CN101679848B - Phosphor paste composition - Google Patents

Phosphor paste composition Download PDF

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CN101679848B
CN101679848B CN200880019127.0A CN200880019127A CN101679848B CN 101679848 B CN101679848 B CN 101679848B CN 200880019127 A CN200880019127 A CN 200880019127A CN 101679848 B CN101679848 B CN 101679848B
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paste composition
phosphor paste
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CN101679848A (en
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山内健司
福井弘司
宫崎宽子
森田健晴
平池宏至
森口慎太郎
家田泰享
笕鹰縻
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Sekisui Chemical Co Ltd
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7797—Borates
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    • H05B33/00—Electroluminescent light sources
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Abstract

An object of the invention is to provide a phosphor paste composition, which is capable of printing by screen printing, has good phosphor dispersibility, is excellent in storage stability and can be degreased at a low temperature. The invention is directed to the phosphor paste composition containing a (meth)acrylic resin, a phosphor, an organic solvent and a polyoxyethylenesorbitan fatty acid ester having an HLB value of 9 or more, wherein a viscosity when measured by setting a probe revolution at 23 DEG C using a B-type viscometer to 10 rpm is 8 to 40 Pas.

Description

Phosphor paste composition
Technical field
The present invention relates to utilize screen printing printing, the good dispersibility and the package stability of fluor are superior, and the phosphor paste composition of degreasing at low temperatures.
Background technology
In recent years, in order to obtain the body that burns till of different shape, use inorganic particles such as electroconductive powder, ceramic powder are scattered in the inorganic particles paste composition in the adhesive resin.Especially, as inorganic particles the phosphor paste composition that fluor is scattered in the adhesive resin is used in organic EL etc., in recent years, demand improves.
With regard to phosphor paste composition, for example, utilize screen printing, used scraper plate etc. coating process, be used to be processed as flaky teeming practice etc. and be processed as the shape of regulation after, burn till, can form the body that burns till of necessary shape thus.Wherein, screen printing is especially to be fit to a large amount of methods that generate.
The phosphor paste composition that in screen printing, uses preferably has thixotropy.Thixotropy is for example to have estimated under the situation of viscosity with rotational viscosimeter, and (displacement that strain rate is high) viscosity is low under the high situation of rotating speed, (displacement that strain rate is low) character that viscosity is high under the low situation of rotating speed.Require when applying for phosphor paste composition, viscosity is low fully, applies easily, on the other hand, after coating, leaves standstill and when dry, viscosity is high fully, because the character of vertical (curtain coating) is not flowed in deadweight.
As the adhesive resin that in phosphor paste composition, uses, use cellulose-based resins such as having thixotropic TKK 021 usually.But, fluor is scattered in the phosphor paste composition of cellulose-based resin does not then carry out thermolysis if do not burn till at high temperature.Thereby, there is the big energy of needs in the production process, or problem such as firing time is elongated.
To such problem, inquired into to use and compared, at low temperatures the method for the acrylic resin of degreasing with cellulose-based resin.For example, the phosphor paste composition that has used acrylic resin is disclosed in patent documentation 1.
Yet the tackiness that the acrylic resin of such phosphor paste composition causes shows very by force, under the situation of having carried out screen printing, wire drawing (prolonging yarn) takes place, the processing when being difficult to carry out screen printing on plate for screen printing.In addition, the situation of the cellulose-based resin low with having used tackiness is compared, and prints as attenuation sometimes.In addition, in order to remove acrylic resin, need the long-time plate for screen printing that cleans.Additions through reducing acrylic resin etc. can reduce tackiness, but follow in this; The viscosity of phosphor paste composition significantly reduces; Therefore, under the situation of the high fluor of minute bulk specific gravity, there is the problem of so-called " package stability " variation of fluor sedimentation or cohesion.
Therefore, also considered to reduce the addition of acrylic resin, improved the viscosity of phosphor paste composition, kept the method for package stability through increasing the molecular weight of acrylic resin.But, if improve the molecular weight of acrylic resin, then exist wire drawing takes place tempestuously, or the become problem of difficulty of screen printing.
To such problem, for example, the method for in phosphor paste composition, adding thixotropic agent such as fatty acid amide ester, hydrogenated castor oil, polyamino acid is disclosed in patent documentation 2.Yet these thixotropic agent are the additive of the viscosity that is used to increase phosphor paste composition, are not enough to obtain being fit to the phosphor paste composition of screen printing.And then, also there are the pyrolytic variation of phosphor paste composition, residual problem.
In patent documentation 3,, disclose in phosphor paste composition and to have added the method that Triple Pressed Stearic Acid etc. has the compound of an above carboxyl in order to improve the dispersiveness of phosphor paste composition.Disclose the compound that has an above carboxyl through interpolation, carboxyl is adsorbed on the surface of fluor, with the electromotive force neutralization on surface, or makes the inerting of hydrogen bond position, utilizes the stereoeffect of the part beyond the carboxyl, suppresses cohesion, improves the dispersiveness of fluor.But, in such method, be difficult to keep secular package stability, fluor sedimentation sometimes or cohesion.In addition, with regard to the low phosphor paste composition of viscosity, viscosity changes noticeably, and is difficult to obtain being fit to the phosphor paste composition of screen printing.
In patent documentation 4,, disclose in phosphor paste composition to add and comprised that two (2-hydroxyethyl) alkylamines etc. contain the method for nonionic surfactant of the compound of hydroxyalkyl and nitrogen-atoms in order to improve the dispersiveness of fluor.
Yet the viscosity of disclosed phosphor paste composition is 4.4～5.0Pas in the embodiment of patent documentation 3, and therefore, the fluor after just having disperseed shows good dispersiveness, but the sedimentation along with the process of time sometimes.In addition, there is the pyrolytic variation of phosphor paste composition, the problem that residue is residual.
Like this, when being very difficult to guarantee the dispersiveness of fluor, reduce the tackiness of phosphor paste composition, improve screen printing property.
[patent documentation 1] spy opens flat 9-012979 communique
[patent documentation 2] spy opens the 2000-144124 communique
[patent documentation 3] spy opens the 2003-257314 communique
[patent documentation 4] spy opens the 2003-292947 communique
Summary of the invention
The objective of the invention is to provides and can utilize screen printing printing in view of above-mentioned present situation, and the good dispersibility and the package stability of fluor are superior, and the phosphor paste composition of degreasing at low temperatures.
The present invention is a kind of phosphor paste composition; It is that to contain (methyl) vinyl resin, fluor, organic solvent, HLB value be the phosphor paste composition of the polyoxyethylene sorbitan fatty acid ester more than 9; Wherein, Under 23 ℃, use Brookfield viscometer, the detector rotating speed is made as 10rpm and the viscosity of surveying periodic compsn is 8～40Pas.
