.It was put into through 2 hours by 4- in above-mentioned reaction solution at 120 DEG C
Fluorophenol (0.04mol) is dissolved in solution made of N-Methyl pyrrolidone (88.7g).Maintain react within 1 hour with mutually synthermal
Afterwards, 4- chlorophenol (0.16mol) and potassium carbonate (0.16mol) are added, is stirred 4 hours.Later, reaction solution is cooled to room temperature,
It is expelled in distilled water 3L.The violet precipitate so generated is filtered under diminished pressure, and is washed with methanol.By above-mentioned filtrate
After being re-dissolved in methylene chloride (MC), carries out silica filtration and remove impurity, recrystallized with MeOH, with 40.4%
Yield obtain the compound of chemical formula 4-1, confirm molecular weight be 1198.29.
Synthesis example 5: the synthesis of the compound of chemical formula 4-3
Midbody compound (0.04mol) and N-Methyl pyrrolidone (266.1g) synthesized by above-mentioned synthesis example 3 are molten
It solves after adding potassium carbonate (0.04mol) in liquid, is warming up to 120 DEG C.In above-mentioned reaction solution at 120 DEG C through 2 hours investments by 2,
4- (tert-butyl) phenol (0.04mol) is dissolved in solution made of N-Methyl pyrrolidone (88.7g).1 is maintained with mutually synthermal
After hour reaction, 4- chlorophenol (0.16mol) and potassium carbonate (0.16mol) are added, is stirred 4 hours.Later, reaction solution is cooling
To room temperature, it is expelled in distilled water 3L.The violet precipitate so generated is filtered under diminished pressure, and is washed with methanol.It will be upper
It states after filtrate is re-dissolved in methylene chloride (MC), carries out silica filtration and remove impurity, recrystallized with MeOH,
The compound of chemical formula 4-3 is obtained with 37.0% yield, confirming molecular weight is 1236.37.
Synthesis example 6: the synthesis of the compound of chemical formula 4-7
Midbody compound (0.04mol) and N-Methyl pyrrolidone (266.1g) synthesized by above-mentioned synthesis example 3 are molten
It solves after adding potassium carbonate (0.04mol) in liquid, is warming up to 120 DEG C.It was put into through 2 hours by 4- in above-mentioned reaction solution at 120 DEG C
Butyl parabens (0.04mol) are dissolved in solution made of N-Methyl pyrrolidone (88.7g).With mutually synthermal dimension
After holding reaction in 1 hour, 4- chlorophenol (0.16mol) and potassium carbonate (0.16mol) are added, is stirred 4 hours.Later, by reaction solution
It is cooled to room temperature, is expelled in distilled water 3L.The violet precipitate so generated is filtered under diminished pressure, and is washed with methanol.
After above-mentioned filtrate is re-dissolved in methylene chloride (MC), carries out silica filtration and remove impurity, carried out again with MeOH
Crystallization, obtains the compound of chemical formula 4-7 with 68.7% yield, and confirming molecular weight is 1280.35.
Synthesis example 7: the synthesis of the compound of chemical formula 4-10
Midbody compound (0.04mol) and N-Methyl pyrrolidone (266.1g) synthesized by above-mentioned synthesis example 3 are molten
It solves after adding potassium carbonate (0.04mol) in liquid, is warming up to 120 DEG C.It was put into through 2 hours by 4- in above-mentioned reaction solution at 120 DEG C
(tert-butyl) phenol (0.04mol) is dissolved in solution made of N-Methyl pyrrolidone (88.7g).It is small with mutually synthermal maintenance 1
After Shi Fanying, 4- chlorophenol (0.16mol) and potassium carbonate (0.16mol) are added, is stirred 4 hours.Later, reaction solution is cooled to
Room temperature is expelled in distilled water 3L.The violet precipitate so generated is filtered under diminished pressure, and is washed with methanol.It will be above-mentioned
After filtrate is re-dissolved in methylene chloride (MC), carries out silica filtration and remove impurity, recrystallized with MeOH, with
56.5% yield obtains the compound of chemical formula 4-10, and confirming molecular weight is 1370.21.
Synthesis example 8: the synthesis of the compound of chemical formula 4-12
Midbody compound (0.04mol) and N-Methyl pyrrolidone (266.1g) synthesized by above-mentioned synthesis example 3 are molten
It solves after adding potassium carbonate (0.04mol) in liquid, is warming up to 120 DEG C.It was put into through 2 hours by 3- in above-mentioned reaction solution at 120 DEG C
(trifluoromethyl) phenol (0.04mol), which is dissolved in made of N-Methyl pyrrolidone (88.7g), to be dissolved.1 is maintained with mutually synthermal
After hour reaction, 4- chlorophenol (0.16mol) and potassium carbonate (0.16mol) are added, is stirred 4 hours.Later, reaction solution is cooling
To room temperature, it is expelled in distilled water 3L.The violet precipitate so generated is filtered under diminished pressure, and is washed with methanol.It will be upper
It states after filtrate is re-dissolved in methylene chloride (MC), carries out silica filtration and remove impurity, recrystallized with MeOH,
The compound of chemical formula 4-12 is obtained with 40.5% yield, confirming molecular weight is 1248.29.
