CN105467758A - Self emission type photosensitive resin composition and display device comprising color conversion layer prepared thereby - Google Patents

Abstract

The invention provides a self emission type photosensitive resin composition and a display device comprising a color conversion layer prepared thereby; more specifically, the self emission type photosensitive resin composition comprises fluorochrome, antioxidant, alkaline soluble resin, light polymerism compound, photopolymerization initiator and solvent; the display device comprises the color conversion layer prepared by the self emission type photosensitive resin composition; the color conversion layer can eliminate the low lighting efficiency caused by existing color filter, can solve the low lighting efficiency and changing yellow problems caused by the light initiator, and can keep a high brightness and excellent color conversion features and high lighting efficiency when being arranged in the display device, thus realizing high quality and clear images

Description

Autoluminescence photosensitive polymer combination and comprise and utilize it and the display device of color conversion layer that produces

Technical field

The present invention relates to and a kind ofly can guarantee excellent color transfer characteristics and higher fluorescence efficiency, thus realize the autoluminescence photosensitive polymer combination of the image quality of high-quality and comprise and utilize it and the display device (Selfemissiontypephotosensitiveresincomposition, anddisplaydevicecomprisingcolorconversionlayerpreparedth ereby) of color conversion layer that produces.

Background technology

In recent years, in display industry, as from CRT (Cathode-raytube: cathode-ray tube (CRT)) to PDP, the replaced flat-panel monitor such as (plasmadisplaypanel: plasma display panel), OLED (organiclight-emittingdiode: Organic Light Emitting Diode), LCD (liquid-crystaldisplay: liquid crystal display) achieves change sharply.Wherein, LCD is widely used as the image display device in nearly all industry, and its range of application is at continuous enlargement.

The transmitance of LCD is conditioned through while liquid crystal cells at the white light sent from back light unit, and the three kinds of primary colours sent through the color filter of red (Red), green (Green), blue (Blue) are mixed and realize panchromatic.

Although as back light unit light source and use CCFL (ColdCathodeFluorescentLamp: cold-cathode fluorescence lamp), need in this case often to apply power supply to the CCFL of back light unit, therefore can produce the problem of consumes power.In addition, the colorrendering quality also indicating about 70% level compared with existing CRT, the shortcoming of problem of environmental pollution caused because adding mercury.

As the substitute for eliminating the problems referred to above point, implement the research of the back light unit that make use of LED (LightEmittingDiode: light emitting diode) is comparatively active at present.When LED is used as back light unit, exceed 100% as NTSC (NationalTelevisionSystemCommittee: National Television System Committee (NTSC)) color reproduction scope specification, thus distincter image quality can be provided to consumer.

At this, in same industrial community, in order to promote the efficiency of back light and propose the mode of the change of the material and structure etc. by color filter and LCD.

Although be coated with the dispersive composition comprising pigment or dyestuff on color filter after, defined the pixel of shades of colour by pattern formation process, such pigment and dyestuff can cause the problem reduced through efficiency making back light.The described reduction through efficiency finally can make the colorrendering quality of display device reduce, and result is difficult to the picture realizing high-quality.

The problem that colorrendering quality is lower can be eliminated by the increase of the luminescence efficiency of color filter, propose therefrom and make the thickness of color filter increase on this basis, or carry out on this basis stacked or close to and import the mode of color conversion layer (or light conversion layer).

Fig. 1 is the mode chart of the effect of the color conversion layer represented in display device, and as shown in Figure 1, the light source produced by backlight (1) can make luminescence efficiency directly increase by color conversion layer (3) and color filter (5).

So far as color conversion layer composition and using dyestuff or pigment, but being only difficult to realize luminescence efficiency by these dyestuffs and pigment promotes, and can cause the problem that brightness reduces on the contrary.Therefore, the material using fluorescent material as color conversion layer (3) is proposed.

The blue green light that fluorescent material reason backlight (1) sends is excited and the wavelength of described blue green light is changed, and then to frontal injection light, namely injection sends red white light or sends the white lights such as green white light, thus finally makes luminescence efficiency promote.

Patent about the color conversion layer with fluorescent material is applied mostly, wherein, Korean Patent discloses in No. 2012-0048218 and relate to a kind of display device with the light converter section on the top being configured between back light unit and substrate or be configured in shield portion, and described smooth converter section has the fluorescent material incident light of blue-green or ultraviolet wavelength band domain being converted at least one in the light of predetermined wavelength band domain.

Korean Patent discloses in No. 2013-0083807 and proposes a kind of liquid crystal indicator, it possesses back light unit, this back light unit can improving luminous efficiency, now, propose and in order to improving luminous efficiency, the color conversion material as fluorophor, quantum dot (QuantumDot), white scatterer (whitescatteredmatter), electroluminescence (Electroluminescence) material and photoluminescence (Photoluminesence) material is imported.

The brightness in order to promote white light-emitting diode (LED) is proposed and the method for being carried out by the color conversion layer be made up of green-emitting phosphor body importing in No. 2013-077825th, Japanese Patent Publication.

Although these patents comprise the color conversion layer of fluorophor etc. by importing and achieve the quality promoting display device, but now directly do not mention the formation method of color conversion layer, even if or mention the mode that it is also proposed and carry out in a solvent carrying out wet after single dispersing (monodisperse).

Although color conversion layer as shown in Figure 1, the pattern in red (R) and green (G) pixel portion of corresponding color filter respectively can be formed, but the fluorophor now for hundreds of micron-scales of color conversion layer cannot be dissolved in solvent, and exist with the state of dispersion, thus be difficult to realize fine pattern, and adjustment such as the physical property of thickness etc. is not easily implemented.

Such difficulty can realize fine pattern to remove by employing the photolithographicallpatterned of photosensitive polymer combination.

Although when common photosensitive polymer combination, light trigger must be used to be polymerized, but the free radical be not only generated by described light trigger can make the fluorescence efficiency of fluorophor reduce, but also in the post bake can implemented in photo-mask process (post-bake) operation, cause the problem making color conversion layer flavescence etc. new by light trigger.

At first technical literature

Patent documentation

Patent documentation 1: Korean Patent discloses No. 2012-0048218

Patent documentation 2: Korean Patent discloses No. 2013-0083807

Patent documentation 3: No. 2013-077825th, Japanese Patent Publication

Summary of the invention

Invent technical task to be solved

At this, many-sided research has been carried out in order to solve the problem of optical efficiency reduction and the flavescence caused because of the use of above-mentioned specific Photoepolymerizationinitiater initiater, its result is, the applicant confirms when being used as fluorescent dye and the antioxidant of dyestuff with certain content, can not impact brightness and can solve the problem a little, complete the present invention therefrom.

Thus, the object of the present invention is to provide and a kind ofly can guarantee excellent color transfer characteristics and the autoluminescence photosensitive polymer combination of higher fluorescence efficiency.

In addition, another object of the present invention is, provides a kind of and has the display device that the color conversion layer comprising described autoluminescence photosensitive polymer combination also can realize the image quality clearly of high-quality.

For solving the method for problem

In order to reach above-mentioned purpose, the invention is characterized in, comprising fluorescent dye, antioxidant, alkali soluble resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent as the composition for the formation of color conversion layer.

In addition, the feature of display device of the present invention is, comprises the color conversion layer produced by described autoluminescence photosensitive polymer combination.

Invention effect

Autoluminescence photosensitive polymer combination involved in the present invention can eliminate the luminescence efficiency reduction caused because of color filter and the luminescence efficiency caused because of light trigger reduces and the problem of flavescence.

The display device having imported the color conversion layer produced by described autoluminescence photosensitive polymer combination can maintain higher brightness, and excellent color transfer characteristics and higher luminescence efficiency can be guaranteed, and then the image quality clearly of high-quality can be realized.

Accompanying drawing explanation

Fig. 1 is the mode chart of the effect of the color conversion layer represented in display device.

Embodiment

The present invention proposes the autoluminescence photosensitive polymer combination of the color conversion layer that can be used for display device.

Color conversion layer is disposed adjacent with described color filter (with reference to Fig. 1), improve to make the luminescence efficiency causing because of the use of color filter reducing, and be made up of fine pattern in the mode of the redness of corresponding color filter (R), green (G) pattern, now, described fine pattern utilizes photosensitive polymer combination and is formed.