Below, the present invention is detailed.
The inventor etc. have inquired into as follows; That is: in screen printing designs with phosphor paste; Through as adhesive resin, use (methyl) vinyl resin, reduce the addition of (methyl) vinyl resin; The degreasing under the low temperature of phosphor paste composition be can carry out, thereby screen printing property, package stability improved.Yet, only through reducing the vinyl resin addition, regulate under the situation of viscosity, there is screen printing property variation, in addition, fluor sedimentation or cohesion cause the problem of package stability difference.Therefore, the inventor etc. find through the result of further intent discussion, as adhesive resin; Use (methyl) vinyl resin,, use the polyoxyethylene sorbitan fatty acid ester of specific structure as tensio-active agent; Regulate the viscosity of phosphor paste composition; Can access screen printing property thus, package stability is superior, and the phosphor paste composition of degreasing at low temperatures, thus accomplished the present invention.
Phosphor paste composition of the present invention contains: (methyl) vinyl resin, fluor, organic solvent and HLB value are the polyoxyethylene sorbitan fatty acid ester more than 9.
Phosphor paste composition of the present invention contains (methyl) vinyl resin.Above-mentioned (methyl) vinyl resin has the effect as tackiness agent.
As above-mentioned (methyl) vinyl resin; So long as can be in low temperature (below 400 ℃) degreasing; Just do not limit especially; But for example, can use (methyl) acrylate monomer of methyl (methyl) propenoate, ethyl (methyl) propenoate, propyl group (methyl) propenoate, n-butyl (methyl) propenoate, tert-butyl (methyl) propenoate, isobutyl-(methyl) propenoate, cyclohexyl (methyl) propenoate, 2-ethylhexyl (methyl) propenoate, isobornyl (methyl) propenoate, n-stearyl-(methyl) propenoate, benzyl (methyl) propenoate etc. homopolymer or above-mentioned (methyl) acrylate monomer and polypropyleneoxide, gather methyl oxirane, gather ethyl oxyethane, gather trioxin and gather the multipolymer that tetramethyl aldehyde etc. has (methyl) acrylate monomer of polyoxyalkylene structure.At this, for example, (methyl) propenoate is meant propenoate or methacrylic ester.
Wherein, Because when can reduce the content of (methyl) vinyl resin; Obtain being fit to the phosphor paste composition of screen printing property, therefore, preferably with second-order transition temperature (Tg) height; And the methyl acrylate monomer of degreasing contains as component of polymer at low temperatures, and the homopolymer that especially is fit to the methyl acrylate monomer is a polymethylmethacrylate.
Above-mentioned (methyl) vinyl resin preferably has polar group at molecule chain end.Thus, can improve printing, utilize screen printing to come suitably to print.
If have above-mentioned polar group at molecular side chain, then (methyl) vinyl resin and organic solvent mix, and the viscosity of resin solution is step-down terrifically, in order to keep viscosity, need add the more resin of volume.Its result, tackiness uprises, and therefore, in printed patterns, occurs cotton-shaped part sometimes, maybe can not print.
Be not present in side chain through above-mentioned polar group; And being present in molecule chain end, (methyl) vinyl resin and organic solvent are immiscible, show be separated (microphase-separated) of appropriateness; Even be lower molecular weight and few resin content, also can guarantee the viscosity that the printshop needs.Its result, the tackiness of phosphor paste composition tails off, and is difficult to take place wire drawing, and therefore, it is good that printing treatment property becomes.
Wherein, even use the phosphor paste composition of long-term keeping, also can access good printed patterns; Package stability is superior; Therefore, preferably use polar group not to be present in the molecular side chain of (methyl) vinyl resin, and exist only in (methyl) vinyl resin of molecule chain end.
The especially preferred hydrogen bond property functional group of above-mentioned polar group.
As above-mentioned hydrogen bond property functional group, do not limit especially, for example, can enumerate hydroxyl, carboxyl, amino, polyoxyalkylene ether etc.Wherein, owing to can not have the reason etc. of residue ground thermolysis at low temperatures (methyl) vinyl resin, suitable hydroxyl, carboxyl.
In addition, above-mentioned hydrogen bond property functional group is at least one and gets final product, but many more, phase separation structure is got over stabilization, and the tackiness of phosphor paste composition reduces, and therefore, wire drawing etc. does not take place, the raising of screen printing property, from but effectively.
As the method that imports polar group to the molecule chain end of above-mentioned (methyl) vinyl resin; Specifically; For example; Can enumerate based on chain-transfer agent, utilize radical polymerization, active group polymerization, chain rupture to shift known method in the past such as (イ ニ Off ア one タ one) polymerization, anionic polymerization, active anionic polymerization method, the method for above-mentioned (methyl) vinyl resin monomer polymerization or copolymerization with polar group.
In addition, have the polymerization starters such as organic peroxide evocating agent or azo series initiators of polar group through use, also can import polar group to (methyl) acrylic molecules chain end.
Molecule chain end to (methyl) vinyl resin imports under the situation of polar group, for example, can pass through 13C-NMR confirms.
As chain-transfer agent with above-mentioned polar group; Especially preferably the chain-transfer agent that has hydrogen bond property functional group; For example can enumerate; Have mercapto-propanediol, thioglycerin, have mercaptosuccinic acid, mercaptoacetic acid, have ethylamine mercaptan as the amino of hydrogen bond property functional group etc. as the carboxyl of hydrogen bond property functional group as the hydroxyl of hydrogen bond property functional group.
As organic peroxide evocating agent with above-mentioned polar group; Especially preferably the organic peroxide evocating agent that has hydrogen bond property functional group; For example, can enumerate P-methane hydroperoxide (day oily corporate system " but Pa Ming H "), diisopropyl benzene hydroperoxide (day oily corporate system " Parker Milutinovic P "), 1,2,3,3-tetramethyl butyl hydroperoxide (day oily corporate system " Pa Angkete H "), cumenyl hydroperoxide (day oily corporate system " Parker Milutinovic H-80 "), t-butyl hydroperoxide (day oily corporate system " Pa Dingji H-69 "), cyclohexanone peroxide (day oily corporate system " handkerchief six H "), 1,1,3,3-tetramethyl butyl hydroperoxide, t-butyl hydroperoxide, t-amyl group hydroperoxide, disuccinic acid peroxide (Paro Yi Lu SA) etc.
