CN107479327A - Manufacture method, color conversion substrate and the display device of color conversion substrate - Google Patents

Manufacture method, color conversion substrate and the display device of color conversion substrate Download PDF

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Publication number
CN107479327A
CN107479327A CN201710826724.5A CN201710826724A CN107479327A CN 107479327 A CN107479327 A CN 107479327A CN 201710826724 A CN201710826724 A CN 201710826724A CN 107479327 A CN107479327 A CN 107479327A
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China
Prior art keywords
methyl
color conversion
conversion substrate
light
filler
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CN201710826724.5A
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Chinese (zh)
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水泽龙马
高木利哉
门胁真也
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Tokyo Ohka Kogyo Co Ltd
Sharp Corp
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Tokyo Ohka Kogyo Co Ltd
Sharp Corp
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Publication of CN107479327A publication Critical patent/CN107479327A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

The present invention is provided to form the photosensitive composite, pattern and the figuratum display device of tool of the pattern with light scattering function used in a display device.Photosensitive composite for forming the pattern with light scattering function used in a display device contains TiO2Filler, optical polymerism (methyl) acrylic monomers, alkali soluble resin, Photoepolymerizationinitiater initiater and organic solvent, above-mentioned TiO2Filler is in above-mentioned TiO2In the range of shared ratio is 10~35 mass % in the total amount of filler, optical polymerism (methyl) acrylic monomers and alkali soluble resin.

Description

Manufacture method, color conversion substrate and the display device of color conversion substrate
The application is divisional application, and applying date of its parent application is on January 18th, 2013, international application no PCT/ JP2013/050883, into the Application No. 201380006593.6 of National Phase in China, entitled " photosensitive composition Thing, pattern and the figuratum display device of tool ".
Technical field
The present invention relates to the photosensitive composition for forming the pattern with light scattering function used in a display device Thing, pattern and the figuratum display device of tool.
Background technology
In the past, using white light backlight non-spontaneous light type full-color display device mainly by the backlight and optical gate Form.For example, liquid crystal display device has the light sources such as LED or cold-cathode tube, light guide plate and optical sheet as backlight, and have There is liquid crystal panel as optical gate.Above-mentioned liquid crystal panel includes two panels polarizer, a pair of substrates and the liquid crystal being enclosed between the substrate Layer, the colour filter (CF) of TFT patterns and red, green, blue (RGB) color is respectively equipped with above-mentioned a pair of substrates.But go out from light source The white light penetrated is colored device and absorbs light in addition to above-mentioned color, therefore only transmits 1/3 or so.I.e., in the above-described configuration, The utilization ratio of white light is low.
Therefore, in order to improve the utilization ratio of light, and a kind of liquid crystal display device is proposed, it uses the backlight of blue light Source, and there is liquid crystal panel, absorb blue light and send the red-emitting phosphors of red light and absorb blue light and send green The green-emitting phosphor (patent document 1,2) of light.In the above-described configuration, the light for being colored device absorption tails off, therefore makes the utilization of light Efficiency improves.And then, it is also proposed that a kind of liquid crystal display device, it in the side of fluorophor by forming reflecting layer to make along horizontal stroke The light being emitted to (direction parallel with transparency carrier) reflects and is emitted from transparency carrier, the utilization ratio of light is improved (patent Document 5).
But in above-mentioned each composition, it is emitted from the red light of red-emitting phosphors outgoing and from green-emitting phosphor green The orientation characteristic of coloured light shows lambertian distribution (light intensity distributions), on the other hand, used blue light be not through fluorophor and In fluorophor straightline propagation or reflect, therefore, the orientation characteristic of blue light does not show lambertian distribution.That is, blue light takes It is different from the orientation characteristic of red light and green light to characteristic.Therefore, in above-mentioned liquid crystal display device incline direction relative to The colourity change increase of positive direction, thus reduces display quality.
It is proposed to this end that a kind of liquid crystal display device, its by making blue light pass through the scattering layer with light scattering function, So that incline direction changes relative to the colourity of positive direction and reduced in liquid crystal display device, thus display quality is improved (patent document 3,4).
Moreover, in recent years, various researchs have been carried out to the composition for forming above-mentioned scattering layer, such as in patent document A kind of radiation sensitive compositions are proposed in 6, it contains：Carboxylic acid compound, unsaturated compound containing epoxy radicals and olefinic are not The copolymer of saturated compounds, light scattering material, polyfunctional monomer and Photoepolymerizationinitiater initiater.
Prior art literature
Patent document
Patent document 1：Japanese Laid-Open Patent Publication " JP 2000-131683 (on May 12nd, 2000 is open) "
Patent document 2：Japanese Laid-Open Patent Publication " JP 2003-5182 (on January 8th, 2003 is open) "
Patent document 3：Japanese Laid-Open Patent Publication " JP 2009-115925 (on May 28th, 2009 is open) "
Patent document 4：Japanese Laid-Open Patent Publication " JP 2009-244383 (on October 22nd, 2009 is open) "
Patent document 5：Japanese Laid-Open Patent Publication " JP 2010-66437 (on March 25th, 2010 is open) "
Patent document 6：Japanese Laid-Open Patent Publication " JP 2001-316408 (on November 13rd, 2001 is open) "
The content of the invention
The invention problem to be solved
But for the radiation sensitive compositions described in patent document 6, due to effectively scattered reflection Light, realize and (be recorded in paragraph (0006) etc.) for the purpose of the high face illumination of front face brightness, therefore do not particularly contemplate and make display Positive direction in device does not produce colourity change (color shift) with incline direction.That is, radiated in the sense described in patent document 6 In linear combination thing, the light scattering function of making the blue light from light source outgoing be scattered with extensive angle is not particularly contemplated.
In addition, in the conventional light-diffusing films formed comprising acrylic acid filler etc. for display device, through the light The width of the scattering angle of the light of scattering film is narrow and small to 10~30 degree or so.Therefore, conventional light-diffusing films, which have, can not make indigo plant The problem of coloured light is scattered with extensive angle.
In order that the positive direction (normal direction for light-emitting area) in display device does not produce with incline direction Degree of adding lustre to changes (color shift), it is necessary to make the orientation characteristic of blue light display that lambertian distribution (light intensity distributions).In addition, in order to Effectively pattern-making is, it is necessary to make the composition to form diffusion layer have photolithographic characteristics.That is, formed using photosensitive composite Pattern (scattering layer) need with the light scattering function that is scattered with extensive angle of blue light of making from light source outgoing.Therefore, in order to Display quality is improved, and is needed with the photolithographic characteristics for being suitable for display device and with making what blue light was scattered with extensive angle The photosensitive composite of light scattering characteristic, that is, need the photosensitive composition for forming the excellent pattern of above-mentioned light scattering function Thing.
The present invention in view of above-mentioned problem and complete, its main purpose is to provide for forming what is used in a display device The photosensitive composite of pattern with light scattering function.In addition, its another object, which is to provide, uses above-mentioned photosensitive composition Thing and the pattern with light scattering function and the figuratum display device of tool formed.
Means for solving the problem
In order to solve above-mentioned problem, photosensitive composite of the invention, it is characterised in that it is used to be formed with aobvious The pattern with light scattering function used in showing device, the photosensitive composite contain TiO2Filler, optical polymerism (methyl) Acrylic monomers, alkali soluble resin, Photoepolymerizationinitiater initiater and organic solvent, above-mentioned TiO2Filler is in above-mentioned TiO2Filler, light gather In the range of shared ratio is 10~35 mass % in the total amount of conjunction property (methyl) acrylic monomers and alkali soluble resin.
According to above-mentioned composition, due to TiO2Filler is scattered in optical polymerism (methyl) acrylic monomers and alkali-soluble In resin, i.e. TiO2Filler is scattered in negative photosensitive resin, therefore can obtain taking into account photolithographic characteristics and light scattering spy The photosensitive composite of property.I.e., it is possible to provide with the photolithographic characteristics for being suitable for display device and with utilizing TiO2Filler Make the photosensitive composite for the light scattering characteristic that blue light scatters with angle more wider array of than incidence angle.
In addition, in order to solve above-mentioned problem, the pattern of the present invention is set to be formed using above-mentioned photosensitive composite.Enter And in order to solve above-mentioned problem, and make the display device of the present invention that there is above-mentioned pattern.