Especially the composition as color conversion layer is proposed in the present invention and the photosensitive polymer combination of the fluorescent dye comprised as neccessary composition and antioxidant, thus guarantee following effect, namely, luminescence efficiency on the whole can be made to promote by the fluorescence efficiency of the spontaneous emission of described fluorescent dye, and photosensitive polymer combination can form fine pattern, and antioxidant prevents the fluorescence efficiency reduction of photosensitive polymer combination because of light trigger and the effect of flavescence phenomenon.

With described fluorescent dye and antioxidant in the lump, autoluminescence photosensitive polymer combination involved in the present invention also comprises alkali soluble resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent.

Below each composition is described.

Fluorescent dye for color conversion layer can make the light of the particular wavelength region had in the incident light of presetted wavelength scope be converted to visible light, as long as and have in material the present invention of fluorescent characteristic and be not construed as limiting, all can use.

Be preferably, spendable fluorescent dye uses the one be selected from Coumarins, naphthalimide, quinacridine ketone, flower cyanines class, xanthine, pyridines, low molecule luminescent material, high-molecular luminous material and their combination.

Specifically, described fluorescent dye can use the Fluorescent Brightening agents based on Coumarin being selected from and comprising 3-(2-[4-morpholinodithio base)-7-diethyl amino coumarin (coumarin 6), 3-(2-benzimidazolyl)-7-diethyl amino coumarin (cumarin 7) and coumarin 1 35 etc.; Comprise the naphthalimide fluorescent dyestuff of solvent yellow (SolventYellow) 43, solvent yellow 44 etc.; The quinacridone fluorochrome of diethyl quinacridone (DEQ) (diethylquinacridone) etc.; Comprise the colored cyanine fluorochrome of 4-(dicyano methylene)-2-methyl-6-(to dimethylaminostyryl)-4H-pyrans (DCM-1 (I)), DCM-2 (II), DCJTB (Ш) etc.; Comprise the xanthine fluorescent dye of rhodamine B and rhodamine 6G etc.; Comprise the pyridines fluorescent dye of pyridine 1; 4,4-bis-fluoro-1,3,5,7-tetraphenyl-4-boron-3a, 4a-diaza-s-indenes alkene [4,4-difluorm-1,3,5,7-tetra-phenyl-4-bora-3a, 4a-diaza-s-indacene] (IV), LumogenF are red, the low molecule luminescent material of Nile red (V) etc.; Comprise the high-molecular luminous material of polyphenyl (polyphenylene), poly-virtue (polyarylene), polyfluorene (polyfluorene) etc.; And the one in their combination.Being preferably, using Fluorescent Brightening agents based on Coumarin as fluorescent dye, and when using with other fluorochrome combinations, be effectively used to the situation of the wavelength convert wider width as changed to red light by blue green light.

In addition, described fluorescent dye can list, and is categorized as solvent (Solvent), acid (Acid), alkalescence (Basic), active (Reactive), directly (Direct), dispersion (Disperse) or reduces the dyestuff etc. of (Vat) in Colour Index (ColourIndex) (Britain dyeing [0119] worker learn publish) (TheSocietyofDyers [0119] andColourists publishes).More specifically, the dyestuff of following Colour Index (C.I.) number can be listed, but be not defined to this.

C.I. solvent yellow 25,79,81,82,83,89;

C.I. Indian yellow 7,23,25,42,65,76;

C.I. reactive yellow 2,76,116;

C.I. direct Huang 4,28,44,86,132;

C.I. disperse yellow (DisperseYellow) 54,76;

C.I. solvent orange 41,54,56,99;

C.I. acid orange 56,74,95,108,149,162;

C.I. reactive orange 16;

C.I. direct orange 26;

C.I. solvent red 24,49,90,91,118,119,122,124,125,127,130,132,160,218;

C.I. acid red 73,91,92,97,138,151,211,274,289;

C.I. acid violet 102;

C.I. solvent green 1,5;

C.I. acid green 3,5,9,25,28;

C.I. Viride Nitens 1;

C.I. vat green 1

In composition in its entirety mass percent 100%, such fluorescent dye can service property (quality) number percent 0.1% ~ mass percent 10%, preferred service property (quality) number percent 0.2% ~ mass percent 5%.Such content is consider to guarantee that higher luminescence efficiency and brightness reduce problem and chosen scope, if be less than described scope, protect luminescence efficiency Wu Fa Indeed, thus sufficiently cannot guarantee the color transfer characteristics that the present invention will obtain, on the contrary, even if exceed described scope, also cannot realize the further lifting of luminescence efficiency, the cost of manufacture of color-conversion filters can be increased because of high cost, therefore need suitably to carry out regulating and using in above-mentioned scope.

The antioxidant of feature of the present invention is become in the lump as mentioned above for solving by the problem of Photoepolymerizationinitiater initiater with described fluorescent dye.Specifically, although must Photoepolymerizationinitiater initiater be used when manufacturing color conversion layer with photosensitive polymer combination in prior art, but the free radical generated by these Photoepolymerizationinitiater initiaters and cause the reduction of fluorescence efficiency, the post bake operation of carrying out in production process causes and turns yellow.Thus in the present invention, suppress free radical by using antioxidant, thus can solve by the problem of described Photoepolymerizationinitiater initiater.

In addition, although implement exposure process when use sense photosensitive resin composition forms the pattern of color conversion layer, when but the initiating agent be now present in the region be blocked by the mask used during exposure is exposed by diffraction, the bad frequent generation of the graph outline of patterned sides edge.Thus, when autoluminescence photosensitive polymer combination of the present invention uses fortified phenol class antioxidant, effectively catch the free radical that produced by described diffraction and can effectively prevent the bad of the graph outline of patterned sides edge.

As antioxidant, as long as all can use for the antioxidant of photosensitive polymer combination, be not particularly limited in the present invention.Representational antioxidant can be selected from the one in benzotriazole compound, benzophenone compound, thio-ether type compounds, phenol compound, phosphorus species, sulphur compounds and their combination.

More specifically, can be 2-[3-(2H-benzotriazole-2-base)-4-hydroxy phenyl] ethylmethyl acrylate, 2-[2'-hydroxyl-5'-methaciylyloxyethylphenyl]-2H-benzotriazole etc. as benzotriazole antioxidant, can be 4-methacryloxy-2-dihydroxy benaophenonel, 4-acryloxy-2-dihydroxy benaophenonel or 4-allyloxy-2-dihydroxy benaophenonel etc. as benzophenone antioxidant.

Representative illustration as thioether antioxidants can be four [methane-3-(dodecylthio) propionic ester] methane, the two octadecyl of thio-2 acid, the two lauryls of thio-2 acid etc.

As phenolic antioxidants can for have spirocyclic ring scaffold phenol compound, other phenol compounds, be obstructed hydroxyl phenolic compound etc.

In an example, the two [2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1 of 3,9-can be listed as the phenol compound with above-mentioned spirocyclic ring scaffold, 1-dimethylethyloxy]-2,4,8,10-tetra-oxaspiro [5.5] undecane.

Three (3 can be listed as other phenol compounds above-mentioned, 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3,5-tri-(the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl)-isocyanuric acid ester, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxy-hydrocineamide), 4,6-two [(pungent sulfenyl) methyl] orthoresols etc.