As azo series initiators with above-mentioned polar group; Especially preferably the azo series initiators that has hydrogen bond property functional group; For example, can suitably use two [N-(2 the carboxy ethyl)-2-methyl propionyl amidine] hydrates or 2 of 2 '-azo as 2; 2 '-azo two { 2-methyl-N-[1, two (the hydroxymethyl)-2-hydroxyethyls of 1-] propionic acid amides } etc. equally has the polymerization starter of hydroxyl or carboxyl.
Above-mentioned (methyl) vinyl resin be limited to 5000 down based on the preferred of the weight-average molecular weight of polystyrene conversion, be limited to 50000 on preferably.If above-mentioned weight-average molecular weight is less than 5000, then (methyl) vinyl resin and organic solvent can not show be separated (microphase-separated) of appropriateness, therefore, can not get the required viscosity of screen printing sometimes.Be limited to 10000 under above-mentioned weight-average molecular weight preferred.If above-mentioned weight-average molecular weight surpasses 50000, then the wire drawing property of phosphor paste composition (stringiness) uprises, thereby easily wire drawing takes place, therefore, and screen printing property variation sometimes.Be limited to 40000 on above-mentioned weight-average molecular weight preferred, and then preferred upper limit is 30000.Especially, the weight-average molecular weight of above-mentioned (methyl) vinyl resin is under 10000～30000 the situation, when screen printing, obtains distinct picture, and is therefore preferred.
In phosphor paste composition in the past, for keep can screen printing viscosity, used (methyl) vinyl resin than higher molecular weight.With respect to this, in phosphor paste composition of the present invention,, also can bring into play good screen printing property under the situation of (methyl) vinyl resin in weight-average molecular weight is 5000～50000 scope through moderately be separated (microphase-separated).
Also have, just,, for example, can use SHOKO corporate system post LF-804, carry out GPC mensuration and obtain as post based on the mensuration of the weight-average molecular weight of polystyrene conversion.
As the MWD of above-mentioned (methyl) vinyl resin (weight-average molecular weight/number-average molecular weight=Mw/Mn), do not limit especially, but be limited to 3 on preferred.If MWD surpasses 3; Then play a role as softening agent as low-molecular-weight monomer or oligopolymer etc.; Sometimes in phosphor paste composition, can not get sufficient viscosity; Or owing to contain high molecular weight components, the wire drawing that (methyl) vinyl resin causes takes place sometimes, problem takes place when screen printing sometimes.Be limited to 2.5 on MWD preferred.
As the content of above-mentioned (methyl) vinyl resin in the phosphor paste composition of the present invention, do not limit especially, but preferably be limited to 5 weight % down, be limited to 25 weight % on preferably.If the content of above-mentioned (methyl) vinyl resin less than 5 weight %, then can not get the phosphor paste composition of the viscosity of suitable screen printing sometimes.If the content of above-mentioned (methyl) vinyl resin surpasses 25%, then because the viscosity of phosphor paste composition becomes too high, and becoming is difficult to carry out screen printing, or the tackiness grow, therefore, wire drawing takes place easily when screen printing sometimes.
Also have; Preferably as the adhesive resin that in phosphor paste composition of the present invention, uses; (methyl) vinyl resin after the polyreaction is refining and under the situation about using, in phosphor paste composition, do not contain as the monomer of low molecular weight compositions or oligopolymer etc.In phosphor paste composition, contain under the situation as the monomer of low molecular weight compositions or oligopolymer etc., monomer or oligopolymer etc. play a role as softening agent sometimes, cause viscosity to reduce.
It is the polyoxyethylene sorbitan fatty acid ester more than 9 that phosphor paste composition of the present invention contains the HLB value.
, in phosphor paste composition,, used under the situation of (methyl) vinyl resin in the past, inquired into dispersiveness and screen printing property, used the situation of various dispersion agents or tensio-active agent etc. in order to improve fluor as adhesive resin.Especially in the low phosphor paste composition of viscosity, can not guarantee the dispersiveness and the screen printing property of fluor fully, according to the kind of the fluor that uses, dispersiveness and screen printing property significantly reduce sometimes.
In the present invention,, can under the situation of the composition that does not rely on fluor, not damage the degreasing property of tackiness agent, significantly improve dispersiveness and screen printing property through such polyoxyethylene sorbitan fatty acid ester is used as tensio-active agent.
The HLB value of above-mentioned polyoxyethylene sorbitan fatty acid ester is more than 9.If above-mentioned HLB value is more than 9, then can access the dispersiveness and the superior phosphor paste composition of screen printing property of fluor.The HLB of above-mentioned polyoxyethylene sorbitan fatty acid ester value less than 9 situation under, the viscosity of phosphor paste composition of the present invention reduces.
If contain above-mentioned polyoxyethylene sorbitan fatty acid ester, then the dispersiveness of fluor becomes well, but the viscosity of phosphor paste composition reduces sometimes.In the present invention, be made as more than 9, can not reduce the viscosity of phosphor paste composition, can access the phosphor paste composition that is fit to screen printing through HLB value with above-mentioned polyoxyethylene sorbitan fatty acid ester.Also have, be limited to 9.5 under above-mentioned HLB value preferred, be limited to 17.0 on preferably.
At this, wetting ability that above-mentioned HLB value is the presentation surface promoting agent or oil loving equilibrated index, more near 0, oleophilicity is high more, and more near 20, wetting ability is high more.Also have, above-mentioned HLB value is a value of for example using the formula of following Griffin to calculate.
[(molecular weight of hydrophilic segment) ÷ (whole molecular weight) * 100]/5
In addition, above-mentioned polyoxyethylene sorbitan fatty acid ester is preferably by the compound of following chemical formula (1) expression and/or by the compound of following chemical formula (2) expression or the compound of being represented by following chemical formula (3).
[changing 1]
Figure G2008800191270D00081
[changing 2]
Figure G2008800191270D00082
[changing 3]
Figure G2008800191270D00083
R 1, R 2And R 3Be C nH 2n-1Or C nH 2n+1(n is the integer more than 5), a+b+c=20, d+e+f=20, g+h+i+j=20.
R in the above-mentioned chemical formula 1, R 2And R 3Be C nH 2n-1Or C nH 2n+1(n is the integer more than 5).If n is less than 5, then above-mentioned polyoxyethylene sorbitan fatty acid ester does not play a role as tensio-active agent, and the dispersiveness of the fluor in the phosphor paste composition reduces sometimes, or screen printing property variation.
In addition, in above-mentioned chemical formula, a+b+c=20, d+e+f=20, g+h+i+j=20.
At this, a+b+c=20 is meant that a, b and c are respectively the integer more than 1, and the summation of a, b and c is 20 the meaning.
In addition, d+e+f=20 is meant that d, e and f are respectively the integer more than 1, and the summation of d, e and f is 20 the meaning.