According to above-mentioned composition, because the orientation characteristic of blue light shows lambertian distribution (light intensity distributions), therefore can be with Offer makes the display device that positive direction does not produce colourity change (color shift) with incline direction and display quality is improved.
Invention effect
According to the photosensitive composite of the present invention, following effect has been given play to：It can provide to have and be suitable for display device Photolithographic characteristics and with utilizing TiO2Filler makes the photosensitive of the light scattering characteristic that blue light scatters with angle more wider array of than incidence angle Property composition.In addition, according to the pattern of the present invention and the display device of the present invention, following effect has been given play to：Due to making blueness The orientation characteristic of light shows lambertian distribution (light intensity distributions), therefore can provide makes positive direction not produce color with incline direction The display device that degree change (color shift) and display quality are improved.
Brief description of the drawings
Fig. 1 is the block diagram for the schematic configuration of one for representing the display device of the present invention.
Fig. 2 is the block diagram for the schematic configuration of another for representing the display device of the present invention.
Fig. 3 is the sectional view of the schematic configuration of one of the major part for representing above-mentioned display device.
Fig. 4 is the sectional view for the schematic configuration of one for representing above-mentioned display device possessed color conversion substrate.
Fig. 5 is the sectional view for the schematic configuration of another for representing above-mentioned display device possessed color conversion substrate.
Fig. 6 is the sectional view of the schematic configuration for the another example for representing above-mentioned display device possessed color conversion substrate.
Relative value when Fig. 7 is so that the luminous intensity of the positive direction in display device is set into " 1 " represents the present invention's The chart of light intensity distributions shown in the pattern of embodiment 1.
Relative value when Fig. 8 is so that the luminous intensity of the positive direction in display device is set into " 1 " represents comparative example 1 The chart of light intensity distributions shown in pattern.
Fig. 9 is the figure of one of the major part for representing above-mentioned display device, wherein, (a) for representing schematic configuration is to cut open View, (b) are the front view watched from viewable side.
Figure 10 is the figure of another of the major part for representing above-mentioned display device, wherein, (a) for representing schematic configuration is Sectional view, (b) are the front view watched from viewable side.
Embodiment
Hereinafter, an embodiment of the invention is entered successively according to the order of photosensitive composite, pattern, display device Row explains.
(photosensitive composite)
The photosensitive composite of the present invention contains TiO2Filler, optical polymerism (methyl) acrylic monomers, alkali-soluble tree Fat, Photoepolymerizationinitiater initiater and organic solvent, above-mentioned TiO2Filler is in above-mentioned TiO2Filler, optical polymerism (methyl) acrylic monomers And in the range of the ratio shared by the total amount of alkali soluble resin is 10~35 mass %.Hereinafter, each composition is illustrated.
<TiO2Filler>
TiO2, therefore, should as long as filler can play the particle diameter for the light scattering function of making blue light scattering, shape Particle diameter, shape are not particularly limited, but specifically, average grain diameter be more preferably 100~1,000nm in the range of, further In the range of preferably 150~250nm.If average grain diameter is less than 100nm, it is difficult to play light scattering function sometimes.It is if average Particle diameter is then difficult to make blue light pass through pattern sometimes more than 1,000nm.
In addition, TiO2Filler is in TiO2In the total amount of filler, optical polymerism (methyl) acrylic monomers and alkali soluble resin Shared ratio be preferably 10~35 mass % in the range of, in the range of more preferably 20~30 mass %.If TiO2Filler Ratio be less than 10 mass %, then be difficult to play light scattering function.If TiO2The ratio of filler is then difficult to make more than 35 mass % Blue light passes through pattern.
<Optical polymerism (methyl) acrylic monomers>
Optical polymerism (methyl) as long as acrylic monomers intramolecular have the functional group containing ethylenically unsaturated group be third Enoyl- (- CH=CH-CO-) or methylacryloyl (- CH=C (CH3)-CO-) and can carry out (methyl) third of photopolymerization Acrylic monomer.Optical polymerism (methyl) acrylic monomers forms negative photosensitive resin together with alkali soluble resin.
Above-mentioned optical polymerism (methyl) if acrylic monomers be specially selected from simple function (methyl) acrylic monomers and At least one of polyfunctional (methyl) acrylic monomers.That is, above-mentioned optical polymerism (methyl) acrylic monomers can be with It is made up of, can also be made up of polyfunctional (methyl) acrylic monomers (methyl) acrylic monomers of simple function, can also be by The mixture of (methyl) acrylic monomers of simple function and polyfunctional (methyl) acrylic monomers is formed.
As (methyl) acrylic monomers of above-mentioned simple function, specifically, such as can enumerate：(methyl) acrylamide, Methylol (methyl) acrylamide, methoxy (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxyl group Methyl (methyl) acrylamide, butoxymethoxy methyl (methyl) acrylamide, N- methylols (methyl) acrylamide, N- hydroxyls Methyl (methyl) acrylamide, (methyl) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, lemon health Acid, citraconic anhydride, crotonic acid, 2- acrylamide-2-methyl propane sulfonics, tert-butyl acrylamide sulfonate, (methyl) acrylic acid first Ester, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) acrylate Ester, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (first Base) acrylic acid 2- phenoxy group -2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, phthalic acid 2- (first Base) acryloxy -2- hydroxy propyl esters, phthalic acid 2- (methyl) acryloyl-oxyethyl -2- hydroxy propyl esters, glycerine list (methyl) acrylate, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) dimethylaminoethyl acrylate, the contracting of (methyl) acrylic acid Water glyceride, (methyl) acrylic acid 2,2,2- trifluoro ethyl esters, the tetrafluoro propyl ester of (methyl) acrylic acid 2,2,3,3-, phthalic acid spread out (methyl) acrylate half ester of biology etc..(methyl) acrylic monomers of these simple functions can be used alone, and can also combine Using two or more.
As above-mentioned polyfunctional (methyl) acrylic monomers, specifically, such as can enumerate：Ethylene glycol two (methyl) third Olefin(e) acid ester, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylic acid Ester, polypropylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine two (methyl) acrylic acid Ester, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylic acid Double (4- (methyl) propylene of ester, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 2,2- Acyloxy diethoxy phenyl) propane, 2,2- double (4- (methyl) acryloxypolyethoxyphenyl) propane, (methyl) propylene Sour 2- hydroxyls -3- (methyl) acryloxies propyl ester, ethylene glycol diglycidyl base ether two (methyl) acrylate, diethylene glycol Diglycidyl ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, glycerine Poly- (methyl) acrylate of triacrylate, glycerine poly epihydric alcohol base ether, carbamate (methyl) acrylate (i.e. first Phenylene diisocyanate), trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate and (methyl) acrylic acid 2- hydroxyls Reactant, di-2-ethylhexylphosphine oxide (methyl) acrylamide, (methyl) acrylamide methylene ether, polyalcohol and the N- methylols of base ethyl ester The condensation product of (methyl) acrylamide, (methyl) acrylic acid adduct of bisphenol-A diglycidyl ether etc..In addition, it is used as more (methyl) acrylic monomers of function, triacryl formal (triacrylformal) can also be used.These are multifunctional (methyl) acrylic monomers may be used alone, can also be used in combination it is two or more.
In foregoing illustrative optical polymerism (methyl) acrylic monomers, more preferably phthalic acid 2- (methyl) acryloyl Epoxide ethyl -2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, (first of bisphenol-A diglycidyl ether Base) acrylic acid adduct, further preferred phthalic acid 2- methacryloxyethyl -2- hydroxy propyl esters, acrylic acid 2- The methacrylic acid addition product of hydroxyl -3- phenoxy-propyls, bisphenol-A diglycidyl ether.
<Alkali soluble resin>
As long as alkali soluble resin is soluble in the resin of alkaline aqueous solution, therefore its structure is not particularly limited, But in the range of the soluble index i.e. acid number for specifically, more preferably making resin is 50~250mgKOH/g.If alkali-soluble The acid number of resin is less than 50mgKOH/g, then is difficult to be dissolved in alkaline aqueous solution sometimes.If the acid number of alkali soluble resin exceedes 250mgKOH/g, then reduce alkali resistance sometimes.In addition, alkali soluble resin can have acryloyl group or methyl in intramolecular Acryloyl group.