Production Example: bonding agent resin
Prepare the flask for having blender, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe.As monomer
Dropping funel, by benzyl maleimide 74.8g (0.20 mole), acrylic acid 43.2g (0.30 mole), vinyltoluene
118.0g (0.50 mole), tert-butyl hydroperoxide -2 ethyl hexanoic acid ester 4g, propylene glycol monomethyl ether (PGMEA) 40g are thrown
It after entering, is stirred mixing and prepares, as chain-transferring agent dropwise adding tank, prepare that n-dodecane mercaptan 6g, PGMEA24g is added simultaneously
Substance made of being stirred.Later, PGMEA 395g is imported in flask, and the atmosphere in flask is become into nitrogen from air
Afterwards, the temperature of flask is warming up to 90 DEG C while stirring.Then, monomer and chain-transferring agent are added dropwise since dropping funel.
It carries out 2 hours, 110 DEG C are risen to after 1 hour and maintains 3 hours respectively while maintaining 90 DEG C when dropwise addition, be then introduced into gas
Ingress pipe 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 '-di-2-ethylhexylphosphine oxide (4-
Methyl-6-tert-butylphenol) 0.4g, triethylamine 0.8g put into flask, carries out reacting for 8 hours at 110 DEG C, obtain solid at
Dividing acid value is the bonding agent resin of 70mgKOH/g.Weight average molecular weight by the polystyrene conversion of GPC measurement is 16,000,
Molecular weight distribution (Mw/Mn) is 2.3.
Device: HLC-8120GPC (Tosoh (strain) manufacture)
Column: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection)
Column temperature: 40 DEG C
Mobile phase solvent: tetrahydrofuran
Flow velocity: 1.0ml/ minutes
Injection rate: 50 μ l
Detector: RI
Measure sample solution concentration: 0.6 mass % (solvent=tetrahydrofuran)
Correct standard substance: TSK standard polystyren F-40, F-4, F-1, A-2500, A-500 (Tosoh (strain) manufactures)
The ratio between weight average molecular weight obtained above and number-average molecular weight are set as molecular weight distribution (Mw/Mn).
Examples 1 to 6 and comparative example 1~3
Each self-luminous according to composition and content the manufacture Examples 1 to 6 and comparative example 1~3 that are shown in following table 1 is photosensitive
Property resin combination.
[table 1]
(unit: parts by weight)
TAP-1: synthesis example 1
TAP-2: synthesis example 2
TAP-3: compare synthesis example 1
TAP-4: compare synthesis example 2
A-1: synthesis example 4
A-2: synthesis example 5
A-3: synthesis example 6
A-4: synthesis example 7
A-5: synthesis example 8
B: the bonding agent resin of Production Example
C: dipentaerythritol hexaacrylate (Kayarad DPHA: Japanese chemical drug (strain) manufacture)
D-1:2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- ketone (Irgacure369；Vapour bar essence
Change the manufacture of (Ciba Specialty Chemical) company)
Bis- (dimethylamino) benzophenone (EAB-F of D-2:4,4 '-；Hodogaya chemical (strain) manufacture)
E: propylene glycol monomethyl ether (PGMEA)
The Production Example of color conversion layer
Color is manufactured using the self-luminous photosensitive polymer combination manufactured in above-described embodiment 1~6 and comparative example 1~3
Conversion layer.That is, being placed in and adding after above-mentioned each self-luminous photosensitive polymer combination is coated on glass substrate using spin-coating method
On hot plate, is maintained 3 minutes in 100 DEG C of temperature and form film.Then, ultraviolet light is irradiated on the above-mentioned films.At this point, ultraviolet
The extra-high-pressure mercury vapour lamp (trade name USH-250D) that linear light source uses oxtail motor (strain) to make, under air atmosphere, with 40mJ/
cm2Light exposure (365nm) carry out light irradiation, and without use special optical filter.By what is irradiated through above-mentioned ultraviolet light
After film is developed 60 seconds in the KOH aqueous development solution of pH12.5 using spray development device, in 220 DEG C of heated oven
It heats 20 minutes and manufactures pattern.The film thickness of the self-luminous colored color conversion layer pattern of above-mentioned manufacture is 3.0 μm.Color turns
The thickness for changing layer can be controlled diversely to 500 μm.