In addition, g+h+i+j=20 is meant that g, h, i and j are respectively the integer more than 1, and the summation of g, h, i and j is 20 the meaning.
As polyoxyethylene sorbitan fatty acid ester by above-mentioned chemical formula (1) and/or above-mentioned chemical formula (2) expression; For example, can enumerate T 46155 (20) sorbitan monolaurate (KAO. Corp. SA's system " Lyons Dorr TW-L120 " H L B value 16.7), T 46155 (20) sorbitan monostearate (KAO. Corp. SA's system " Lyons Dorr TW-S120V " HLB value 10.5), T 46155 (20) dehydrated sorbitol mono-fatty acid ester (KAO. Corp. SA's system " Lyons Dorr TW-O120V " HLB value 15), T 46155 (20) sorbitan monopalmitate (KAO. Corp. SA's system " Lyons Dorr TW-P120 " HLB value 15.6) etc.
As polyoxyethylene sorbitan fatty acid ester by above-mentioned chemical formula (3) expression; For example, can enumerate polyoxyethylene sorbitol acid anhydride list coconut fatty acid ester (the first industrial drugmaker system " rope reed rhizome TW-20 " HLB value 16.7), polyox-yethylene sorbitan monostearate (the first industrial drugmaker system " rope reed rhizome TW-60 " HLB value 14.9), polyoxyethylene sorbitan monooleate (the first industrial drugmaker system " rope reed rhizome TW-80 " HLB value 15) etc.
As the content of the above-mentioned polyoxyethylene sorbitan fatty acid ester in the phosphor paste composition of the present invention, do not limit especially, but preferably be limited to 0.01 weight % down, be limited to 5 weight % on preferably.If the content of above-mentioned polyoxyethylene sorbitan fatty acid ester less than 0.01 weight %, then manifests the effect of the dispersiveness that improves phosphor paste composition sometimes or improves the effect of screen printing property.If the content of above-mentioned polyoxyethylene sorbitan fatty acid ester surpasses 5 weight %, then the viscosity of phosphor paste composition reduces sometimes, is not suitable for screen printing.Be limited to 0.05 weight % under the content of above-mentioned polyoxyethylene sorbitan fatty acid ester preferred, and then be limited to 1 weight % on preferred.
In addition; Phosphor paste composition of the present invention is for be separated (microphase-separated) of stabilization appropriateness; It is the Voranol EP 2001 more than 11 that phosphor paste composition of the present invention contains the HLB value, can access screen printing property and then superior phosphor paste composition thus.As above-mentioned HLB value is the Voranol EP 2001 more than 11, do not limit especially, for example, can polyoxyethylene lauryl ether, T 46155 n-Hexadecane ether, polyoxyethylene stearyl acyl group ether etc.
Phosphor paste composition of the present invention preferably adds together with above-mentioned polyoxyethylene sorbitan fatty acid ester, and the nonionic that contains the HLB value and be more than 10 is a tensio-active agent.
As above-mentioned HLB value is that nonionic more than 10 is a tensio-active agent; Do not limit especially, but be adapted at the aliphatic chain addition nonionic of alkylene ether be tensio-active agent, specifically; For example, be fit to use polyoxyethylene lauryl ether, T 46155 n-Hexadecane ether etc.Also have; Above-mentioned nonionic is that the pyrolytic of tensio-active agent is good; But adding under a large amount of situation, the heat decomposition temperature of phosphor paste composition uprises sometimes, or produces residue; Therefore, the above-mentioned nonionic in the phosphor paste composition is to be limited to 5 weight % on content preferred of tensio-active agent.
Phosphor paste composition of the present invention contains fluor.
As above-mentioned fluor, do not limit especially, for example, can enumerate CRT with fluor, lamp with fluor, PDP with fluor, X line with fluor, hold the fluor that light fluor etc. uses in various uses.Specifically, for example, can enumerate Y 2O 3: Eu, Y 2O 2S:Eu, YBO 3: Eu, (Y, Gd) BO 3: Eu, Y (P, V) O 4: Eu, GdBO 3: Eu, Y 2SiO 5: Eu, Y 3Al 5O 12: Eu, ScBO 3: Eu, LuBO 3: red-emitting phosphors such as Eu, ZnS:Cu, Al, LaPO 4: Ce, Tb, CaMgSi 2O 6: Eu, (Ba, Sr, Mg) OaAl 2O 3Mn, (Y, Gd) BO 3: Tb, Zn 2SiO 4: Mn, BaAl 12O 19: Mn, BaMgAl 10O 17: Mn, BaMgAl 10O 17: Mn, Eu, BaMgAl 14O 23: Mn, CaAl 12O 19: Mn, SrAl 12O 19: Mn, YBO 3: Tb, LuBO 3: Tb, GdBO 3: Tb, Gd 2O 2S:Tb, ScBO 3: Tb, Sr 4Si 3O 8Cl 4: green-emitting phosphors such as Eu, ZnS:Ag, Al, (SrCaBaMg) 5(PO 4) 3Cl:Eu, BaMgAl 10O 17: Eu, BaMgAl 14O 23: Eu, Y 2SiO 5: Ce, CaWO 4, CaWO 4: Pb, (Ca, Sr) MgSi 2O 6: Eu, (Ca, Sr) Mg 2Si 2O 7: Eu, (Ca, Sr) 2MgSi 2O 7: blue emitting phophors such as Eu, Sr 4Al 14O 25: Eu, blue-greenish colour fluor, Ca such as Dy 10(PO 4) 6FCl:Sb, white phosphors such as Mn etc.
In phosphor paste composition of the present invention, wherein, since dispersed superior, therefore, use BaMgAl 10O 17: blue emitting phophor or Zn such as E u 2SiO 4: green-emitting phosphor or (Y, Gd) BO such as Mn 3: under the situation of red-emitting phosphors such as Eu, can bring into play effect of the present invention fully.Especially of the back, as dispersion agent, use glycerine, poly carboxylic acid, polyether ester amine salt, can guarantee thus and then superior dispersiveness.
Phosphor paste composition of the present invention is containing under the situation of above-mentioned red-emitting phosphors, also is fit to use.
Usually, therefore the proportion of red-emitting phosphors, contain at phosphor paste composition under the situation of red-emitting phosphors than other fluorescence heights, the easy sedimentation of red-emitting phosphors, and package stability is insufficient.To this, in phosphor paste composition of the present invention, under the situation of the imidazolium compounds of having stated after having added, contain under the situation of red-emitting phosphors, red-emitting phosphors can sedimentation yet, and package stability is superior.This thinks because above-mentioned imidazole compound forms the settled structure that suppresses red-emitting phosphors.