As the monomer of the above-mentioned alkali soluble resin of composition, such as can enumerate：Unsaturated carboxylic acid class, esters of acrylic acid, first Base esters of acrylic acid, acrylic amide, methacryl amine, allyl compound, vinyl ethers, vinyl ester, benzene Vinyl etc..That is, alkali soluble resin is to make the polymer or copolymer that at least one of these monomers monomer is polymerized.
As above-mentioned unsaturated carboxylic acid class, specifically, such as can enumerate：Acrylic acid, methacrylic acid, crotonic acid etc. are single Carboxylic acid；The dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid；And acid anhydrides of these dicarboxylic acids etc..
As aforesaid propylene esters of gallic acid, specifically, such as can enumerate：Methyl acrylate, ethyl acrylate, acrylic acid third The tertiary monooctyl ester of ester, isopropyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, 2-ethyl hexyl acrylate, acrylic acid Deng acrylic acid straight-chain or branched-chain alkyl ester；Cyclohexyl acrylate, acrylic acid bicyclopentyl ester, acrylic acid 2- methyl cyclohexanes The acrylate ring type alkyl such as ester, acrylic acid bicyclopentyl ester, acrylic acid bicyclopentyl epoxide ethyl ester, isobornyl acrylate Ester；Acrylic acid chloroethene ester, acrylic acid 2,2- dimethyl hydroxyls propyl ester, acrylic acid 2- hydroxy methacrylates, acrylic acid 5- hydroxyls pentyl ester, three Hydroxymethyl-propane mono acrylic ester, pentaerythrite mono acrylic ester, benzyl acrylate, methoxyethyl benzyl ester, acrylic acid chaff Base ester, acrylic acid tetrahydro furfuryl ester, aryl acrylate (such as phenyl acrylate etc. can be enumerated) etc..
As above-mentioned methyl acrylic ester, specifically, such as can enumerate：Methyl methacrylate, methacrylic acid Ethyl ester, propyl methacrylate, isopropyl methacrylate, n-BMA, Isobutyl methacrylate, methyl-prop The first such as the secondary butyl ester of olefin(e) acid, Tert-butyl Methacrylate, pentylmethacrylate, hexyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester Base acrylic acid straight-chain or branched-chain alkyl ester；Cyclohexyl methacrylate, methacrylic acid bicyclopentyl ester, methacrylic acid The methacrylic acid alicyclic rings such as 2- methyl cyclohexyls, methacrylic acid bicyclopentyl epoxide ethyl ester, IBOMA Formula Arrcostab；GMA etc. contains epoxymethacrylate；2-hydroxyethyl methacrylate, methyl Acrylic acid 4- hydroxybutyls, methacrylic acid 5- hydroxyls pentyl ester, methacrylic acid 2,2- dimethyl -3- hydroxy propyl esters, three hydroxyl first Base propane monomethacrylates, pentaerythrite monomethacrylates；Methacrylic acid furfuryl group ester, methacrylic acid tetrahydrochysene chaff The methacrylates containing cyclic ether group such as base ester；Benzyl methacrylate, methacrylic acid benzyl chloride ester, phenyl methacrylate, Arylmethacrylates such as methyl methacrylate phenyl ester (cresyl methacrylate), methacrylic acid naphthalene ester etc..
As aforesaid propylene amide-type, specifically, such as can enumerate：Acrylamide, (alkyl is excellent for N- alkyl acrylamides Elect the alkyl of carbon number 1~10 as, such as methyl, ethyl, propyl group, butyl, the tert-butyl group, heptyl, octyl group, hexamethylene can be enumerated Base, hydroxyethyl, benzyl etc.), N- aryl acrylamides (as aryl, such as phenyl, tolyl, nitrobenzophenone, naphthalene can be enumerated Base, hydroxy phenyl etc.), N, N- dialkylacrylamides (alkyl is preferably the alkyl of carbon number 1~10), N, N- aryl propylene Acid amides (as aryl, such as phenyl etc. can be enumerated), N- Methyl-N-phenyls acrylamide, N- hydroxyethyl-N- methacryls Amine, N-2- acetamide ethyl-N- acetylacrylamides etc..
As above-mentioned methacryl amine, specifically, such as can enumerate：Methacrylamide, N- alkyl methyls third (alkyl is preferably the alkyl of carbon number 1~10 to acrylamide, such as can enumerate methyl, ethyl, the tert-butyl group, ethylhexyl, hydroxyl Ethyl, cyclohexyl etc.), N- aryl methacrylamides (as aryl, such as phenyl etc. can be enumerated), N, N- dialkyl methyls third Acrylamide (as alkyl, such as ethyl, propyl group, butyl etc. can be enumerated), N, N- diarylmethyls acrylamide (as aryl, Such as phenyl etc. can be enumerated), N- hydroxyethyl-N- methyl methacrylamides, N- methyl-N-phenylmethyls acrylamide, N- Ethyl-N-phenylmethyl acrylamide etc..
As above-mentioned allyl compound, specifically, such as allyl esters (such as allyl acetate, caproic acid can be enumerated Allyl ester, allyl octanoate, bay allyl propionate, palm allyl propionate, stearic allyl propionate, allyl benzoate, acetyl second Allyl propionate, allyl lactate etc.), allyloxyethanol etc..
As above-mentioned vinyl ethers, specifically, such as alkyl vinyl ether can be enumerated (such as hexyl ethene can be enumerated Base ether, octyl vinyl ether, decave, ethylhexyl vinyl ether, methoxy-ethylvinyl ether, ethoxyethyl group Vinyl ethers, chloroethyl vinyl ether, 1- methyl -2,2- dimethylpropyl vinyl ether, 2- ethylbutyl vinyl ethers, hydroxyl Ethyl vinyl ether, diethylene glycol vinyl ethers, dimethyl aminoethyl vinyl base ether, diethylamino ethyl vinyl ether, Butylaminoethyl vinyl ethers, benzyl vinyl ether, tetrahydrofurfuryl vinyl ethers etc.), ethenyl aromatic yl ether (such as can enumerate Vinyl phenyl ether, vinyltoluene base ether, vinyl chloride phenyl ether, vinyl -2,4- dichlorophenyl ether, vinyl naphthyl Ether, vinyl anthryl ether etc.) etc..
As above-mentioned vinyl ester, specifically, such as vinyl butyrate, vinyl isobutyrate ester, trimethyl can be enumerated Vinyl acetate, diethacetic acid vinyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate Ester, vinyl methoxyacetate ester, butoxy acetic acid vinyl acetate, vinyl phenylacetate ester, acetoacetate vinyl acetate, lactate Ester, beta-phenyl vinyl butyrate, vinyl benzoate, vinyl salicylate, chlorobenzoic acid vinyl acetate, tetrachloro-benzoic acid ethene Ester, naphthoic acid vinyl acetate etc..
As above-mentioned phenylethylene, specifically, such as styrene can be enumerated, ring-alkylated styrenes (such as can enumerate methyl Styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl, isopropyl styrene, butyl benzene Ethene, hexyl styrene, cyclohexylstyrenes, decyl styrene, benzylstyrene, 1-chloro-4-methyl-benzene, trifluoromethylbenzene second Alkene, ethoxyl methyl styrene, acetoxymethylstyrene etc.), alkoxystyrene (such as methoxybenzene second can be enumerated Alkene, 4- methoxyl group -3- methyl styrenes, dimethoxy styrene etc.), halogenated styrenes (such as chlorostyrene, dichloro can be enumerated Styrene, trichlorostyrene, tetrachloro styrene, pentachloro- styrene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorophenethyl The bromo- 4- trifluoromethyl styrenes of alkene, trifluorostyrene, 2-, the fluoro- 3- trifluoromethyl styrenes of 4- etc.) etc..
These monomers of composition alkali soluble resin may be used alone, can also be used in combination two or more.
In foregoing illustrative monomer, more preferably methacrylic acid, methyl methacrylate, Isobutyl methacrylate, GMA, benzyl methacrylate, further preferred methacrylic acid and methyl propenoic acid glycidyl The combination of ester and benzyl methacrylate and the group of methacrylic acid and methyl methacrylate and Isobutyl methacrylate Close.That is, alkali soluble resin is more preferably the polymer or copolymer that these monomers are polymerized.
In addition, in the range of if acid number is 50~250mgKOH/g, alkali soluble resin can make to include above-mentioned example The copolymer that the copolymerization of the monomer composition of at least one of monomer shown monomer and other monomers forms.