The described hydroxyl phenolic compound that is obstructed can be represented by following chemical formula 1:

[chemical formula 1]

(in above-mentioned chemical formula 1, R1 ~ R5 is separately identical or different each other, the monoalkyl propionic ester of the alkyl of hydrogen, C1 ~ C20, the naphthenic base of C3 ~ C8 or C4 ~ C20 or dialkyl group propionic ester, wherein at least one is the tert-butyl group, the integer of 1≤n≤4)

Be preferably, compound when said n is 1 can be represented by following chemical formula 2:

[chemical formula 2]

(in above-mentioned chemical formula 2, R1 ~ R5 is described above)

Specifically, the compound of above-mentioned chemical formula 2 can list 2-TBP, 2,6-DI-tert-butylphenol compounds, 2,4-DTBP, 2-sec-butyl phenol, 2,6-di sec-butylphenol, 2,4-di sec-butylphenol, 2,6-di-t-butyl-4-ethyl-phenol, 2-isopropyl-phenol, 2,6-Bis(1-methylethyl)phenol, 2,4-diisopropyl phenol, 2-tert-octyl phenol, 2,6-bis-tert-octyl phenol, 2,4-bis-tert-octyl phenol, 2-cyclopentylphenol, 2,6-bicyclopentyl phenol, 2,4-bicyclopentyl phenol, 2-Butylated Hydroxytoluene, 2,6-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol, 6-butyl o-cresol, the tertiary dodecyl phenol of 2,6-bis-, the tertiary dodecyl phenol of 2,4-bis-, 2-sec-butyl paracresol, 2,6-bis-tert-octyl phenol, 2,4-bis-tert-octyl phenol, 6-sec-butyl orthoresol, the tertiary octyl group paracresol of 2-, the tertiary dodecyl paracresol of 2-, the 2-tert-butyl group-6-propofol, the tertiary octyl group orthoresol of 6-, the tertiary dodecyl orthoresol of 6-, octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester etc.

Said n has two when being more than 2-, three-or four-structure, above-mentioned R1 ~ R5 is combined mutually symmetrically by connection base (X).

As an example, compound when n is more than 2 can be represented by following chemical formula 3:

[chemical formula 3]

(in described chemical formula 3, R1 ~ R5 can be as mentioned above, the alkyl propionate that X can be the alkyl of C1 ~ C6, phenyl, benzyl, O or S, L can be singly-bound or C4 ~ C20)

Specifically, n be 2 compound can list 4,4'-fourth subunit two (the 6-tert-butyl group-3-methylphenol), 2,2'-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 4,4'-thiobis (3 methy 6 tert butyl phenol), 1, two [the 3-(3 of 6-hexanediol, 5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], 2,2-sulfo-divinyl two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] etc.

In addition, compound when n is 3 can be represented by following chemical formula 4:

[chemical formula 4]

(in described chemical formula 4, R1 ~ R5, X and L are for such as described in chemical formula 3)

Specifically, the compound of above-mentioned chemical formula 4 can list 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-tri-(4-hydroxybenzyl) benzene, 1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene etc.

And, n be 4 compound can be represented by following chemical formula 5:

[chemical formula 5]

(in described chemical formula 5, R1 ~ R5, X and L are for such as described in chemical formula 3)

Specifically, the compound of described chemical formula 5 can list pentaerythrite four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester].

The described hydroxyl phenolic compound that is obstructed not is defined in the compound of the condition meeting above-mentioned chemical formula 1.

Can be 3 as phosphorus antioxidants, 9-two (2,6-di-t-butyl-4-methylphenoxy)-2,4,8, the bi-ester of phosphite with spirocyclic ring scaffold of 10-tetra-oxa--3,9-bis-phospha spiral shell [5.5] undecane, diiso decyl pentaerythritol diphosphites, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites etc., 2, 2'-di-2-ethylhexylphosphine oxide (4, 6-di-t-butyl-1-phenoxy group) (2-ethyl hexyl oxy) phosphorus, 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxyl group]-2, 4, 8, 10-tetra-tert dibenzo [d, f] [1, 3, 2] dioxy phospha (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy]-2, 4, 8, 10tetra-tert-butyl-dibenzo [dmf] [1, 3, 2]-dioxaphosphepin), triphenyl phosphite, diphenylisodecyl base ester, diisodecyl phenyl phosphite, 4, two (the 3-methyl-6-tert butyl phenyl double tridecyl) phosphite ester of 4 '-butylidene, phosphorous acid stearyl, three (nonyl phenyl) phosphite ester, 9, assorted-10-the phosphine of 10-dihydro-9-oxy is mixed phenanthrene-10-oxide, 10-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-9, assorted-10-the phosphine of 10-dihydro-9-oxy is mixed phenanthrene-10-oxide, 10-oxygen in last of the ten Heavenly stems base-9, assorted-10-the phosphine of 10-dihydro-9-oxy is mixed phenanthrene-10-oxide, three (2, 4-di-tert-butyl-phenyl) phosphite ester, ring-type neopentane four base two (2, 4-di-tert-butyl-phenyl) phosphite ester (Cyclicneopentanetetraylbis (2, 4-di-t-butyl-phenyl) phosphite), ring-type neopentane four base two (2, 6-di-tert-butyl-phenyl) phosphite ester, 2, 2-di-2-ethylhexylphosphine oxide (4, 6-di-tert-butyl-phenyl) octyl group phosphite ester, three (2, 4-di-tert-butyl-phenyl) phosphite ester, four (2, 4-di-tert-butyl-phenyl) [1, 1-xenyl]-4, 4'-bis-base bis-phosphite (Tetrakis (2, 4-di-t-butylphenyl) [1, 1-biphenyl]-4, 4'-diylbisphosphonite), two [2, 4-two (1, 1-dimethyl ethyl)-6-aminomethyl phenyl] ethyl ester (Bis [2, 4-bis (1, 1-dimethylethyl)-6-methylphenyl] ethylester), phosphonic acids etc.

Can be 2 as sulphur class antioxidant, two ({ [3-(dodecylthio) propiono] oxygen base } methyl)-1 of 2-, two [3-(dodecylthio) propionic ester] (2 of 3-propane two base, 2-bis ([3-(dodecylthio) propionyl] oxy}methyl)-1, 3-propane-diyl-bis [3-(dodecylthio) propionate]), 2-sulfydryl benzene, 3, 3 '-thio-2 acid two (dodecyl) ester, 3, 3 '-thio-2 acid two (myristyl) ester, 3, 3 '-thio-2 acid two (octadecyl) ester, pentaerythrite-four (3-dodecylthio propionic ester) etc. has the compound of sulfide based structural, 2-sulfydryl benzene etc.

Such antioxidant is in composition in its entirety mass percent 100%, and service property (quality) number percent 0.1% ~ mass percent 10%, is preferably service property (quality) number percent 0.2% ~ mass percent 7%.Such content is relative to Photoepolymerizationinitiater initiater, and relieving light efficiency reduces and yellowing problems, considers that brightness reduces problem and chosen scope, is used in particular for Photoepolymerizationinitiater initiater with the weight ratio of particular range.Be preferably, to have antioxidant: Photoepolymerizationinitiater initiater is the mode of the weight ratio of 1:1.2 ~ 1:5, make it be no more than the content of Photoepolymerizationinitiater initiater.If, when content ratio between the content of antioxidant and Photoepolymerizationinitiater initiater is less than described scope, optical efficiency cannot be guaranteed, and fully cannot guarantee the color transfer characteristics that will obtain in the present invention, if when exceeding described scope on the contrary, there is the worry that brightness reduces, thus suitably regulate in described scope and use.

With such fluorescent dye and antioxidant in the lump, autoluminescence photosensitive composite involved in the present invention also comprises alkali soluble resin.

Alkali soluble resin has by the reactivity of light or heat effect and alkaline solubility, and as fluorescent dye spreading agent and play a role, as long as this for the manufacture of the adhesive resin dissolving in alkaline-based developer used in the development phase of filtrator, then all can use.

Be preferably, the selected alkali soluble resin with the acid number of 20 ~ 200 (KOHmg/g) of above-mentioned alkali soluble resin uses.Acid number for as in the amount (mg) of the potassium hydroxide needed for acrylic polymers 1g and determined value and relevant to dissolubility.As long as the acid number of resin belongs to above-mentioned scope, then tool has the following advantages, namely, the dissolubility in developer solution is made to promote and make non-exposed division easily be dissolved and sensitivity is increased, the pattern of exposed division finally can be made residual when developing, thus improve membrane left rate (filmremainingratio).

In addition, the restriction of molecular weight for above-mentioned alkali soluble resin and molecular weight distribution rate (MW/MN) can be considered, promote skin hardness for color conversion layer.Be preferably, make weight-average molecular weight become 3,000 ~ 200,000 and more preferably become 5,000 ~ 100,000, make molecular weight distribution rate have 1.5 ~ 6.0 and the mode being preferably the scope of 1.8 ~ 4.0 is carried out direct polymerization or buying and uses.The alkali soluble resin of the molecular weight and molecular weight distribution rate with described scope can not only realize that the hardness mentioned promotes, higher membrane left rate, and the dissolubility of non-exposed division in developer solution is comparatively remarkable and can promote resolution.