Content as above-mentioned fluor; Do not limit especially; But the mixture with respect to (methyl) vinyl resin, organic solvent and polyoxyethylene sorbitan fatty acid ester is adhesive resin composition 100 weight parts; The preferred of the content of above-mentioned fluor is limited to 10 weight parts down, is limited to 300 weight parts on preferably.If the content of above-mentioned fluor less than 10 weight parts, then can not get the phosphor paste composition of the viscosity of suitable screen printing sometimes,, then in adhesive resin composition, be difficult to disperse fluor sometimes if surpass 300 weight parts.Be limited to 50 weight parts under the content of above-mentioned fluor preferred, be limited to 250 weight parts on preferred.
Phosphor paste composition of the present invention contains organic solvent.
Above-mentioned organic solvent preferably has at least one hydroxyl or acetoxyl at molecule.Thus; Be presented at be separated (microphase-separated) of appropriateness that above-mentioned molecule chain end has (methyl) vinyl resin and the organic solvent of polar group easily; When keeping the viscosity (thixotropy) that is fit to screen printing; Reduce the content of (methyl) vinyl resin, easy thereby the degreasing under the low temperature becomes.
As the boiling point of above-mentioned organic solvent, do not limit especially, but preferably be limited to 170 ℃ down, be limited to 280 ℃ on preferably.If the boiling point of above-mentioned organic solvent is less than 170 ℃, then in screen printing, the organic solvent volatilization, the operating efficiency variation of screen printing sometimes, if surpass 280 ℃, then sometimes can not be with phosphor paste composition of the present invention degreasing at low temperatures.Be limited to 200 ℃ under the boiling point of above-mentioned organic solvent preferred, be limited to 250 ℃ on preferred.
As organic solvent; Do not limit especially, for example can enumerate glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, TC, diethylene glycol monomethyl ether, Diethylene Glycol list isobutyl ether, neopentyl glycol mono isobutyrate, Diethylene Glycol single-butyl ether, Diethylene Glycol single-butyl ether acetic ester, terpinol, film coalescence aid, isophorone, lactic acid butyl ester, dioctyl phthalate (dop), dioctyl adipic acid ester, benzyl alcohol, phenyl glycol phenyl Ucar 35, cresols etc.
Wherein, Be fit to TC, diethylene glycol monomethyl ether, Diethylene Glycol list isobutyl ether, Diethylene Glycol single-butyl ether, Diethylene Glycol single-butyl ether acetic ester, terpinol, film coalescence aid; And then; Wherein, especially be fit to Diethylene Glycol list isobutyl ether, Diethylene Glycol single-butyl ether, Diethylene Glycol single-butyl ether acetic ester, terpinol, film coalescence aid, especially be fit to use Diethylene Glycol single-butyl ether, Diethylene Glycol single-butyl ether acetic ester, terpinol, film coalescence aid.
Also have, these organic solvents can use separately, share two or morely also can.
Preferably be made as SP in SP with above-mentioned (methyl) vinyl resin M, the SP of above-mentioned organic solvent is made as SP SThe time, above-mentioned organic solvent satisfies following mathematical expression (4) or following mathematical expression (5).
At this, SP (the following SP value that also is called) is the value of only being calculated by the chemical structure of the material of record in polymer engineering & science 14 147 (1974) etc., can obtain through following mathematical expression (5 ').Mix between the approaching material of SP value, the SP value away from material between be separated from each other.
Satisfy following mathematical expression (4) or following mathematical expression (5) through above-mentioned organic solvent, show be separated (microphase-separated) of the appropriateness of (methyl) vinyl resin and organic solvent easily, obtain the viscosity (thixotropy) of appropriateness, make screen printing property more superior.
[several 1]
-1.0+SP M≤SP S≤-0.2+SP M (4)
[several 2]
0.2+SP M≤SP S≤2.0+SP M (5)
[several 3]
SP S = ( Ev V ) 1 / 2 = ( ΣΔei ΣΔVi ) 1 / 2 - - - ( 5 , )
Ev: evaporation energy (J/mol)
V: mole volume (m 3/ mol)
Δ ei: the evaporation energy of atom or atomic group (cal/mol)
Δ Vi: molecular volume (cm 3/ mol)
Phosphor paste composition of the present invention preferably contains dispersion agent.
As above-mentioned dispersion agent,, use to have the organic cpds of three above hydroxyls, organic cpds, polyether ester amine acid salt etc. with three above carboxyls preferably according to the kind of fluor.These dispersion agents have the effect of the package stability that improves phosphor paste composition.Especially, under the situation of using low viscous phosphor paste composition, importantly,, select the dispersion agent corresponding with the composition of fluor in order to ensure the dispersiveness of fluor.
As organic cpds with above-mentioned hydroxyl more than three, do not limit especially, for example, can enumerate polyalcohols such as glycerine, W 166, polytetramethylene glycol.
As above-mentioned organic cpds with three above carboxyls, do not limit especially, for example, can enumerate terminal olefin-copolymer-maleic anhydride, unsaturated polyester carboxylic-acid, aliphatics polyvalent carboxylic acid's class etc.
These dispersion agents through with the synergy of above-mentioned polyoxyethylene sorbitan fatty acid ester, at fluor, use BaMgAl as low viscous phosphor paste composition 10O 17: under the situation of blue emitting phophors such as Eu, also can realize superior dispersiveness.Especially,, use under glycerine or polyvalent carboxylic acid compounds's the situation, can access the phosphor paste composition of the extremely superior package stability of demonstration as dispersion agent.
As the content of the dispersion agent in the phosphor paste composition of the present invention, do not limit especially, but preferably be limited to 0.1 weight % down, be limited to 5 weight % on preferably.If the content of above-mentioned dispersion agent then can not be kept the dispersion state of the fluor in the phosphor paste composition less than 0.1 weight %, sometimes owing to fluor sedimentation or cohesion, generation problem on package stability.Content at above-mentioned dispersion agent surpasses under the situation of 5 weight %, also can not get further package stability sometimes, or the pyrolytic of phosphor paste composition reduces.Be limited to 1 weight % under the content of above-mentioned organic cpds with three above hydroxyls preferred, be limited to 3 weight % on preferred.
Phosphor paste composition of the present invention is preferred and then contain by following chemical formula (6) or by the imidazole compound of following chemical formula (7) expression.
[changing 4]
Figure G2008800191270D00141
R 4Expression C nH 2n+1(n is the integer more than 5) or C nH 2n-1(n is the integer more than 5), R 5Expression H, C nH 2n+1(n is 1～5 integer) or C nH 2nOH (n is 1～5 integer), R 6Expression H, C nH 2n+1(n is 1～5 integer) or C nH 2nO H (n is 1～5 integer), R 7Expression H or C nH 2n+1(n is 1～5 integer).