Experimental example: the measurement of luminous intensity
By the self-luminous photosensitive polymer combination for using above-described embodiment 1~6 and comparative example 1~3 manufacture with a thickness of
3.0 μm of self-luminous colored pattern is measured using quantum efficiency test device (QE-1000, big tomb corporation) for each coating base
Plate shines (Photo Luminescence, PL), and is recorded in following table 2.It may determine that, the luminous intensity measured is got over
Height has more excellent fluorescence efficiency characteristic.
[table 2]
| It distinguishes | Luminous intensity (λmax:620) |
| Embodiment 1 | 4,500 |
| Embodiment 2 | 5,500 |
| Embodiment 3 | 4,700 |
| Embodiment 4 | 5,000 |
| Embodiment 5 | 5,100 |
| Embodiment 6 | 5,700 |
| Comparative example 1 | 3,000 |
| Comparative example 2 | 10 |
| Comparative example 3 | 150 |
Referring to above-mentioned table 2 it is found that Examples 1 to 6 has higher luminous intensity values compared with comparative example 1~3, therefore make
The fluorescence efficiency and comparative example 1 of the color conversion layer manufactured with the self-luminous photosensitive polymer combination based on Examples 1 to 6
~3 compared to more excellent.
Claims (12)
1. a kind of self-luminous photosensitive polymer combination, which is characterized in that comprising dyestuff and there is aluminium (Al) or silicon (Si) to make
For the tetraazatetradecane porphyrin based compound of center metal.
2. self-luminous photosensitive polymer combination according to claim 1, which is characterized in that the tetraazatetradecane porphyrin system
Closing object is compound represented by following chemical formula 1,
Chemical formula 1
In the chemical formula 1, R26~R33It is each independently hydrogen, non-substituted phenyl, the alkyl of carbon atom number 1~8, carbon atom
The alkoxy of number 1~8, nitro, halogen atom, cyano, the alkyl amino of carbon atom number 1~8, carbon atom number 1~8 amino alkane
Base or be selected from the alkoxy of carbon atom number 1~8, the alkyl of carbon atom number 1~8, nitro, halogen atom, carbon atom number 1
The phenyl of~8 alkyl amino, more than one substituent group in the aminoalkyl and cyano of carbon atom number 1~8,
M is with the more than one ligand in ammonia, the water and halogen atom or not no Al or Si of ligand.
3. self-luminous photosensitive polymer combination according to claim 1, which is characterized in that the dyestuff is fluorescence dye
Material.
4. self-luminous photosensitive polymer combination according to claim 3, which is characterized in that the fluorescent dye is red
Fluorescent dye.
5. self-luminous photosensitive polymer combination according to claim 4, which is characterized in that the red fluorescence dyestuff is
Imidodicarbonic diamide based compound.
6. self-luminous photosensitive polymer combination according to claim 5, which is characterized in that the imidodicarbonic diamide system
Closing object is compound represented by following chemical formula 2,
Chemical formula 2
In the chemical formula 2, R1 and R2 be each independently substituted or non-substituted aryl, substituted or non-substituted heterocycle,
Or substituted or non-substituted linear or branched alkyl group,
R3, R4, R5 and R6 are each independently hydrogen atom, halogen atom, hydroxyl, substituted or non-substituted carbon atom number 1~10
Alkoxy, substituted or non-substituted phenoxy group, represented by substituted or non-substituted thio phenoxy group or following chemical formula 3
Substituent group, and R3, R4, R5 and R6 are all different,
Chemical formula 3
In the chemical formula 3, X1 and X5 are hydrogen atom,
X2, X3 and X4 are each independently hydrogen atom or halogen atom, and the above are halogens by least one of X2, X3 and X4
Atom,
Y is oxygen atom or sulphur atom.
7. self-luminous photosensitive polymer combination according to claim 5, which is characterized in that the imidodicarbonic diamide system
Closing object is compound represented by following chemical formula 4,
Chemical formula 4
In the chemical formula 4, R1 and R2 be each independently substituted or non-substituted aryl, substituted or non-substituted heterocycle,
Substituted or non-substituted straight chained alkyl or substituted or non-substituted branched alkyl,
R11, R12, R13 and R14 are each independently selected from halogen atom, the linear or branched alkyl group of carbon atom number 1~10, carbon
The halogenated alkyl of atomicity 1~10, hydroxyl, the alkoxy of carbon atom number 1~10, carbon atom number 1~10 ester group and amino in
Substituent group, and the position of the type of at least one of R11, R12, R13 and R14 and remaining substituent group or substituent group is not
Together,
Y1、Y2、Y3And Y4It is each independently oxygen (O) atom or sulphur (S) atom,
A, b, c and d are each independently 1~5 integer.