Above-mentioned alkali soluble resin comprise be selected from containing carboxyl unsaturated monomer polymkeric substance or can and the monomer with unsaturated link of its copolymerization between co-polymer and one in their combination.

Now, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid etc. can be used containing carboxyl unsaturated monomer.Specifically, as unsaturated monocarboxylic acid, such as, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid etc. can be listed.As unsaturated dicarboxylic acid, such as, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. can be listed.Unsaturated polybasic carboxylic acid can be acid anhydrides, specifically, can list maleic anhydride, itaconic anhydride, citraconic anhydride etc.In addition, unsaturated polybasic carboxylic acid also can be its single (2-(methyl) acryloxyalkyl) ester, such as, mono succinate (2-acryloyl-oxyethyl) ester (2-(ACRYLOYLOXY) ETHYLHYDROGENSUCCINATE), mono succinate (2-methacryloxyethyl) ester, phthalic acid list (2-acryloyl-oxyethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc. can be listed.List (methyl) acrylate of unsaturated polybasic carboxylic acid can also to be two end the be polymkeric substance of dicarboxyl, such as, can list ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc.These carboxyl group-containing monomers can be used alone separately or be use mixing two or more.

In addition, can can use with the monomer containing the copolymerization of carboxyl unsaturated monomer and be selected from aromatic ethenyl compound, unsaturated carboxylic ester compound, unsaturated carboxylic acid aminoalkyl ester compounds (Unsaturatedcarboxylicacidaminoalkylestercompound), unsaturated carboxylic acid epihydric alcohol ester compound, vinyl esters of carboxylic acids compound, unsaturated ethers compound, vinyl cyanide compound (vinylcyanidecompound), unsaturated acyl imine compound, aliphatic conjugated diene compounds, there is at the end of strand the huge monomer of single acryloyl group or monomethacrylate acyl group, one in bulky monomer and their combination.

More specifically, above-mentioned copolymerizable monomer can use the aromatic ethenyl compound of styrene, α-methyl styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, indenes etc., methyl acrylate, methyl methacrylate, ethyl acrylate, β-dimethyl-aminoethylmethacrylate, n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, the secondary butyl ester of methacrylic acid, tert-butyl acrylate, Tert-butyl Methacrylate, acrylic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacry-late, 2-hydroxypropyl acrylate, 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, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-ihethoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxyl diethylene glycol acrylate, methoxyl diethylene glycol methacrylate, methoxy triethylene acrylate, methoxy triethylene methacrylate, MPEG acrylate, MPEG methacrylate, methoxyl dipropylene glycol acrylate, methoxyl dipropylene glycol methyl acrylate, isobornyl acrylate, isobornyl methacrylate, bicyclopentadiene acrylate, bicyclopentadiene methacrylate, adamantyl (methyl) acrylate, bornyl (methyl) acrylate, acrylic acid-2-hydroxyl-3-phenoxy-propyl, methacrylic acid-2-hydroxyl-3-phenoxy-propyl, single glycerol acrylate, the esters of unsaturated carboxylic acids of glycerol monomethacrylate etc., 2-aminoethylacrylate, 2-amidoethyl methacrylate, 2-dimethyl amino ethyl acrylate, 2-dimethyl amino ethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate ester, 2-dimethylaminopropylacryl acid esters, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate ester, 3-dimethylaminopropylacryl acid esters, the unsaturated carboxylic acid glyceride compounds of 3-dimethylaminopropyl methacrylate etc., the unsaturated carboxylic acid epihydric alcohol ester compound of glycidyl acrylate, glycidyl methacrylate etc., the generating vinyl carboxylate ester compounds of vinyl acetate, propionate, vinyl butyrate, vinyl benzoate etc., the unsaturated ethers compound of methoxy ethylene, ethyl vinyl ether, allyl glycidyl ether etc., the vinyl cyanide compound of the sub-ethene (vinylidenecyanide) of vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, dicyan etc., the unsaturated acyl amine such as acrylamide, Methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide, the unsaturated acyl amines of maleimide, benzyl maleimide, N-benzyl maleimide, N-N-cyclohexylmaleimide etc., 1, the aliphatic conjugated diene class of 3-butadiene, isoprene, chlorbutadiene etc., the positive butyl ester of polystyrene, polymethyl acrylate, polymethylmethacrylate, polyacrylic acid, Vinalac 5920, there is at the end of the polymer molecular chain of polysiloxane the bulky monomer of the huge monomer class of single acryloyl group or monomethacrylate acyl group, the monomer with the borneol skeleton that can reduce dielectric constant values, the monomer with adamantane framework, the monomer with rosin skeleton etc.

Such alkali soluble resin, can service property (quality) number percent 5% ~ mass percent 85%, preferably service property (quality) number percent 7% ~ mass percent 50% in composition in its entirety mass percent 100%.Such content is that many-side considers the scope be selected relative to the solubleness and pattern formation etc. of developer solution, when using in described scope, make fully to be easy to pattern relative to the dissolubility of developer solution to be formed, and can prevent when developing the film of the pixel portion in exposure portion from reducing thus making the leakage of non-pixel portion good.

Photopolymerizable compound is the compound that can carry out being polymerized under the effect of Photoepolymerizationinitiater initiater, can use monofunctional monomer, bifunctional monomer and polyfunctional monomer etc. in addition.

As the concrete example of monofunctional monomer, nonyl phenyl carbitol acrylate, 2-hydroxyl-3-phenoxypropylacrylate, 2-ethylhexyl carbitol acrylate (2-ethylhexylcarbitolacrylate), acrylic acid-2-hydroxyl ethyl ester, NVP etc. can be listed.As the concrete example of bifunctional monomer, two (acryloyl-oxyethyl) ether (Bis (acryloyloxyethyl) ether), 3-methyl pentanediol two (methyl) acrylate (3-methyl-pentanedioldi (meth) acrylate) etc. of 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A can be listed.As the concrete example of other polyfunctional monomer, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc. can be listed.Wherein, the polyfunctional monomer using more than difunctionality is preferably.

Such photopolymerizable compound, can service property (quality) number percent 1% ~ mass percent 50%, preferably service property (quality) number percent 4% ~ mass percent 20% in composition in its entirety mass percent 100%.Such content is that many-side considers the scope making the intensity in pixel portion and flatness become good tendency etc. to be selected, if its content is less than above-mentioned scope, the problem of intensity and flatness deficiency can be there is, on the contrary, if exceed above-mentioned scope, then can there is the problem of easily carrying out pattern formation because of higher intensity, thus need suitably to use in above-mentioned scope.

Photoepolymerizationinitiater initiater is the compound of the polymerization for causing described photopolymerizable compound, preferably uses acetophenone compounds in the present invention.

Acetophenone compounds can be diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone (2-hydroxy-2-methyl-1-phenylPropane-1-one), benzoin dimethylether (benzildimethylketal), 2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl]-2-methyl isophthalic acid-acetone, 1-hydroxycyclohexyl phenyl ketone (1-hydroxycyclohexylphenylketone), 2-methyl isophthalic acid-(4-methylphenyl-sulfanyl)-2-morpholinyl-1-acetone (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one), 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butane-1-one), the oligomer etc. of 2-hydroxy-2-methyl [4-(1-methyl ethylene) phenyl]-1-acetone (2-hydroxy-2-methyl [4-(1-methylvinyl) phenyl] propan-1-one), wherein preferably can use 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone.

In Photoepolymerizationinitiater initiater involved in the present invention, autoluminescence photosensitive polymer combination is made to expose the time and is shortened by highly sensitiveization, thereby, it is possible to promote with throughput rate and the mode maintaining higher resolution regulates its content.Be preferably, described Photoepolymerizationinitiater initiater can service property (quality) number percent 0.1% ~ mass percent 40%, preferably service property (quality) number percent 0.5% ~ mass percent 30% in composition in its entirety.If its content is less than described scope, polymerization speed slowly, on the contrary, if exceed described scope, can make because of excessive reaction cross-linking reaction excessive, make the physical property of film reduce on the contrary, thus need suitably to use in described scope.