[changing 5]
Figure G2008800191270D00142
R 8Expression C nH 2n+1(n is the integer more than 5) or C nH 2n-1(n is the integer more than 5), R 9Expression H, C nH 2n+1(n is 1～5 integer) or C nH 2nOH (n is 1～5 integer), R 10Expression H, C nH 2n+1(n is 1～5 integer) or C nH 2nOH (n is 1～5 integer), R 11Expression H or C nH 2n+1(n is 1～5 integer).
In this manual, imidazole compound is meant by the imidazolinium compounds (glyoxalidine) of above-mentioned chemical formula (6) expression, and by the imidazolium compounds of above-mentioned chemical formula (7) expression.
Wherein, phosphor paste composition of the present invention preferably contains the imidazole compound by above-mentioned chemical formula (6) expression.
In above-mentioned chemical formula (6), R 4For by C nH 2n+1(n is the integer more than 5) or C nH 2n-1The structure of (n is the integer more than 5) expression, but R 4Preferably by C nH 2n+1(n is 5～30 integer) or C nH 2n-1The structure of (n is 5～30 integer) expression.If n less than 5, then obtains the package stability of phosphor paste composition sometimes, if n surpasses 30, then the chain length of alkyl or alkenyl is long, therefore, under the situation with easy fired, produces residue sometimes.
And then, R 4More preferably by C nH 2n+1(n is 10～20 integer) or C nH 2n- 1The structure of (n is 10～20 integer) expression, and be linear chain structure.In above-mentioned chemical formula (6), R 4Under the situation for linear chain structure, can access the superior phosphor paste composition of package stability.
In above-mentioned chemical formula (6), R 5So long as by H, C nH 2n+1(n is 1～5 integer) or, C nH 2nThe structure of OH (n is 1～5 integer) expression does not just limit especially, but wherein preferred H or C 2H 4OH.
In above-mentioned chemical formula (6), R 6So long as preferred H, C nH 2n+1(n is 1～5 integer) or C nH 2nThe structure of OH (n is 1～5 integer) expression does not just limit especially, but wherein preferred H.
In above-mentioned chemical formula (6), R 7So long as by H or C nH 2n+1The structure of (n is 1～5 integer) expression does not just limit especially, but wherein preferred H.
In above-mentioned chemical formula (7), R 8For by C nH 2n+1(n is the integer more than 5) or C nH 2n-1The structure of (n is the integer more than 5) expression, but R 8Preferably by C nH 2n+1(n is 5～30 integer) or C nH 2n-1The structure of (n is 5～30 integer) expression.If n less than 5, then can not get the package stability of phosphor paste composition sometimes, if n surpasses 30, then the chain length of alkyl or alkenyl is long, therefore, under the situation with easy fired, produces residue sometimes.
And then, R 8More preferably by C nH 2n+1(n is 10～20 integer) or C nH 2n- 1The structure of (n is 10～20 integer) expression, and be linear chain structure.In above-mentioned chemical formula (7), R 8Under the situation for linear chain structure, can access the superior phosphor paste composition of package stability.
In above-mentioned chemical formula (7), R 9So long as by H, C nH 2n+1(n is 1～5 integer) or C nH 2nThe structure of OH (n is 1～5 integer) expression does not just limit especially, but wherein, preferred H or C 2H 4OH.
In above-mentioned chemical formula (7), R 10So long as by H, C nH 2n+1(n is 1～5 integer) or, C nH 2nThe structure of OH (n is 1～5 integer) expression does not just limit especially, but wherein preferred H.
In above-mentioned chemical formula (7), R 11So long as by H or, C nH 2n+1The structure of (n is 1～5 integer) expression does not just limit especially, but wherein preferred H.
As the concrete example of above-mentioned imidazole compound, do not limit especially, as imidazole compound, for example, can enumerate 2-(8-17 thiazolinyls)-2-tetrahydroglyoxaline-1-ethanol (R by above-mentioned chemical formula (6) expression 4Be C 7H 14-CH=CH-C 8H 17, R 5Be C 2H 4OH, R 6Be H, R 7Be H), 2-undecyl imidazole quinoline (R 4Be C 11H 23, R 5Be H, R 6Be H, R 7Be H), 2-heptadecyl tetrahydroglyoxaline (R 4Be C 17H 35, R 5Be H, R 6Be H, R 7Be H) etc.Wherein, used under 2-(8-17 thiazolinyls)-2-tetrahydroglyoxaline-1-alcoholic acid situation, can access the superior phosphor paste composition of package stability, therefore, can suitably use.
As imidazole compound, can enumerate 2-(8-17 thiazolinyls)-2-imidazoles-1-ethanol (R by above-mentioned chemical formula (7) expression 8Be C 7H 14-CH=CH-C 8H 1 7, R 9Be C 2H 4OH, R 10Be H, R 11Be H), 2-undecyl imidazole (R 8Be C 11H 23, R 9Be H, R 10Be H, R 11Be H), 2-heptadecyl imidazoles (R 8Be C 17H 35, R 9Be H, R 10Be H, R 11Be H) etc.
As the content of the above-mentioned imidazole compound in the phosphor paste composition of the present invention, do not limit especially, but be limited to 0.01 weight % on preferred, be limited to 10 weight % on preferred.If the content of above-mentioned imidazole compound then can not obtain the package stability of phosphor paste composition sometimes fully less than 0.01 weight %,, then under situation, produce residue sometimes with easy fired if surpass 10 weight %.Be limited to 0.1 weight % under the content of above-mentioned imidazole compound preferred, be limited to 5 weight % on preferred.
Phosphor paste composition of the present invention uses down Brookfield viscometers at 23 ℃, and the detector rotating speed is made as the following 8Pas of being limited to that 10rpm surveys periodic viscosity, on be limited to 40Pas.If the viscosity of phosphor paste composition of the present invention then can not be kept the dispersion state of the fluor in the phosphor paste composition less than 8Pas, sometimes owing to fluor sedimentation or cohesion, generation problem on package stability.In addition, if the viscosity of phosphor paste composition of the present invention surpasses 40Pas, tackiness grow sometimes then, the printing difficulty that becomes.
As the method for making phosphor paste composition of the present invention, do not limit especially, can enumerate method in the past, for example, can enumerate and use ball mill, agitator mill, three various mixing machines such as roller, mix the method for each composition etc.Specifically; Can enumerate the use mixing machine; Mix above-mentioned (methyl) vinyl resin, above-mentioned organic solvent, dispersion agent, polyoxyethylene sorbitan fatty acid ester; After making adhesive resin composition, in this adhesive resin composition, add above-mentioned fluor, and then use mixing machine to come method of mixing etc.