The manufacture method of alkali soluble resin, the polymerization of i.e. above-mentioned monomer are not particularly limited, and can be used conventional Known polymerization.In addition, the weight average molecular weight (Mw) of alkali soluble resin is not particularly limited, but more preferably 5,000 In the range of~80,000.
<Photoepolymerizationinitiater initiater>
As long as Photoepolymerizationinitiater initiater can make above-mentioned optical polymerism (methyl) acrylic monomers and alkali soluble resin (its In, there is acryloyl group or methylacryloyl for intramolecular) initiator of photopolymerization is carried out, have no special limit It is fixed, known Photoepolymerizationinitiater initiater can be used.
As above-mentioned Photoepolymerizationinitiater initiater, specifically, such as 1- hydroxycyclohexylphenylketones, 2- hydroxyls -2- can be enumerated Methyl isophthalic acid-phenyl-propane -1- ketone, 1- (4- (2- hydroxyl-oxethyls) phenyl) -2- hydroxy-2-methyl -1- propane -1- ketone, 1- (4- Isopropyl phenyl) -2- hydroxy-2-methyl propane -1- ketone, 1- (4- dodecylphenyls) -2- hydroxy-2-methyl propane -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, double (4- dimethylaminophenyls) ketone, 2- methyl isophthalic acids-(4- (methyl mercapto) Phenyl) -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butane -1- ketone, 1- [9- Ethyl -6- (2- methyl benzoyls) -9H- carbazole -3- bases] ethyl ketone -1- (O- acetyl oxime), 2,4,6- trimethylbenzoyls two Phenyl phosphine oxide, 4- benzoyls -4 '-methyl dimethoxy base thioether, 4- dimethylaminobenzoic acids, 4- dimethylaminobenzoic acids Methyl esters, EDMAB, 4- dimethylaminobenzoic acids butyl ester, 4- dimethylamino -2- ethylhexyl benzene Formic acid, 4- dimethylamino -2- isoamyl benzenes formic acid, benzyl-'beta '-methoxy ethyl acetal, benzil dimethyl ketal, 1- Phenyl -1,2- pentanedione -2- (O- ethoxy carbonyls) oxime, o-benzoyl yl benzoic acid methyl esters, 2,4- diethyl thioxanthones, 2- The chloro- 4- propoxythioxanthones of clopenthixal ketone, 2,4- dimethyl thioxanthones, 1-, thioxanthene, 2- diurils ton, 2,4- diethyl thioxanthene, 2- Methyl thioxanthene, 2- isopropylthioxanthones, 2- EAQs, prestox anthraquinone, 1,2- benzos anthraquinone, 2,3- diphenyl anthraquinone, azo Double isobutyronitriles, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2- mercaptobenzoxazoles, 2- sulfydryl benzo thiophenes Azoles, 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazoles dimer, 2- (Chloro-O-Phenyl) -4,5- bis- (methoxyphenyl) imidazoles dimerization Thing, 2- (o-fluorophenyl) -4,5- diphenyl-imidazoles dimer, 2- (o-methoxyphenyl) -4,5- diphenyl-imidazoles dimer, 2- (p-methoxyphenyl) -4,5- diphenyl-imidazoles dimer, 2,4,5- triarylimidazoles dimers, benzophenone, 2- chlorodiphenyls Ketone, 4,4 '-bis- (dimethylamino) benzophenone (i.e. Michler's keton), 4,4 '-bis- (diethylamino) benzophenone (i.e. ethyls Michler's keton), 4,4 '-dichloro benzophenone, 3,3- dimethyl -4- methoxy benzophenones, benzil, benzoin, benzoin first Base ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, the benzoin tert-butyl group Ether, acetophenone, 2,2- diethoxy acetophenones, to dimethyl acetophenone, to dimethylamino propiophenone, dichloroacetophenone, three Chloro-acetophenone, p-tert.-butyl acetophenone, to dimethylamino benzoylformaldoxime, to tert-butyl group trichloroacetophenone, to tert-butyl group dichloro-benzenes Ethyl ketone, α, α,α-dichloro-4-phenoxy acetophenone, thioxanthones, 2- methyl thioxanthones, ITX, Dibenzosuberone (dibenzosuberone), 4- dimethylaminobenzoic acids pentyl ester, 9- phenylacridines, 1,7- pairs-(9- acridinyls) heptane, 1,5- Double-(9- acridinyls) pentane, 1,3- be double-(9- acridinyls) propane, to methoxyl group triazine, 2,4,6- tri- (trichloromethyl) equal three Double (trichloromethyl) s-triazine of piperazine, 2- methyl -4,6-, double (three chloromethanes of 2- [2- (5- methylfuran -2- bases) vinyl] -4,6- Base) s-triazine, double (trichloromethyl) s-triazine of 2- [2- (furans -2- bases) vinyl] -4,6-, 2- [2- (4- diethylaminos - 2- aminomethyl phenyls) vinyl] -4,6- double (trichloromethyl) s-triazine, 2- [2- (3,4- Dimethoxyphenyl) vinyl] -4,6- Double (trichloromethyl) s-triazine, 2- (4- methoxyphenyls) -4,6- double (trichloromethyl) s-triazine, 2- (4- ethoxystyrenes Base) double (trichloromethyl) s-triazine of -4,6-, double (trichloromethyl) s-triazine of 2- (4- n-butoxyphenyls) -4,6-, 2,4- be double - Trichloromethyl -6- (the bromo- 4- methoxyl groups of 3-) phenyl s-triazine, 2,4- pairs-trichloromethyl -6- (the bromo- 4- methoxyl groups of 2-) phenyl is equal Triazine, 2,4- pairs-trichloromethyl -6- (the bromo- 4- methoxyl groups of 3-) styryl phenyl s-triazine, 2,4- pairs-trichloromethyl -6- (the bromo- 4- methoxyl groups of 2-) styryl phenyl s-triazine etc..In addition, as Photoepolymerizationinitiater initiater, can also use as commercially available " IRGACURE OXE02 ", " IRGACURE OXE01 ", " IRGACURE 369 ", " IRGACURE 651 ", " IRGACURE of product 907 " (trade names：Be BASF AG's system), " NCI-831 " (trade name：ADEKA systems) etc..
It is adjacent benzene two in foregoing illustrative Photoepolymerizationinitiater initiater, such as in above-mentioned optical polymerism (methyl) acrylic monomers Formic acid 2- (methyl) acryloyl-oxyethyl -2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, bisphenol-A two During (methyl) acrylic acid adduct of glycidyl ether, more preferably 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- morpholinoes third Alkane -1- ketone.
As long as the addition of Photoepolymerizationinitiater initiater is according to optical polymerism (methyl) acrylic monomers and alkali soluble resin (its In, there is acryloyl group or methylacryloyl for intramolecular) species, ratio set, have no especially Limit, still, relative to above-mentioned TiO2The total amount (100 of filler, optical polymerism (methyl) acrylic monomers and alkali soluble resin Quality %), in the range of more preferably 0.5~10 mass %.
<Organic solvent>
As long as organic solvent can make above-mentioned optical polymerism (methyl) acrylic monomers and alkali soluble resin with required Concentration carries out the solvent of uniform dissolution, is not particularly limited, can use known organic solvent.
As above-mentioned organic solvent, such as can enumerate：Saturated aliphatic hydrocarbon, aromatic hydrocarbon, terpene solvent, lactone, ketone, Polyalcohols, ring type ethers, esters, or ethylene glycol acetate, diethylene glycol monoacetate, Propylene glycol monoacetate, two Propylene glycol monoacetate etc. has the compound of ester bond；The monomethyl of above-mentioned polyalcohols or the above-mentioned compound with ester bond The monoalky lethers or single phenyl ether etc. such as ether, single ethylether, single propyl ether, single-butyl ether have the compound of ehter bond；Deng polyalcohol Derivative of class etc..In the derivative of above-mentioned polyalcohols, more preferably diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether (PGMEA), propylene glycol monoethyl acetic acid esters.