Other Photoepolymerizationinitiater initiater or photopolymerization can also be caused assistant and combinationally use by above-mentioned acetophenones Photoepolymerizationinitiater initiater.

Photoepolymerizationinitiater initiater capable of being combined can be the styrax compounds comprising benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin dimethylether etc., comprise diphenylmethanone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenyl benzophenone, dihydroxy benaophenonel, acrylated benzophenone, 4, the benzophenone compound of 4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone etc., comprise 2, 4, 6-trichloto-s-triazine, 2-phenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(3 ', 4 '-dimethoxy)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4 '-methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methylphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-xenyl-4, two (the trichloromethyl)-s-triazine of 6-, two (trichloromethyl)-6-styryl-s-triazine, 2-(naphthalene-1-base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxynaphthalene-1-base)-4, two (the trichloromethyl)-s-triazine of 6-, 2, 4-trichloromethyl (piperonyl)-6-triazine, 2, the compound in triazine class of 4-trichloromethyl (4 '-methoxyl-styrene)-6-triazine etc., comprise the sulphur compound of thioxanthones, CTX, 2,4-diethyl thioxanthones, 2-methyl thioxanthones, 2-isopropylthioxanthones etc., the anthraquinone analog compound of 2-EAQ, prestox anthraquinone, 1,2-benzo anthraquinone, 2,3-diphenyl anthraquinones etc., the organic peroxide of azoisobutyronitrile, benzoyl peroxide, dicumyl peroxide etc., the thiol base class compound of 2-mercaptobenzoxazole or 2-mercaptobenzothiazole etc.

Described Photoepolymerizationinitiater initiater capable of being combined can use in the weight portion scope relative to acetophenones Photoepolymerizationinitiater initiater 1 weight portion 0.1 ~ 0.5.

Photopolymerization causes assistant for improving polymerization efficiency, can use aminated compounds, alcoxyl anthracene compounds and thioxanthones compounds etc.

As aminated compounds, triethanolamine can be listed, methyldiethanolamine, triisopropanolamine, 4-dimethyl ethyl aminobenzoate, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester (4-dimethylaminobenzoicacidisoamyl), benzoic acid 2-dimethylaminoethyl ester (Benzoicacid2-dimethylaminoethyl), 4-dimethylaminobenzoic acid-2-Octyl Nitrite (4-dimethyl-aminobenzoicacid2-ethylhexyl), n, n-dimethyl-p-toluidine (N, N-dimethylparatoluidine), 4, 4 '-bis-(dimethylamino) benzophenone (4, 4'-bis (dimethylamino) benzophenone) (being commonly called as Michler's keton), 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein be preferably 4, 4 '-bis-(diethylamino) benzophenone.In addition, as alcoxyl anthracene compounds, such as, 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene etc. can be listed.As thioxanthones compounds, such as, ITX, ITX, 2 can be listed, 4-diethyl thioxanthone, 2, the chloro-4-propoxythioxanthone (1-chloro-4-propoxythioxanthone) of 4-bis-clopenthixal ketone (2,4-dichlorothioxanthone), 1-etc.Above-mentioned photopolymerization causes assistant and can directly manufacture or buy commercially available product and use, as an example, and can commodity in use name " EAB-F " [manufacturer: Baotugu Chemical Industrial Co., Ltd] series etc.

Such photopolymerization causes every relative to Photoepolymerizationinitiater initiater 1 mole and usually use in the scope of 0.01 ~ 5 mole below 10 moles, preferably of assistant.Use in above-mentioned scope photopolymerization cause assistant, can polymerization efficiency be improved and realize throughput rate promote effect.

As long as solvent can make above-mentioned mentioned composition dissolve or the solvent of dispersion, then all can use, not limit especially in the present invention.Representatively solvent, can list alkylene glycol monoalkyl ethers (alkyleneglycolmonoalkylether) class, aklylene glycol alkyl ether acetates, arene, ketone, rudimentary and higher alcohols, cyclic ester class etc.More specifically, as described solvent, the alkylene glycol monoalkyl ethers class of glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether etc. can be listed; The diethylene glycol dialkyl ether class of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether etc.; The aklylene glycol alkyl ether acetates of methyl cellosolve acetate (methylcellosolveacetate), acetic acid ethoxy ethyl ester, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate etc.; The arene of benzene,toluene,xylene, sym-trimethyl benzene etc.; The ketone of methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone etc.; The alcohols of ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc.; The ester class of 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate etc.; The cyclic ester class etc. of gamma-butyrolacton etc.

In above-mentioned solvent, following solvent can be listed in coating, drying property, be preferably, the organic solvent of the boiling point that can list 100 DEG C ~ 200 DEG C can be used in above-mentioned solvent, be more preferably, the ester class of aklylene glycol alkyl ether acetates, ketone, 3-ethoxyl ethyl propionate or 3-methoxy methyl propionate etc. can be listed, more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, cyclohexanone, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate etc. can be listed.These solvents (E) individually use or two or more used in combination.

Composition in its entirety is set to mass percent 100%, such solvent assigns to use to meet the mode of composition in its entirety mass percent 100% as remainder.Such content is consider operation easness (such as, coating) in the dispersion stabilization of composition and manufacturing process and chosen scope.In other words, autoluminescence photosensitive polymer combination involved in the present invention can manufacture color-conversion filters by wet, now, as wet method, the apparatus for coating of roll coater (Rollcoater), sol evenning machine (spincoater), spin coater (slitandspincoater), flat painting machine (slitcoater) (also referred to as scraper machine (diecoater)), ink-jet etc. can be used.

And autoluminescence photosensitive polymer combination involved in the present invention can also add known adjuvant according to multiple object.As such adjuvant, can also with adjuvants such as filler, other macromolecular compounds, pigment dispersing agent, adhesion promoter, ultraviolet light absorber, anti-agglomerating agents.These adjuvants can use one or more, consider luminescence efficiency etc. and preferably use mass percent less than 1% in composition in its entirety.

Glass, silicon dioxide, alumina etc. can be used as filler, the thermoplastic resin etc. of the hardening resin such as epoxy resin, maleimide resin, polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-fluoroalkyl, polyester, poly-urethane etc. can be listed as other macromolecular compounds.

Commercially available surfactant can be used as pigment dispersing agent, such as, the surfactant etc. of silicon class, fluorine class, ester class, cationic, anionic species, nonionic class, both sexes etc. can be listed.These can be used alone or are used in combination of two or more.As described surfactant, such as, there is polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyglycol di-esters, sorbitan fatty acid ester class, fatty acid modified polyester (Fattyacid-modifiedpolyester) class, tertiary-amine modified polyurethane (Tertiaryamine-modifiedpolyurethane) class, polyethyleneimine: amines etc., in addition, as trade name, can list KP (Shin-Etsu Chemial Co., Ltd's manufacture), POLYFLOW (Kyoeisha Chemical Co., Ltd.'s manufacture), EFTOP (manufacture of Tochem Products Co., Ltd) (Ltd.TochemProducts), MEGAFAC (Dainippon Ink Chemicals), Flourad (manufacture of Sumitomo 3M Co., Ltd.) (Sumitomo3MLimited), Asahiguard, Surflon (above for Asahi Glass Co., Ltd manufactures), SOLSPERSE (manufacture of ZENECA Co., Ltd.) (ZenecaLtd.), EFKA (manufacture of EFKA chemicals commercial firm) (EFKAChemicalsCo., Ltd.), PB821 (Ajincomoto Co., Inc's manufacture) etc.

As adhesion promoter, such as, vinyltrimethoxy silane can be listed, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidyloxypropyl trimethoxy silane, 3-glycidylpropyl methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropyl trimethoxy silane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane etc.

Ultraviolet light absorber, 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorinated benzotriazole (2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-benzotriazole), alcoxyl benzophenone etc. can be used particularly, as anti-agglomerating agent, specifically sodium polyacrylate etc. can be listed.

Manufacture as the autoluminescence photosensitive composite as described in going forward does not limit in the present invention especially, can according to the manufacture method of known photosensitive composite.

Such autoluminescence photosensitive composite is applicable to display device, preferably requires the color conversion layer of the liquid crystal indicator of other light source.