Phosphor paste composition of the present invention can carry out screen printing through comprising above-mentioned formation, and package stability is superior, and can carry out low-temperature defatted.The skimming temp that loses at 99.5% of this low-temperature defatted initial weight that is meant adhesive resin is cryogenic situation; In this manual; Under the common air atmosphere that does not carry out nitrogen displacement etc., it is low-temperature defatted that skimming temp is that 250～400 ℃ situation is defined as.
Can know that according to the present invention can provide and can carry out screen printing, package stability is superior, and the phosphor paste composition of degreasing at low temperatures.
Description of drawings
Fig. 1 be the expression screen printing mode one the example synoptic diagram.
Embodiment
Below, disclosed embodiment illustrates in greater detail the present invention, but the present invention not only is defined in these embodiment.
(embodiment 1)
Possess whisking appliance, water cooler, TM, hot water bath, and the 2L of nitrogen inlet links mixed methyl methacrylate monomers (MMA) 100 weight parts in the flask (separable flask), as the mercapto-propanediol of chain-transfer agent, as Diethylene Glycol single-butyl ether 100 weight parts of organic solvent, obtained monomer mixed solution.
Use nitrogen, made the monomer mixed solution bubbling that obtains 20 minutes, remove dissolved oxygen thus after, link in the flask with nitrogen replacement, when stirring, be warming up to the hot water bath boiling.The vinyl acetic monomer solution that adds polymerization starter.In addition, in polymerization, add repeatedly the vinyl acetic monomer solution of polymerization starter.
After polymerization begins 7 hours, be cooled to room temperature, polymerization is through with.Thus, obtained only having the Diethylene Glycol single-butyl ether solution of the polymethylmethacrylate (PMMA) of hydroxyl at molecule chain end.About the polymkeric substance that obtains, as post, use SHOKO corporate system post LF-804, carry out result based on the analysis of GPC, as shown in table 1 based on the weight-average molecular weight (Mw) of polystyrene conversion.
Diethylene Glycol single-butyl ether solution for the polymethylmethacrylate that obtains like this; Become table 1 described ratio of components ground and then add Diethylene Glycol single-butyl ether and T 46155 (POE) (20) sorbitan monolaurate (KAO. Corp. SA's system " Lyons Dorr TW-L120 "); Disperse with the high speed dispersion agent, made adhesive resin composition.
For the adhesive resin composition that obtains, become the described ratio of components of table 1 ground and add Zn as fluor 2SiO 4: Mn, use high-speed stirring apparatus, mixing fully, handle to reaching lubricious state with three roller mills, made phosphor paste composition.
(embodiment 2～8)
Use the chain-transfer agent of record in the table 1, regulate addition, obtained having the weight-average molecular weight of record in the table 1, the polymethylmethacrylate of functional end-group thus.Then, become the described ratio of components of table 1 ground and regulate each composition, in addition,, made adhesive resin composition, reached phosphor paste composition with embodiment 1 identical ground.At this; As tensio-active agent, polyoxy lauryl ether (daylight pharmaceutical chemicals corporate system " NIKKOL BL-25 "), POE (20) sorbitan monostearate, POE (20) dehydrated sorbitol mono-fatty acid ester, POE (20) sorbitan monopalmitate, polyoxyethylene sorbitol acid anhydride list coconut fatty acid ester (the first industrial drugmaker system " rope reed rhizome TW-20 "), polyox-yethylene sorbitan monostearate (the first industrial drugmaker system " rope reed rhizome TW-60 "), polyoxyethylene sorbitan monooleate (the first industrial drugmaker system " rope reed rhizome TW-80 ") have been used.
(embodiment 9)
Possess whisking appliance, water cooler, TM, hot water bath, and the 2L of nitrogen inlet links mixed methyl methacrylic ester (MMA) 100 weight parts in the flask, as mercaptosuccinic acid 3.8 weight parts of chain-transfer agent, as 2 of organic solvent; 2; 4-trimethylammonium-1; 3-pentanediol mono isobutyrate (film coalescence aid (テ キ サ ノ one Le)) 100 weight parts have obtained monomer mixed solution.
Use nitrogen, made the monomer mixed solution bubbling that obtains 20 minutes, remove dissolved oxygen thus after, link in the flask with nitrogen replacement, when stirring, be warming up to the hot water bath boiling.The vinyl acetic monomer solution that adds polymerization starter.And then, in polymerization, add repeatedly the vinyl acetic monomer solution of polymerization starter.
After polymerization begins 7 hours, be cooled to room temperature, polymerization is through with.Thus, obtained having endways hydroxyl polymethylmethacrylate (PMMA) 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate solution.About (methyl) vinyl resin that obtains, as post, use SHOKO corporate system post LF-804, carry out result based on the analysis of GPC, as shown in table 1 based on the weight-average molecular weight (Mw) of polystyrene conversion.
For 2 of the polymethylmethacrylate that obtains like this; 2,4-trimethylammonium-1,3-pentanediol mono isobutyrate solution; Become table 1 described ratio of components ground and then add 2; 2,4-trimethylammonium-1,3-pentanediol mono isobutyrate, as T 46155 (POE) (20) sorbitan monolaurate (KAO. Corp. SA's system " Lyons Dorr TW-L120 ") of tensio-active agent, and polyoxyethylene lauryl ether (daylight pharmaceutical chemicals corporate system " NIKKOL BL-25 "); Disperse with the high speed dispersion agent, made adhesive resin composition.
For the adhesive resin composition that obtains, become the described ratio of components of table 1 ground and add Zn as fluor 2SiO 4: Mn (green-emitting phosphor), use high-speed stirring apparatus, mixing fully, carry out mixingly to reaching lubricious state with three roller mills, made phosphor paste composition.
(embodiment 10)
To be made as 0.7 weight part as the mercaptosuccinic acid that chain-transfer agent uses, obtained polymethylmethacrylate after, polymethylmethacrylate, 2; 2; 4-trimethylammonium-1, the content of 3-pentanediol mono isobutyrate, and tensio-active agent be made as the composition shown in the table 1, in addition; With embodiment 9 identical ground, made phosphor paste composition.
(embodiment 11)
As organic solvent, use the α-terpinol of the composition shown in the table 1 and the mixed solvent of acetate of butyl carbitol, tensio-active agent is made as the composition shown in the table 1, in addition,, made phosphor paste composition with embodiment 9 identical ground.