As above-mentioned saturated aliphatic hydrocarbon, the hydrocarbon of straight-chain, branched or ring-type can be enumerated, specifically, such as can be arranged Lift：Hydrocarbon, the carbon atom of the straight-chains such as hexane, heptane, octane, nonane, methyloctane, decane, hendecane, dodecane, tridecane The hydrocarbon of the branched of number 3~15；Hexamethylene, cycloheptane, cyclooctane, decahydronaphthalene, to terpane, adjacent terpane, a terpane, two Phenyl terpane, α-terpinenes, β-terpinenes, γ-terpinenes, Isosorbide-5-Nitrae-terpinum (terpin), 1,8- terpinums, camphane (bornane), norcamphane (norbornane), pinane (pinane), australene, nopinene, thujanes (thujane), α-thujone (thujone), the thujones of β-, carane (carane), longifolene (longifolene) isothrausmatic hydrocarbon；Etc..
As above-mentioned aromatic hydrocarbon, specifically, such as methyl phenyl ethers anisole, ethyl benzyl ether, cresyl methyl ether, two can be enumerated Phenyl ether, dibenzyl ether, phenetole, butyl phenylate etc..In addition, as aromatic hydrocarbon, thick polycycle hydrocarbon can also be used.It is thick The hydrocarbon for the condensed ring that polycycle hydrocarbon refers to the side of one respective ring of more than two monocyclic mutually supplies and formed, preferably using will The hydrocarbon that two monocyclic fusions form.As such hydrocarbon, can enumerate：The combination of five-membered ring and hexatomic ring or two hexatomic rings Combination.As the hydrocarbon for combining five-membered ring and hexatomic ring, such as indenes, pentalene, indane, tetrahydroindene can be enumerated Deng as the hydrocarbon for combining two hexatomic rings, such as naphthalene, naphthane (tetralin) and decahydronaphthalene can be enumerated (decalin) etc..
There is above-mentioned terpene solvent oxygen atom, carbonyl or acetoxyl group etc. to be used as polar group.As the terpene solvent, it is specific and Speech, for example, can enumerate geraniol (geraniol), nerol (nerol), linalool (linalool), citral (citral), Citronellol (citronellol), menthol (menthol), isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpene Product alcohol, terpinenes -1- alcohol, terpinen-4-ols, dihydro-terpineol acetic acid esters (dihydroterpinyl acetate), Isosorbide-5-Nitrae-eucalyptus Set brain (cineole), 1,8- cineoles, borneol, carvol, ionone (ionone), thujones, camphor etc..
As above-mentioned lactone, specifically, such as gamma-butyrolacton etc. can be enumerated.
As above-mentioned ketone, specifically, such as acetone, MEK, cyclohexanone, methyl-n-amyl ketone, methyl can be enumerated Isoamyl ketone, 2-HEPTANONE etc..
As above-mentioned polyalcohols, specifically, such as ethylene glycol, diethylene glycol, propane diols, DPG can be enumerated Deng.
As above-mentioned ring type ethers, specifically, such as dioxane etc. can be enumerated.
As above-mentioned esters, specifically, such as can enumerate methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, Butyl acetate, methyl pyruvate, ethyl pyruvate, methoxy methyl propionate, ethoxyl ethyl propionate etc..
These organic solvents can be used alone, and also can be combined two or more and is used as mixed solvent.
It is phthalic acid in foregoing illustrative organic solvent, such as in above-mentioned optical polymerism (methyl) acrylic monomers 2- (methyl) acryloyl-oxyethyl -2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, bisphenol-A two shrink During (methyl) acrylic acid adduct of glyceryl ether, the more preferably derivative of polyalcohols, more preferably diethylene glycol list Butyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether (PGMEA), propylene glycol monoethyl acetic acid esters.
As long as the usage amount of organic solvent according to the species of optical polymerism (methyl) acrylic monomers and alkali soluble resin, Ratio is set, and is not particularly limited, still, relative to above-mentioned TiO2Filler, optical polymerism (methyl) acrylic acid list The total amount of body and alkali soluble resin (100 mass %), in the range of more preferably 3~20 mass %.
<The manufacture method of photosensitive composite>
By above-mentioned TiO2Filler, optical polymerism (methyl) acrylic monomers, alkali soluble resin, Photoepolymerizationinitiater initiater and have Solvent is mutually mixed, and by TiO2Filler is in TiO2Filler, optical polymerism (methyl) acrylic monomers and alkali soluble resin Total amount in the range of shared proportion adjustment is 10~35 mass %, it is hereby achieved that the photosensitive composition of the present invention Thing.TiO2Filler, optical polymerism (methyl) acrylic monomers, alkali soluble resin, Photoepolymerizationinitiater initiater and organic solvent it is mixed Conjunction order is not particularly limited, but from the easy degree of mixing, more preferably adds TiO in organic solvent2Filler, light Polymerism (methyl) acrylic monomers and alkali soluble resin and mixed.In addition, as mixed method, for example, can enumerate as Lower method：By TiO2Filler, optical polymerism (methyl) acrylic monomers, alkali soluble resin, Photoepolymerizationinitiater initiater and organic molten Agent is added in container and is stirred, and after substantially mixing, is further mixed using the dispersion machines such as three-roll mill, mixer Close.But as long as it can equably mix and make TiO2The scattered method of uniform filling, is not particularly limited.
Moreover, by making TiO within the scope of the invention2The ratio and average grain diameter and optical polymerism (first of filler Base) composition of acrylic monomers and alkali soluble resin optimizes, can obtain being suitable for being formed special with light scattering of object Property pattern and with photolithographic characteristics photosensitive composite.
(pattern)
Pass through optical polymerism (methyl) acrylic monomers and alkali soluble resin for making to contain in above-mentioned photosensitive composite (wherein, there is acryloyl group or methylacryloyl for intramolecular) polymerization, i.e., by by with the upper of photolithographic characteristics State photosensitive composite to be coated on such as transparency carrier and be dried, expose and develop and form overlay film, it is possible thereby to effectively Ground forms the pattern with light scattering function of the present invention.
As the coating method of photosensitive composite, such as the method using spreader can be enumerated, as long as but can The method of uniform thickness is coated into according to the viscosity of photosensitive composite, then is not particularly limited.In addition, coating when temperature, As long as the application conditions such as humidity are appropriately configured according to composition of photosensitive composite etc..
As the drying means to the photosensitive composite after coating, such as it can enumerate and be carried out using heaters such as hot plates The method for heating (baking processing), still, as long as photosensitive composite can be integrally uniformly heated up and be made organic The method that solvent fully volatilizees, is not particularly limited.As long as in addition, the drying condition such as heating-up temperature, heat time according to The species of organic solvent, thickness of photosensitive composite etc. are appropriately configured.
As the exposure method to dried photosensitive composite, such as it can enumerate and be used using solidifications such as ultrahigh pressure mercury lamps The method that light source carries out light irradiation across mask corresponding with required pattern, still, as long as can be whole to photosensitive composite The method that body carries out uniform exposure, is not particularly limited.In addition, the conditions of exposure such as the species of light, intensity, irradiation time is only To be appropriately configured according to the thickness etc. of the species of Photoepolymerizationinitiater initiater, photosensitive composite.
As the developing method to the photosensitive composite after exposure, such as injection sodium carbonate (Na can be enumerated2CO3) water-soluble The alkaline aqueous solutions such as liquid, tetramethylammonium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium hydrate aqueous solution, which are developed, (to be sprayed Penetrate development) method, still, as long as method that the alkali soluble resin of uncured portion fully dissolves can be made, i.e. can The method for removing photosensitive composite, is not particularly limited.In addition, the species of alkaline aqueous solution, concentration, developing time etc. As long as development conditions are appropriately configured according to the thickness etc. of the species of alkali soluble resin, photosensitive composite.
By making the photosensitive composite after exposure be developed, the overlay film as solidfied material can be effectively obtained, i.e., The required pattern with light scattering function of the present invention can effectively be obtained.The pattern of the present invention can be suitable as example showing The scattering layer of showing device.Moreover, the pattern of the present invention can be formed using photoetching, therefore in the manufacture method of display device It can be aligned with the other patterns (substrate) formed before scattering layer is formed with high accuracy, therefore being capable of fine landform Into the pattern.