After coating, lithographically can carry out pattern formation to the importing in color conversion layer, thus form the pattern of R, G of corresponding color filter.Photoetching process does not limit in the present invention especially, as long as the known method of use sense photosensitive resin composition all can be applied.

As an example, be implemented the color conversion layer of pattern formation by obtaining with the next stage:

A) autoluminescence photosensitive composite is coated on the stage of substrate surface;

B) by presulfurization (precure), solvent is carried out dry stage (front baking) (pre-bake);

C) on obtained overlay film, enclose photomask (photomask) and irradiate active ray (activelight) thus make the stage hardened in exposure portion;

D) implement the stage of developing procedure, that is, utilize alkaline aqueous solution to dissolve unexposed portion;

E) stage that is dry and post bake (post-bake) is implemented.

Aforesaid substrate can use glass substrate or macromolecule plate.As glass substrate, especially preferably use soda-lime glass (Soda-limeglass), containing strontium barium glass, lead glass, aluminosilicate glass, pyrex, barium pyrex or quartz etc.In addition PC, acrylic acid, polyethylene terephthalate (PETP), polyether sulfides or poly-sulphur etc. can be listed as macromolecule plate.

Now, in order to obtain desired thickness, coating can use roll coater, sol evenning machine, spin coater, flat painting machine (also referred to as scraper machine), ink-jet etc. to use the wet method of apparatus for coating.

Front baking is implemented by being undertaken heating by baking oven, hot plate etc.Heating-up temperature and the heat time of front baking are appropriately selected by used solvent, such as, at the temperature of 80 ~ 150 DEG C, carry out 1 ~ 30 minute.

In addition, the exposure implemented after front baking is implemented by exposure machine and utilizes photomask exposure, thus only makes the part corresponding to pattern carry out photosensitive.Now, the light of irradiation such as can use visible rays, ultraviolet, X ray and electron ray etc.

Alkaline development after exposure is implemented for the purpose of the resist of the not removed part to non-exposed part is removed, thus can form desired pattern by this development.As the developer solution being suitable for this alkaline development, such as, the aqueous solution etc. of the carbonate of alkaline metal or alkaline-earth metal can be used.Especially use the alkaline aqueous solution that comprises the carbonate such as sodium carbonate, sal tartari, lithium carbonate of mass percent 1% ~ mass percent 3% 10 ~ 50 DEG C, preferably utilize developing machine or supersonic wave cleaning machine etc. to implement in the temperature of 20 ~ 40 DEG C.

Post bake be in order to improve be implemented pattern formed color conversion layer and substrate between compactedness and implement, at 80 ~ 220 DEG C and to be implemented by thermal treatment under the condition of 10 ~ 120 minutes.Post bake is same with front baking to be used baking oven, hot plate etc. to implement.

The color conversion layer obtained by such method is with the thickness of enough sizes, several microns ~ several millimeters, be preferably 0.1 ~ 100 μm, more preferably 1 ~ 50 μm thickness and be formed, so that higher brightness can be maintained and can guarantee excellent color transfer characteristics and higher luminescence efficiency.

As long as above-mentioned color conversion layer then optional position between light source and color filter, although adopt structure based on light source/color conversion layer/color filter, color conversion layer and color filter also can be adopted directly to be connected or the structure that is inserted with other films or substrate imports.

Now, light source can use LED, cold-cathode tube, inorganic EL, organic EL fluorescent light or incandescent lamp etc., is preferably the liquid crystal indicator that use take LED as light source.

The display device possessing such light source and color conversion layer maintains higher brightness and guarantees excellent color transfer characteristics and higher luminescence efficiency, thus can realize high-quality and image quality clearly.

Below, although pointed out preferred embodiment to help to understand the present invention, but following embodiment is as an illustration of the present invention, can carry out numerous variations and amendment is that those skilled in the art can understand within the scope of scope of the present invention and technological thought, such distortion and amendment also belong to the scope of accompanying claim certainly.In addition, represent that " % " and " part " of content is benchmark with quality when not illustrating hereinafter.

Production Example 1: the manufacture of alkali soluble resin A

As tap funnel, carry out being uniformly mixed after adding benzyl maleimide 74.8g (0.20 mole), acrylic acid 43.2g (0.30 mole), vinyltoluene 118.0g (0.50 mole), t-butylperoxy-2 ethyl hexanoic acid ester 4g, propylene glycol monomethyl ether acetate (PGMEA) 40g and for subsequent use, and drip tank (chaintransferagentdriptank) as chain-transferring agent, carry out after adding n-dodecyl mercaptan 6g, PGMEA24g being uniformly mixed and for subsequent use.

Afterwards, in flask, import PGMEA395g, and after the environment in flask is set to nitrogen by air, stir the temperature to 90 DEG C making flask.Next, start to drip monomer and chain-transferring agent from tap funnel.Dropping liquid maintain 90 DEG C constant, carry out 2 hours respectively, after 1 time, be warming up to 110 DEG C and maintain after 3 hours, importing gas conduit, start the bubbling into oxygen/nitrogen=5/95 (v/v) mixed gas.

Next, by glycidyl methacrylate 28.4g [(0.10 mole), (the acrylic acid carboxyl relatively for this reaction is molar percentage 33%)], 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol) 0.4g, triethylamine 0.8g to drop in flask and at 110 DEG C sustained response 8 hours, thus to obtain solid content acid number be the Resin A of 70mgKOH/g.

The weight-average molecular weight of the polystyrene conversion measured by GPC is 16,000, and molecular weight distribution (Mw/Mn) is 2.3.

Production Example 2: the manufacture of alkali soluble resin B

To possessing stirring machine, thermometer reflux condensing tube, in the flask of tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether acetate 182g, and after the environment in flask is set to nitrogen by air, be warming up to after 100 DEG C, to comprising benzyl methacrylate 70.5g (0.40 mole), methacryloxyethyl acid 45.0g (0.50 mole), the solution of azoisobutyronitrile 3.6g is with the addition of in single methyl acrylate 44.5g (0.10 mole) of different circulation skeleton and the potpourri of propylene glycol monomethyl ether acetate 136g, by tap funnel to flask carry out dropping liquid 2 hours and at 100 DEG C further Keep agitation 5 hours.

Next, environment in flask is set to air by nitrogen, glycidyl methacrylate 30g [0.2 mole, (carboxyl of methacrylic acid relatively used in this reaction is molar percentage 40%)], three (dimethylaminomethyl) phenol 0.9g and p-dihydroxy-benzene 0.145g to be put in flask and at 110 DEG C sustained response 6 hours, thus obtain the resin B that solid content acid number is 99mgKOH/g.

The weight-average molecular weight of the polystyrene conversion measured by GPC is 28,000, and molecular weight distribution (Mw/Mn) is 2.2.

Production Example 3: the manufacture of alkali soluble resin C

To possessing stirring machine, thermometer reflux condensing tube, propylene glycol monomethyl ether acetate 182g is imported in the flask of tap funnel and nitrogen ingress pipe, and after the environment in flask is set to nitrogen by air, be warming up to after 100 DEG C, to comprising benzyl methacrylate 70.5g (0.40 mole), methacrylic acid 45.0g (0.50 mole), the solution of azoisobutyronitrile 3.6g is with the addition of in the potpourri of 2-(2-methyl) adamantyl methyl acrylate 22.0g (0.10 mole) and propylene glycol monomethyl ether acetate 136g, by tap funnel to flask carry out dropping liquid 2 hours and at 100 DEG C further Keep agitation 5 hours.

Next, environment in flask is set to air by nitrogen, and glycidyl methacrylate 30g [0.2 mole, (carboxyl of methacrylic acid relatively used in this reaction is molar percentage 40%)], three (dimethylaminomethyl) phenol 0.9g and p-dihydroxy-benzene 0.145g to be put in flask and at 110 DEG C sustained response 6 hours, thus obtain the resin C that solid content acid number is 99mgKOH/g.

The weight-average molecular weight of the polystyrene conversion measured by GPC is 23,000, and molecular weight distribution (Mw/Mn) is 2.3.

Utilize GPC method under the following conditions to weight-average molecular weight (Mw) and number mean molecular weight (Mn) the enforcement mensuration of above-mentioned resin, now, using the ratio of each numerical value of acquisition as molecular weight distribution (Mw/Mn).