8. self-luminous photosensitive polymer combination according to claim 1, which is characterized in that the self-luminous photonasty tree
Oil/fat composition is used to form color conversion layer.
9. self-luminous photosensitive polymer combination according to claim 1, which is characterized in that the self-luminous photonasty tree
Oil/fat composition further includes bonding agent resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent.
10. self-luminous photosensitive polymer combination according to claim 9, which is characterized in that relative to the self-luminous
The total weight of the solid component of photosensitive polymer combination includes 5~85 weight % of bonding agent resin and photopolymerizable compound 5
~50 weight %,
It include Photoepolymerizationinitiater initiater relative to the total weight of the bonding agent resin and the solid component of photopolymerizable compound
0.1~40 weight %,
It include tetraazatetradecane porphyrin based compound 0.001~15 relative to the total weight of the self-luminous photosensitive polymer combination
60~90 weight % of weight %, 0.001~30 weight % of dyestuff and solvent.
11. a kind of color conversion layer, which is characterized in that by self-luminous photonasty tree according to any one of claims 1 to 10
Oil/fat composition manufacture.
12. a kind of display device, which is characterized in that include the color conversion layer described in claim 11.
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| KR20180002870 | 2018-01-09 | ||
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| JP7291620B2 (en) * | 2019-12-27 | 2023-06-15 | 大日本印刷株式会社 | Tetraazaporphyrin compound, ink composition, film, optical material, optical film, display surface film, and display device |
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| US6572977B1 (en) * | 2000-09-12 | 2003-06-03 | 3M Innovative Properties Company | Fluorescent red composition and articles made therefrom |
| JP2006127841A (en) | 2004-10-27 | 2006-05-18 | Dainippon Printing Co Ltd | Gas barrier film for electronic display medium |
| JPWO2008105235A1 (en) * | 2007-02-26 | 2010-06-03 | コニカミノルタホールディングス株式会社 | Composition, optical filter and front filter for display |
| WO2009037874A1 (en) | 2007-09-19 | 2009-03-26 | Fuji Electric Holdings Co., Ltd. | Color conversion filter, and process for producing color conversion filter and organic el display |
| US9442372B2 (en) * | 2007-09-26 | 2016-09-13 | Fujifilm Corporation | Pigment dispersion composition, photocurable composition and color filter |
| JP2011219644A (en) | 2010-04-12 | 2011-11-04 | Konica Minolta Business Technologies Inc | Colorant composition, electrophotographic toner, and color filter |
| KR101426542B1 (en) * | 2010-06-23 | 2014-08-06 | 서울대학교산학협력단 | Photosensitive resin composition, and color filter using the same |
| KR101785642B1 (en) | 2010-11-05 | 2017-10-16 | 엘지이노텍 주식회사 | color filter and display apparatus using the same |
| JP5770672B2 (en) * | 2012-03-30 | 2015-08-26 | 富士フイルム株式会社 | Colored curable composition, color filter, method for producing color filter, and display device |
| KR20130123486A (en) * | 2012-05-03 | 2013-11-13 | 삼성디스플레이 주식회사 | Photoresist composition for forming a color filter and method of manufacturing a substrate for a display device |
| CN103454859A (en) * | 2012-05-29 | 2013-12-18 | 住友化学株式会社 | Colored curable resin composition |
| JP6115281B2 (en) | 2012-06-07 | 2017-04-19 | Jsr株式会社 | Coloring composition, color filter and display element |
| KR20140076750A (en) * | 2012-12-13 | 2014-06-23 | 제일모직주식회사 | Photosensitive resin composition for color filter, and color filter using the same |
| JP6340871B2 (en) | 2014-03-31 | 2018-06-13 | 東洋インキＳｃホールディングス株式会社 | Coloring composition for color filter, and color filter |
| KR102201361B1 (en) * | 2014-09-26 | 2021-01-11 | 동우 화인켐 주식회사 | Self emission type photosensitive resin composition, and display device comprising color conversion layer prepared thereby |
| JP6741427B2 (en) | 2015-01-13 | 2020-08-19 | 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． | Self-luminous photosensitive resin composition, display device including color conversion layer produced therefrom |
| KR102204534B1 (en) * | 2015-01-13 | 2021-01-20 | 동우 화인켐 주식회사 | Self emission type photosensitive resin composition, and display device comprising color conversion layer prepared thereof |
| KR101992009B1 (en) | 2017-02-03 | 2019-06-21 | 동우 화인켐 주식회사 | Self Emission Type Photosensitive Resin Composition, Color Filter Comprising Color Conversion Layer Using the Same and Display Device |
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