The thickness that the overlay film of above-mentioned pattern is formed as using the photosensitive composite of the present invention is more preferably adapted to In the range of 5~20 μm that scattering layer as the display device of the present invention uses, more preferably 5~15 μm of scope It is interior, in the range of particularly preferably 7~12 μm.By making the thickness of overlay film within the above range, it is possible thereby to take into account blue light Orientation characteristic and photolithographic characteristics.In addition, the overlay film as above-mentioned pattern more preferably has the display dress for being suitable as the present invention Following physical properties that the scattering layer put uses.That is, the haze value measured using haze meter is more preferably more than 90%, total light transmission Rate and diffusional permeability are more preferably more than 30%.In addition, the orientation of the blue light measured using beam splitting type angle colour difference meter is special Property is more preferably：Compared with the lambertian distribution (light intensity distributions) in calculating, drop into and the display quality of display device is seen It can be allowed as when examining in the fluctuation in the range of ± the 5% of commodity.Therefore, it is seen that angle is more preferably ± 80 degree.In addition, Lambertian distribution refers to：When the luminous intensity of the normal direction (θ=0) for light-emitting area is set into I0, formula " I (θ)=10 Light intensity distributions (I (θ)) shown in × COS θ ".
As described later, pattern of the invention by by red-emitting phosphors and green-emitting phosphor form together color conversion substrate and Used as the scattering layer of the display device of the present invention.Go out from the red light of red-emitting phosphors outgoing and from green-emitting phosphor The orientation characteristic for the green light penetrated shows lambertian distribution (light intensity distributions).Therefore, in order that positive direction in display device Color shift is not produced with incline direction, it is necessary to make the orientation characteristic of blue light display that lambertian distribution.The pattern of the present invention dissipates Penetrate layer have light scattering function and its be orientated characteristic and show lambertian distribution, therefore make in display device incline direction relative to just The colourity change in face direction reduces, it is possible thereby to improve the display quality of display device.
(display device)
For example, as shown in figure 1, the display device of the present invention has at least by backlight 1, optical gate 2 and the structure of color conversion substrate 3 Into display device (display part).In addition, the manufacture method of display device (display part) and the manufacture method of display device can be with Using known manufacture method, it is not particularly limited.
Backlight 1 is so-called sidelight (edge light) type, and it is by the light with blue led or blue cold-cathode tube etc. Source 11 and light guide plate 12 are formed.Light guide plate 12 has following function：Light guide plate 12 is incided in the blue light being emitted from light source 11 End face when, export the blue light and from the side surface of optical gate 2 be emitted.It is provided with for example in the side surface of optical gate 2 of the light guide plate 12 Optical sheet (not shown) with prism shape.Thus the light guide plate 12 is allow to be emitted the high parallel blue light of directive property.
In addition, for example, as shown in Fig. 2 the display device of the present invention can have backlight 1 to include multiple light sources 11 The display device of so-called " full run-down type " backlight.In the display device, multiple light sources 11 are carried out in a manner of opposed with optical gate 2 Configuration, therefore more preferably there is the high blue led of directive property.
Above-mentioned optical gate 2 is for example by liquid crystal panel or transmission-type MEMS (MEMSs；Micro Electro Mechanical System) form, it has following function：When the blue light being emitted from backlight 1 incides optical gate 2, control The transmitance of the blue light, and it is emitted to the side of color conversion substrate 3, i.e. viewable side.
Above-mentioned optical gate 2 is further described for the situation of liquid crystal panel.As shown in Fig. 3 and Fig. 9 (a), as optical gate 2 Liquid crystal panel by stacked gradually from the side of backlight 1 light source side polarizer 21, light source side substrate 22, liquid crystal layer 23, Side base plate 24 and viewable side polarizer 25 and form.Moreover, the liquid crystal panel passes through being sealing into above-mentioned a pair of substrates 22,24 Liquid crystal layer 23 apply voltage and the transmitance for the blue light for inciding liquid crystal panel can arbitrarily be controlled.
As shown in figure 3, above-mentioned color conversion substrate 3 at least possesses：Transparency carrier 31；Make via the incident blue light of optical gate 2 Carry out the fluorophor 32,33 of wavelength conversion；And make the scattering layer 34 scattered via the incident blue light of optical gate 2.I.e., originally The display device of invention using outgoing blue light light source 11 and blue light is transformed to red light and green using fluorophor 32,33 Coloured light uses, and the blue light from light source 11 is used directly in the form of blue light simultaneously.Referring to Fig. 4~6 pair The specific composition of color conversion substrate 3 is further illustrated.In addition, for convenience of description, the discoloration in paper shown in Fig. 4~6 Change the opposite up and down of the color conversion substrate 3 shown in upper and lower and Fig. 3 of substrate 3.
As shown in figure 4, color conversion substrate 3 possesses：Visible region it is substantially transparent such as the material shape as glass Into transparency carrier 31；It will go out via the incident blue light progress wavelength conversion of optical gate 2 into red light and to the side of transparency carrier 31 The red-emitting phosphors 32 penetrated；Wavelength conversion will be carried out via the incident blue light of optical gate 2 into green light and to the side of transparency carrier 31 The green-emitting phosphor 33 of outgoing；And make via the incident blue light scattering of optical gate 2 and the scattering being emitted to the side of transparency carrier 31 Layer 34.Above-mentioned red-emitting phosphors 32, green-emitting phosphor 33 and scattering layer 34 are regularly arranged relative to transparency carrier 31, The pattern for forming pixel is consequently formed, and it can be made to be shown as display device.
More specifically, it is shown in the front view i.e. Fig. 9 (b) such as watched from viewable side, red-emitting phosphors 32, green is glimmering Body of light 33 and scattering layer 34, successively with latticed array, are consequently formed the pattern for forming pixel relative to transparency carrier 31.Form Each red-emitting phosphors 32 of one pixel, the size of green-emitting phosphor 33 and scattering layer 34 and shape are not particularly limited, but It is that the rectangle of usually 90~360 μm or so of 30~120 μ m (in Fig. 9 (a), is watched from the viewable side being depicted with arrows Size and shape).
As long as the fluorescent material for forming above-mentioned red-emitting phosphors 32 and green-emitting phosphor 33 considers the fluorophor 32,33 Thickness (thickness), excited fluophor material blue light absorptivity, the red light or green light that are emitted from fluorophor 32,33 The various conditions such as transmitance and from various fluorophor such as organic fluorescent material, inorganic phosphor material, nano fluorophor materials Carry out suitably selecting in material.Fluorescent material receives blue light and is excited, produce as exciting light red light or Green light, and be emitted to the side of transparency carrier 31.As organic fluorescent material, such as can enumerate：Rhodamine B (rhodamine The red fluorescence pigment of rhodamine system pigment etc. such as B)；The green fluorescence pigment of the coumarin series pigments such as coumarin 6 etc..As nothing Machine fluorescent material, such as CdSe, ZnS etc. can be enumerated.As nano fluorophor material, such as it can enumerate and make by CdSe or ZnS Nano-particle Deng formation is uniformly spread to such as silicone-based resin, epoxy system resin, (methyl) acrylic resin in fact The material formed in the adhesive formed in matter by transparent resin.
Above-mentioned scattering layer 34 is the pattern of the present invention, and its above-mentioned light contained in photosensitive composite by making the present invention gathers The membranaceous solidfied material (overlay film) that the solidifications such as conjunction property (methyl) acrylic monomers form is formed.Scattering layer 34 preferably has and red The substantially identical orientation characteristic of the orientation characteristic of fluorophor 32 and green-emitting phosphor 33.It is in addition, " substantially identical in the present invention Orientation characteristic " refers to that the display quality of display device can be allowed as the orientation characteristic of the state of commodity.
It is in addition, (uneven with transparency carrier 31 in the side of above-mentioned red-emitting phosphors 32, green-emitting phosphor 33 and scattering layer 34 Capable face) portion forms reflecting layer 35 as needed.Reflecting layer 35 has such as direction horizontal stroke side for making not to be emitted from transparency carrier 31 To the light reflection in (direction parallel with transparency carrier 31) etc. and the function being emitted from transparency carrier 31.It is possible thereby to further carry The utilization ratio of bloom.
And then between above-mentioned red-emitting phosphors 32, green-emitting phosphor 33 and scattering layer 34 (between on transparency carrier 31 Gap) black matrix" (not shown) can be formed as needed.Red-emitting phosphors 32, green-emitting phosphor are filled using black matrix" Between 33 and scattering layer 34, the crosstalk (crosstalk) of the light of outgoing thus it can be prevented that.It is in addition it is also possible to black instead of being formed Colour moment battle array and the reflecting layer 35 of red-emitting phosphors 32, green-emitting phosphor 33 and scattering layer 34 is will be formed in as shown in Fig. 9 (a) It is connected with each other to prevent crosstalk.