Device: HLC-8120GPC (TOSOH Co., Ltd's manufacture)

Post: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow velocity: 1.0ml/ divides

Injection rate IR: 50 μ l

Detector: RI

Measure reagent concentration: 0.6 quality % (solvent=tetrahydrofuran)

Correction standard substance: TSKSTANDARDPOLYSTYRENEF-40, F-4, F-1, A-2500, A-500 (TOSOH Co., Ltd's manufacture)

Embodiment 1 ~ 11 and comparative example 1 ~ 7: color conversion layer manufacture

After mixer adds solvent, add dyestuff at this, antioxidant adds alkali soluble resin, photopolymerizable compound and Photoepolymerizationinitiater initiater, and mix by stirring and produce autoluminescence photosensitive polymer combination.Now, composition is according to the composition of following table 1.

Above-mentioned obtained photosensitive polymer combination is utilized after spin-coating method is coated with above glass substrate, place on hot plate and maintain 3 minutes at the temperature of 100 DEG C, thus forming film.

Next, to described film irradiation ultraviolet radiation.Now, ultraviolet light source uses the ultrahigh pressure mercury lamp (trade name USH-250D) of USHIO Electric Co., Ltd manufacture under atmospheric environment with 40mJ/cm ²exposure (365nm) carry out illumination and penetrate, do not use special optical filter.

Utilize spray development machine by after being developed 60 seconds in the KOH aqueous development solution of pH12.5 by the film of above-mentioned Ultraviolet radiation, heat 20 minutes in the heated oven of 220 DEG C, thus produce pattern.Thus, make above-mentioned manufactured go out the thickness of color conversion layer be formed as 3.0 μm.

[table 1]

[table 2]

Experimental example 1: the luminous intensity of color conversion layer measures

In order to whether confirm the increase of the fluorescence efficiency of the color conversion layer obtained by described embodiment and comparative example, quantum efficiency tester (QE-1000, great Zhong Inc.) is used to measure luminous PL.The result obtained is shown in shown in following table 3, and more high fluorescence efficiency is also higher now to mean the tested luminous intensity made.

[table 3]

	Luminous intensity (λ max:500)
		Embodiment 1	11669
Embodiment 2	14000
		Embodiment 3	11600
Embodiment 4	12272
		Embodiment 5	12000
Embodiment 6	11100
		Embodiment 7	10200
Embodiment 8	12000
		Embodiment 9	13270
Embodiment 10	12560
		Embodiment 11	9500
Comparative example 1	8100
		Comparative example 2	9000
Comparative example 3	9448
		Comparative example 4	9200
Comparative example 5	8000
		Comparative example 6	7000
Comparative example 7	10000

As above known shown in table 3, by using fluorescent dye and antioxidant simultaneously in the present invention, thus fluorescence efficiency is raised.

Even if confirm that content at antioxidant and Photoepolymerizationinitiater initiater is than in controlled situation in addition, the change of fluorescence efficiency also can meaningfully occur.

Experimental example 2: the tapering of color conversion layer and flatness evaluation

The constituent obtained in described embodiment and comparative example and manufactured color filter are as object SEM (10,000 multiplying power) observe tapering (taper) and the pattern flatness of the shape of Pixel surface, and the results are shown in following table 4.At this moment tapering and pattern flatness as follows.

< tapering >

Zero: pattern contour (Patternprofile) is good

Ⅹ: pattern contour (Patternprofile) is bad

< flatness >

Zero: the flatness deviation in pattern edge (Patternedge) portion is below 1 μm

Ⅹ: pattern edge (Patternedge) portion flatness deviation is more than 1 μm.

[table 4]

	Tapering	Flatness
			Embodiment 1	○	○
Embodiment 2	○	○
			Embodiment 3	○	○
Embodiment 4	○	○
			Embodiment 5	○	○
Embodiment 6	○	○
			Embodiment 7	○	○
Embodiment 8	○	○
			Embodiment 9	○	○
Embodiment 10	○	○
			Embodiment 11	○	○
Comparative example 1	X	X
			Comparative example 2	X	X
Comparative example 3	X	X
			Comparative example 4	X	X
Comparative example 5	X	X
			Comparative example 6	X	X
Comparative example 7	X	X

Known with reference to above-mentioned table 4, when forming pattern by photosensitive compoistion involved in the present invention, tapering and the flatness of pattern are more excellent.

Utilizability in industry

Autoluminescence photosensitive polymer combination involved in the present invention is directed in the color conversion layer of display device, thus can maintain the color reproduction of higher level and brightness and can realize high-grade image quality clearly.

Symbol description

1: substrate;

3: color conversion layer;

5: color filter.

Claims (20)

1. an autoluminescence photosensitive polymer combination, it comprises fluorescent dye, antioxidant, alkali soluble resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent as the composition for the formation of color conversion layer.

2. autoluminescence photosensitive polymer combination as claimed in claim 1, is characterized in that,

Composition in its entirety is set to mass percent 100%, described autoluminescence photosensitive polymer combination comprises in the mode met when composition in its entirety mass percent is 100%:

Fluorescent dye mass percent 0.1% ~ mass percent 10%;

Antioxidant mass percent 0.1% ~ mass percent 10%;

Alkali soluble resin mass percent 5% ~ mass percent 85%;

Photopolymerizable compound mass percent 1% ~ mass percent 50%;

Photoepolymerizationinitiater initiater mass percent 0.1% ~ mass percent 40%;

As the solvent of remainder.

3. autoluminescence photosensitive polymer combination as claimed in claim 1, is characterized in that,

Antioxidant is comprised with the mass ratio of 1:1.2 ~ 1:5: Photoepolymerizationinitiater initiater in autoluminescence photosensitive polymer combination.

4. autoluminescence photosensitive polymer combination as claimed in claim 1, is characterized in that,

Described fluorescent dye comprises the one be selected from Coumarins, naphthalimide, quinacridine ketone, flower cyanines class, xanthine, pyridines, low molecule luminescent material, high-molecular luminous material and their combination.

5. autoluminescence photosensitive polymer combination as claimed in claim 1, is characterized in that,

Described antioxidant is comprise the one be selected from benzotriazole compound, benzophenone compound, thio-ether type compounds, the phenol compound with spirocyclic ring scaffold, other phenol compounds, the phosphide with spirocyclic ring scaffold, phosphorus species, sulphur compounds and their combination, wherein

Benzotriazole compound comprises the benzotriazole compound of 2-[3-(2-H-benzotriazole-2-base)-4-hydroxy phenyl] ethylmethyl acrylate and 2-[2 '-hydroxyl-5 '-methaciylyloxyethylphenyl]-2H-benzotriazole;

Benzophenone compound comprises 4-methacryloxy-2-dihydroxy benaophenonel, 4-acryloxy-2-dihydroxy benaophenonel and 4-allyloxy-2-dihydroxy benaophenonel;

Thio-ether type compounds comprises four [methane-3-(dodecylthio) propionic acid] methane ester, the two octadecyl of thio-2 acid and the two lauryl of thio-2 acid;

The phenol compound with spirocyclic ring scaffold comprises two [2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1,1-dimethylethyloxy]-2,4,8,10-tetra-oxaspiro [5.5] undecanes of 3,9-;

Other phenol compounds comprise three-(3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3,5-tri-(the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, N, two (3, the 5-di-t-butyl-4-hydroxy-hydrocineamide) hydrocinnamamide of N'-hexa-methylene, 4,6-two [(pungent sulfenyl) methyl] orthoresols;

The phosphide with spirocyclic ring scaffold comprises 3,9-two (2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetra-oxa--3,9-bis-phospha spiral shell [5.5] undecane, diiso decyl pentaerythritol diphosphites and two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites;