In addition, for the shape of above-mentioned red-emitting phosphors 32, green-emitting phosphor 33 and scattering layer 34, when in its side When portion is formed with reflecting layer 35, preferably makes and the section of incident blue parallel light is the trapezoidal shape opened up to the side of transparency carrier 31 Shape, but when not forming reflecting layer 35 in its side surface part, the section is not limited to trapezoidal shape, or for example rectangular The shape of shape.
Pattern of the invention, the i.e. scattering layer 34 formed using the photosensitive composite of the present invention has light scattering work( Energy.That is, the display device in the present invention has above-mentioned pattern.Above-mentioned red-emitting phosphors 32, green-emitting phosphor 33 and scattering layer 34 Thickness, i.e. the thickness of pattern be not particularly limited, but in the range of more preferably 3~20 μm, more preferably 5~10 μm In the range of.When thickness is less than 3 μm, scattering layer 34 is set not have sufficient light scattering function sometimes.In thickness more than 20 μm When, make color conversion substrate 3 thickening sometimes.
According to above-mentioned composition, can provide make positive direction and incline direction do not produce colourity change (color shift) and The display device that display quality is improved.
As shown in figure 5, color conversion substrate 3 can be in transparency carrier 31, red-emitting phosphors 32, green-emitting phosphor 33 and scattering Further there is low-index layer 36 between layer 34.Above-mentioned low-index layer 36 has following function：It can make from red fluorescence In the light that body 32, green-emitting phosphor 33 and scattering layer 34 are emitted for example towards transverse direction (direction parallel with transparency carrier 31) Deng light (light being emitted with less angle) reflection and return to the side of reflecting layer 35, it is reflected again, and from transparency carrier 31 outgoing.It is possible thereby to further improve the utilization ratio of light.
As shown in fig. 6, color conversion substrate 3 can further have colour filter between transparency carrier 31 and low-index layer 36 Device 37.Above-mentioned colour filter 37 includes red filter 37a, green filter 37b, blue filter 37c and black matrix" 37d.It is above-mentioned red Color filter 37a, green filter 37b and blue filter 37c are individually configured in from red-emitting phosphors 32, green-emitting phosphor 33 and dissipated The incident position of the light of the outgoing of layer 34 is penetrated, the excitation of incident light is improved and is emitted to the side of transparency carrier 31.In addition, Red filter 37a and green filter 37b also has following function：Contained by will be from the incident exterior light in the side of transparency carrier 31 Blue light remove, thus suppress the generation of red-emitting phosphors 32 and the unwanted exciting light in green-emitting phosphor 33.Blueness Filter 37c also has following function：By will be contained in addition to blue light from the incident exterior light in the side of transparency carrier 31 Light removes, and thus suppresses the scattering of the light in scattering layer 34.Black matrix" 37d in advance with fill red filter 37a, green filter Mode between device 37b and blue filter 37c is formed, to prevent from red-emitting phosphors 32, green-emitting phosphor 33 and scattering layer 34 The crosstalk of the light of outgoing.Thus, it is possible to further improve display quality.
And then as shown in Figure 10 (a), (b), color conversion substrate 3 can be with glimmering to fill red-emitting phosphors 32, green The composition for the black matrix" 37d that mode between body of light 33 and scattering layer 34 is formed.In this composition, red-emitting phosphors 32, The side surface part of green-emitting phosphor 33 and scattering layer 34 does not form reflecting layer 35, makes with the section of the blue parallel light of incidence in rectangular Shape shape.Above-mentioned black matrix" 37d can be prevented from the light of red-emitting phosphors 32, green-emitting phosphor 33 and scattering layer 34 outgoing Crosstalk.It is possible thereby to further improve display quality.
Embodiment
Hereinafter, based on embodiment, the present invention will be described in more detail, but the present invention not shall be limited only to the extent following implementation The composition of example.
(embodiment 1)
By TiO2Filler (average grain diameter 200nm), as optical polymerism (methyl) acrylic monomers acrylic acid 2- hydroxyls- 3- phenoxy-propyls, benzyl methacrylate (BZMA)/methacrylic acid (MAA)/metering system as alkali soluble resin Acid glycidyl ester (GMA) copolymer, 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- morpholinoes as Photoepolymerizationinitiater initiater Propane -1- ketone and diethylene glycol monobutyl ether/propylene glycol monomethyl ether mixed solvent as organic solvent, with Weight ratio reaches 30: 40 successively：30: 3: 100 mode is added in container and is stirred, and after substantially mixing, uses three rollers Grinding machine is further mixed.Thus producing dispersed has TiO2The photosensitive composite of filler.
Above-mentioned BZMA/MAA/GMA copolymers use is by BZMA, MAA and GMA with weight ratio 75: 16.8: 8.2 (due to GMA For MAA glycidyl compound, therefore BZMA and MAA weight ratio is 75: 25) is copolymerized the copolymer formed.BZMA/ The weight average molecular weight (Mw) of MAA/GMA copolymers is 10,000, acid number 131mgKOH/g.In addition, diethylene glycol monobutyl ether/ Propylene glycol monomethyl ether mixed solvent using by diethylene glycol monobutyl ether and propylene glycol monomethyl ether to weigh Measure 1: 1 mixed solvent mixed of ratio.
23 DEG C of temperature, humidity 40% application conditions under, the photosensitive composite of gained is coated on using spreader On the glass substrate formed by soda-lime glass.Then, the photosensitive composite after coating is heated 3 points on hot plate with 110 DEG C Clock (carries out baking processing), above-mentioned mixed solvent is volatilized.Thus the coated film that thickness is 8 μm is obtained.
Afterwards, using ultrahigh pressure mercury lamp, (Bai Dong (strain) makes；MAT-2500), in above-mentioned coated film between with 30 μm 3,000mJ/cm is carried out every the chrome mask that width is formed2Light irradiation, so as to be exposed.After exposure, in above-mentioned coated film On with 30 DEG C injection 30 seconds concentration 0.5% Na2CO3The aqueous solution, developed (spray developing), thus by uncured portion Coated film removes.Thus it is 8 μm of pattern to obtain the overlay film as solidfied material, the i.e. thickness with light scattering function.
The result confirmed to the width (interval width) of gained pattern is 35.9 μm, and pattern repeats are good.Thus Judge to utilize and be lithographically formed the pattern with light scattering function.
Physical property, i.e. evaluation result possessed by above-mentioned pattern is as described below.That is, using haze meter (the electric color of Japan Industrial (strain) system；NDH2000 the haze value) measured is 91.4%, total light transmittance 33.3%, diffusional permeability 30.4%. In addition, using beam splitting type angle colour difference meter, (Japan's electric color industrial (strain) makes；GC5000 the orientation characteristic of the blue light) measured is such as It is consistent with lambertian distribution (light intensity distributions) essence in calculating as shown in Figure 7.Visibility angle is ± 80 degree.In addition, Fig. 7 is Following chart：Transverse axis is set to light angle (degree), the longitudinal axis is set to luminous intensity (being recorded as intensity (a.u.)), and that will show When the luminous intensity of positive direction (normal direction, light angle=0 degree for light-emitting area) in showing device is set to " 1 " Relative value represent the light intensity distributions shown in pattern.
Therefore judge：The pattern formed using the photosensitive composite of the present invention can reduce inclination side in display device To the colourity change relative to positive direction, it is possible thereby to improve the display quality of display device.
The evaluation result of the composition of photosensitive composite and pattern is concluded and is shown in Table 1.In addition, in table 1, by pattern Reappearance is that good situation is recorded as "○", and pattern repeats are recorded as the situation of bad (or coated film is uncured) “×”.In addition, the orientation characteristic of pattern is substantially shown that the situation of lambertian distribution is recorded as "○", by the orientation characteristic of pattern Do not show that the situation of lambertian distribution is recorded as "×", the situation unconfirmed to orientation characteristic is recorded as "-".
(embodiment 2)
Make TiO2Filler, acrylic acid 2- hydroxyl -3- phenoxy-propyls, BZMA/MAA/GMA copolymers, 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- morpholinoes propane -1- ketone and diethylene glycol monobutyl ether/propylene glycol monomethyl ether mixing is molten The weight ratio of agent reaches 10: 50: 40: 3: 100 successively, in addition, operate with the operation identical of embodiment 1, thus Photosensitive composite and pattern are manufactured.The evaluation result of the composition of the photosensitive composite of gained and pattern is concluded and is shown in table In 1.
(embodiment 3)
As optical polymerism (methyl) acrylic monomers, the methacrylic acid addition of bisphenol-A diglycidyl ether is used Thing replaces acrylic acid 2- hydroxyl -3- phenoxy-propyls, in addition, operate with the operation identical of embodiment 1, thus Photosensitive composite and pattern are manufactured.The evaluation result of the composition of the photosensitive composite of gained and pattern is concluded and is shown in table In 1.
(embodiment 4)
As alkali soluble resin, methyl methacrylate (MMA)/Isobutyl methacrylate (IBMA)/methyl is used Acrylic acid (MAA) copolymer replaces BZMA/MAA/GMA copolymers, in addition, carries out the operation identical with embodiment 1 Operation, has thus manufactured photosensitive composite and pattern.Above-mentioned MMA/IBMA/MAA copolymers use by MMA, IBMA and MAA with Weight is copolymerized the copolymer formed than 50: 25: 25.The weight average molecular weight (Mw) of MMA/IBMA/MAA copolymers is 14,900, acid It is worth for 171mgKOH/g.The evaluation result of the composition of the photosensitive composite of gained and pattern is concluded and is shown in Table 1.
(embodiment 5)
As optical polymerism (methyl) acrylic monomers, acrylic acid 2- hydroxyl -3- phenoxy-propyls and bisphenol-A two are shunk The methacrylic acid addition product of glyceryl ether is used in mixed way with weight than 1: 1, in addition, carries out the operation phase with embodiment 1 Same operation, has thus manufactured photosensitive composite and pattern.By the evaluation of the composition of the photosensitive composite of gained and pattern As a result conclude and be shown in Table 1.
(embodiment 6)
Make TiO2Filler, acrylic acid 2- hydroxyl -3- phenoxy-propyls, BZMA/MAA/GMA copolymers, 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- morpholinoes propane -1- ketone and diethylene glycol monobutyl ether/propylene glycol monomethyl ether mixing is molten The weight ratio of agent reaches 35: 40: 25: 3: 100 successively, in addition, operate with the operation identical of embodiment 1, thus Photosensitive composite and pattern are manufactured.The evaluation result of the composition of the photosensitive composite of gained and pattern is concluded and is shown in table In 1.
(comparative example 1)
Instead of TiO2Filler and use acrylic acid filler (ponding finished industrial (strain) made；SSX-102, the μ of average grain diameter 2 M), in addition, carry out operating with the operation identical of embodiment 1, thus manufactured the photosensitive composite and ratio compared Compared with pattern.Wherein, the thickness of coated film is set to 20 μm, and luminous intensity during exposure is set to 6,000mJ/cm2.It is above-mentioned relatively to use Pattern thickness be 20 μm.
The result confirmed to the width (interval width) of gained pattern is 40.9 μm, and pattern repeats are good.But The orientation characteristic of the blue light measured similarly to Example 1 as shown in Figure 8 not with the lambertian distribution (light intensity in calculating Degree distribution) it is completely the same.Narrow and small to ± 30 degree of visibility angle.By the photosensitive composite of the comparison of gained and the figure compared The evaluation result of case is concluded and is shown in Table 1.
For the pattern of comparison for comparative example 1, due to TiO is not used2Filler, thus while photoetching can be utilized Pattern is formed, but the pattern does not have sufficient light scattering function.That is, the transmitance in 0 degree direction is high, still -80~-5 degree And 5~80 degree of directions are low relative to the ratio between the transmitance in 0 degree of direction, therefore do not have sufficient light scattering function.
(comparative example 2)
Make TiO2Filler, acrylic acid 2- hydroxyl -3- phenoxy-propyls, BZMA/MAA/GMA copolymers, 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- morpholinoes propane -1- ketone and diethylene glycol monobutyl ether/propylene glycol monomethyl ether mixing is molten The weight ratio of agent reaches 40: 30: 30: 3: 100 successively, in addition, operate with the operation identical of embodiment 1, thus The photosensitive composite compared and the pattern compared are manufactured.By the photosensitive composite of the comparison of gained and compare use Pattern evaluation result conclude be shown in Table 1.
For the pattern of comparison for comparative example 2, due to TiO2The ratio of filler makes exposure more than 35 mass % When light do not reach the inside of coated film, thus while surface portion solidifies, but internal and uncured.Therefore, lead Cause that pattern can not be formed even the coated film of pattern forming portion is also removed in development.
【Table 1】
In addition, the present invention is not limited to above-mentioned embodiment, can be carried out in the scope shown in claim each Kind change, by the technological means disclosed in embodiment it is appropriately combined obtained by embodiment be also contained in the present invention technology model In enclosing.
Industrial applicability
Photosensitive composite, pattern and the figuratum display device of tool of the present invention can be suitable for manufacture and possess this The various electronic products of display device.
Symbol description
1 backlight
2 optical gates
3 color conversion substrates
11 light sources
12 light guide plates
21 light source side polarizers
22 light source side substrates
23 liquid crystal layers
24 viewable side substrates
25 viewable side polarizers
31 transparency carriers
32 red-emitting phosphors
33 green-emitting phosphors
34 scattering layers
35 reflecting layer
36 low-index layers
37 colour filters

Claims (13)

1. a kind of manufacture method of color conversion substrate, it is characterised in that the color conversion substrate has：
Transparency carrier with interarea,
The multiple fluorophor and at least one scattering layer of the interarea are formulated in,
The manufacture method includes：
TiO will be included2The photosensitive composite coating of filler, optical polymerism acrylic monomers, alkali soluble resin and organic solvent In the process of the interarea；
Light irradiation is carried out to the photosensitive composite across mask, the process for solidifying photosensitive composite；With
The process for removing the uncured part of the photosensitive composite and forming the scattering layer,
TiO2Filler is in the TiO2Filler, the optical polymerism acrylic monomers, the alkali soluble resin total amount in it is shared Ratio be more than 10 mass % and below 35 mass %.
2. the manufacture method of color conversion substrate according to claim 1, wherein, the TiO2The average grain diameter of filler is More than 150nm and below 250nm.
3. the manufacture method of color conversion substrate according to claim 1 or 2, wherein, optical polymerism (methyl) propylene Acid monomers are at least one of (methyl) acrylic monomers selected from simple function and polyfunctional (methyl) acrylic monomers (first Base) acrylic monomers.
4. the manufacture method of color conversion substrate according to claim 1 or 2, wherein, the acid number of the alkali soluble resin In the range of 50~250mgKOH/g.
5. the manufacture method of color conversion substrate according to claim 1 or 2, wherein, the thickness of scattering layer is 3~20nm.
6. a kind of color conversion substrate, it is characterised in that have：
Transparency carrier with interarea,
The multiple fluorophor and at least one scattering layer of the interarea are formulated in,
Wherein,
The multiple fluorophor and the scattering layer are each spaced apart by and are formed,
The scattering layer includes TiO2Filler and alkali soluble resin,
The haze value more than 90% of the scattering layer, and total light transmittance is more than 30%.
7. color conversion substrate according to claim 6, wherein, the TiO2The average grain diameter of filler be more than 150nm and Below 250nm.
8. the color conversion substrate according to claim 6 or 7, wherein, optical polymerism (methyl) acrylic monomers is choosing From (methyl) acrylic monomers of simple function and (methyl) propylene of at least one of polyfunctional (methyl) acrylic monomers Acid monomers.
9. the color conversion substrate according to claim 6 or 7, wherein, the acid number of the alkali soluble resin for 50~ In the range of 250mgKOH/g.
10. the color conversion substrate according to claim 6 or 7, wherein, scattering layer thickness is 3~20nm.
11. the color conversion substrate according to claim 6 or 7, wherein, in the transparency carrier and the fluorophor or described Formed with low-index layer between scattering layer.
12. the color conversion substrate according to claim 6 or 7, wherein, the scattering layer is and the multiple fluorophor essence Identical is orientated characteristic.
13. a kind of display device, it possesses：Possesses the color conversion substrate described in blue led, claim 6 or 7.
CN201710826724.5A 2012-01-26 2013-01-18 Manufacture method, color conversion substrate and the display device of color conversion substrate Pending CN107479327A (en)

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