Phosphorus species comprises 2,2'-di-2-ethylhexylphosphine oxide (4,6-di-t-butyl-1-phenoxy group) (2-ethyl hexyl oxy) phosphorus, 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxyl group]-2,4,8,10-tetra-tert dibenzo [d, f] [1,3,2] dioxy phosphas, triphenyl phosphite, diphenylisodecyl base ester, phenyl two isodecyl phosphite ester, 4, two (the 3-methyl-6-tert butyl phenyl double tridecyl) phosphite ester of 4 '-butylidene, 18 phosphite esters, three (nonyl phenyl) phosphite ester, assorted-10-the phosphine of 9,10-dihydro-9-oxy is mixed phenanthrene-10-oxide, assorted-10-the phosphine of 10-(3,5-di-tert-butyl-4-hydroxyl benzyl)-9,10-dihydro-9-oxies is mixed phenanthrene-10-oxide, assorted-10-the phosphine of 10-oxygen in last of the ten Heavenly stems base-9,10-dihydro-9-oxy is mixed phenanthrene-10-oxide, three (2,4-di-tert-butyl-phenyl) phosphite ester, ring-type neopentane four base two (2,4-di-tert-butyl-phenyl) phosphite ester, ring-type neopentane four base two (2,6-di-tert-butyl-phenyl) phosphite ester, 2,2-di-2-ethylhexylphosphine oxide (4,6-di-tert-butyl-phenyl) octyl group phosphite ester, three (2,4-di-tert-butyl-phenyl) phosphite ester, four (2,4-di-tert-butyl-phenyl) [1,1-xenyl]-4,4'-bis-base bis-phosphite, two [2,4-two (1,1-dimethyl ethyl)-6-aminomethyl phenyl] ethyl ester and phosphonic acids,

Sulphur compounds comprises 2; 2-pair (3-(dodecylthio) propiono] and oxygen base } methyl)-1; 3-propane two base-bis-[3-(dodecylthio) propionic ester], 2-sulfydryl benzene, 3; 3 '-thio-2 acid two (dodecyl) ester, 3; 3'-thio-2 acid two (myristyl) ester, 3,3 '-thio-2 acid two (octadecyl) ester and pentaerythrite-four (3-dodecylthio propionic ester).

6. autoluminescence photosensitive polymer combination as claimed in claim 1, is characterized in that,

Described antioxidant is the hydroxyl phenolic compound that is obstructed.

7. autoluminescence photosensitive polymer combination as claimed in claim 6, is characterized in that,

The described hydroxyl phenolic compound that is obstructed can be represented by following chemical formula 1,

In described chemical formula 1, R1 ~ R5 is separately identical or different each other, the monoalkyl propionic ester of the alkyl of hydrogen, C1 ~ C20, the naphthenic base of C3 ~ C8 or C4 ~ C20 or dialkyl group propionic ester, and wherein at least one is the integer of the tert-butyl group and 1≤n≤4.

8. autoluminescence photosensitive polymer combination as claimed in claim 7, is characterized in that,

The compound of described chemical formula 1 is by any one in the compound represented in following chemical formula 2 ~ 5,

In described chemical formula 2 ~ 5, R1 ~ R5 is as mentioned above,

X is the alkyl of C1 ~ C6, phenyl, benzyl, O, S, and L is the alkyl propionate of singly-bound or C4 ~ C20

9. autoluminescence photosensitive polymer combination as claimed in claim 8, is characterized in that,

The compound of described chemical formula 2 is 2-TBP, 2,6-DI-tert-butylphenol compounds, 2,4-DTBP, 2-sec-butyl phenol, 2,6-di sec-butylphenol, 2,4-di sec-butylphenol, 2,6-di-t-butyl-4-ethyl-phenol, 2-isopropyl-phenol, 2,6-Bis(1-methylethyl)phenol, 2,4-diisopropyl phenol, 2-tert-octyl phenol, 2,6-bis-tert-octyl phenol, 2,4-bis-tert-octyl phenol, 2-cyclopentylphenol, 2,6-bicyclopentyl phenol, 2,4-bicyclopentyl phenol, 2-Butylated Hydroxytoluene, 2,6-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol, 6-butyl o-cresol, the tertiary dodecyl phenol of 2,6-bis-, the tertiary dodecyl phenol of 2,4-bis-, 2-sec-butyl paracresol, 2,6-bis-tert-octyl phenol, 2,4-bis-tert-octyl phenol, 6-sec-butyl orthoresol, the tertiary octyl group paracresol of 2-, the tertiary dodecyl paracresol of 2-, the 2-tert-butyl group-6-propofol, the tertiary octyl group orthoresol of 6-, the tertiary dodecyl orthoresol of 6-or octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester,

The compound of described chemical formula 3 is 4,4'-fourth subunit two (the 6-tert-butyl group-3-methylphenol), 2,2'-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 4,4'-thiobis (3 methy 6 tert butyl phenol), 1, two [the 3-(3 of 6-hexanediol, 5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester] or 2, two [the 3-(3 of 2-sulfo--divinyl, 5-di-tert-butyl-hydroxy phenyl) propionic ester]

The compound of described chemical formula 4 is 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-tri-(4-hydroxybenzyl) benzene, or 1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene

The compound of described chemical formula 5 is pentaerythrite four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester].

10. autoluminescence photosensitive polymer combination as claimed in claim 1, is characterized in that,

Described alkali soluble resin has the acid number of 20 ~ 200 (KOHmg/g).

11. autoluminescence photosensitive polymer combinations as claimed in claim 1, is characterized in that,

The weight-average molecular weight of described alkali soluble resin is 3,000 ~ 200,000.

12. autoluminescence photosensitive polymer combinations as claimed in claim 1, is characterized in that,

Described alkali soluble resin comprise the polymkeric substance that is selected from carboxylic unsaturated monomer or there is the unsaturated link copolymerizable with it with the one in the co-polymer of monomer and their combination.

13. autoluminescence photosensitive polymer combinations as claimed in claim 12, is characterized in that,

Described carboxylic unsaturated monomer comprises the one be selected from unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid and their combination.

14. autoluminescence photosensitive polymer combinations as claimed in claim 12, is characterized in that,

Described copolymerizable monomer comprises and is selected from aromatic ethenyl compound, unsaturated carboxylic ester compound, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated carboxylic acid epihydric alcohol ester compound, vinyl esters of carboxylic acids compound, unsaturated ethers compounds, vinyl cyanide compound, unsaturated acyl imine compound, aliphatic conjugated diene compounds, there is at the end of strand the huge monomer of single acryloyl group or monomethacrylate acyl group, one in bulky monomer and their combination.

15. autoluminescence photosensitive polymer combinations as claimed in claim 1, is characterized in that,

Described photopolymerizable compound comprises and is selected from nonyl phenyl carbitol acrylate, 2-hydroxyl-3-phenoxypropylacrylate, 2-ethylhexyl carbitol acrylate, acrylic acid-2-hydroxyl ethyl ester, NVP, 1, 6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, two (acryloyl-oxyethyl) ethers of bisphenol-A, 3-methyl pentanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, one in dipentaerythritol six (methyl) acrylate and their combination.

16. autoluminescence photosensitive polymer combinations as claimed in claim 1, is characterized in that,

Described Photoepolymerizationinitiater initiater comprises and is selected from diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzoin dimethylether, 2-hydroxyl-1-[4-(2-hydroxy ethoxy) vinyl]-2-methyl isophthalic acid-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methylthio phenyl sulfenyl)-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, a kind of acetophenone compounds in the oligomer of 2-hydroxy-2-methyl [4-(1-methyl ethylene) vinyl]-1-acetone and their combination.

17. autoluminescence photosensitive polymer combinations as claimed in claim 1, is characterized in that,

Described autoluminescence photosensitive polymer combination also comprises more than one the photopolymerization be selected from styrax compounds, benzophenone compound, compound in triazine class, sulphur compound, anthraquinone analog compound, organic peroxide, thiol base class compound and their combination and causes assistant.

18. autoluminescence photosensitive polymer combinations as claimed in claim 1, is characterized in that,

Described solvent comprises the one be selected from alkylene glycol monoalkyl ethers class, aklylene glycol alkyl ether acetates, arene, ketone, rudimentary and higher alcohols, cyclic ester class and their combination.

19. autoluminescence photosensitive polymer combinations as claimed in claim 1, is characterized in that,

Described autoluminescence photosensitive polymer combination comprises the one be selected from filler, other macromolecular compounds, pigment dispersing agent, adhesion promoter, ultraviolet light absorber, anti-agglomerating agent and their combination.

20. 1 kinds of display device, is characterized in that, its color conversion layer comprising autoluminescence photosensitive polymer combination described any one of claim 1 to 19 on substrate top and produce.