(embodiment 12)
As chain-transfer agent; Use mercaptosuccinic acid 0.7 weight part,, use the α-terpinol of the composition shown in the table 1 and the mixed solvent of acetate of butyl carbitol as organic solvent; Polymethylmethacrylate, organic solvent, tensio-active agent are made as the composition shown in the table 1; In addition, with embodiment 9 identical ground, made phosphor paste composition.
(comparative example 1)
Do not add tensio-active agent, in addition,, made phosphor paste composition with embodiment 1 identical ground.
(2 4 of comparative examples)
Used the described tensio-active agent of table 1, in addition,, made phosphor paste composition with embodiment 1 identical ground.
(comparative example 5)
As tensio-active agent; Use sorbitan monostearate (KAO. Corp. SA's system " Lyons Dorr SP-S10V "), and, polyoxyethylene lauryl ether (daylight ケ ミ カ Le ズ corporate system " NIKKOL BL-4.2 "); In addition; With embodiment 1 identical ground, made phosphor paste composition.
(comparative example 6)
As tensio-active agent; Use sorbitan tristearate (KAO. Corp. SA's system " Lyons Dorr SP-S30V "), and, polyoxyethylene lauryl ether (daylight ケ ミ カ Le ズ corporate system " NIKKOL BL-2 "); In addition; With embodiment 1 identical ground, made phosphor paste composition.
< evaluation >
About adhesive resin composition and the phosphor paste composition that in embodiment 1～12 and comparative example 1～6, obtains, the evaluation below having carried out.The result is illustrated in the table 2.
(1) viscosimetric analysis
Use Brookfield viscometer (BROOK FIELD corporate system " DVII+Pro "), under the condition of 23 ℃ of temperature, rotating speed 10rpm,, measured the viscosities il of phosphor paste composition for the phosphor paste composition that obtains 10rpm(Pas).
(2) surfaceness evaluation
The phosphor paste composition that obtains is coated on sliding glass (2cm * 5cm) with becoming thickness 12.5 μ m.The sliding glass that has applied phosphor paste composition after under 120 ℃ dry 10 minutes, has been measured the surface of the phosphor paste composition that applies with surfaceness meter (little slope institute's corporate system " Sa Fu Coud SE-30D ").By following benchmark, estimated surface roughness Ra.
Zero: Ra=is less than 1.0 μ m
*: more than the Ra=1.0 μ m
(3) the dispersed evaluation
With mesh-of-grind appearance (Sven-Gan Eriksson corporate system, 0～15 μ m), for the phosphor paste composition that obtains, measure the distribution density of fluor, observed the scale at the position that the fluor of cohesion manifests.Wherein, carry out 5 times and measure, estimated the graduated MV at the position that the fluor that condense manifest with 10 row.By following benchmark, estimated dispersiveness.
Zero: less than 10 μ m
*: more than the 10 μ m
(4) screen printing
Under the environment of 23 ℃ of temperature, 50 ℃ of humidity,, carried out screen printing to the phosphor paste composition that obtains.
In screen printing; (Tokyo technology service company system " SX230 ° of B " (emulsion 20 μ m, web plate frame 320mm * 320mm)), printed base plate (soda glass 150mm * 150mm, thickness 15mm) have carried out screen printing under the condition of following screen printer to use screen printer (Mike's enlightening gram corporate system " MT-320TV "), web plate plate-making.
Gap: 2.0mm
Squeegee (ス キ one ジ) speed: 50mm/s
Scraper plate (ス Network レ Star パ one) speed: 50mm/s
Squeegee pressure: 0.25MPa
Scraper plate pressure: 0.17MPa
Back pressure: 0.10MPa
Utilize stereomicroscope, the printing picture that obtains with visual observation evaluation.
◎: do not have inequality on the rugosity of printing picture, the printing picture is thick fully, and density is high
Zero: do not have inequality on the rugosity of printing picture
△: the printing picture rugosity on do not have inequality but the printing as extremely thin
*: the printing as on inequality is arranged
Figure G2008800191270D00221
Figure G2008800191270D00231
[table 2]
Figure G2008800191270D00241
(embodiment 13)
Possess whisking appliance, water cooler, TM, hot water bath, and the 2L of nitrogen inlet links mixed methyl methacrylate monomers (MMA) 100 weight parts in the flask, as the mercapto-propanediol of chain-transfer agent, as Diethylene Glycol single-butyl ether 100 weight parts of organic solvent, obtained monomer mixed solution.
Use nitrogen, made the monomer mixed solution bubbling that obtains 20 minutes, remove dissolved oxygen thus after, link in the flask with nitrogen replacement, when stirring, be warming up to the hot water bath boiling.The vinyl acetic monomer solution that adds polymerization starter, and then, in polymerization, add repeatedly the vinyl acetic monomer solution of polymerization starter.
After polymerization begins 7 hours, be cooled to room temperature, polymerization is through with.Thus, obtained having endways the Diethylene Glycol single-butyl ether solution of the polymethylmethacrylate (PMMA) of hydroxyl.About (methyl) vinyl resin that obtains, as post, use SHOKO corporate system post LF-804, carry out result based on the analysis of GPC, as shown in table 3 based on the weight-average molecular weight of polystyrene conversion.
Diethylene Glycol single-butyl ether solution for the polymethylmethacrylate that obtains like this; Becoming table 3 described ratio of components ground and then adding Diethylene Glycol single-butyl ether, glycerine, T 46155 (POE) (20) sorbitan monolaurate (KAO. Corp. SA's system " Lyons Dorr TW-L120 "), reach as nonionic is the polyoxyethylene lauryl ether (daylight pharmaceutical chemicals corporate system " NIKKOL BL-25 ") of tensio-active agent; Disperse with the high speed dispersion agent, made adhesive resin composition.
For the adhesive resin composition that obtains, become the described ratio of components of table 3 ground and add BaMgAl as fluor 10O 17: Eu (blue emitting phophor), use high-speed stirring apparatus, mixing fully, handle to reaching lubricious state with three roller mills, made phosphor paste composition.
(embodiment 14,15,17,18)
Use table 3 described (methyl) vinyl resin, organic solvent, tensio-active agent, dispersion agent, in addition,, made phosphor paste composition with embodiment 13 identical ground.
(embodiment 16)
As chain-transfer agent, use mercaptosuccinic acid, in addition,, made the Diethylene Glycol single-butyl ether solution of polymethylmethacrylate with embodiment 13 identical ground.
Then; The Diethylene Glycol single-butyl ether solution of the polymethylmethacrylate that use obtains, as T 46155 (POE) (20) sorbitan monolaurate (KAO. Corp. SA's system " Lyons Dorr TW-L120 ") of tensio-active agent, and polyoxyethylene lauryl ether (daylight pharmaceutical chemicals corporate system " NIKKOL BL-25 "); In addition; With embodiment 13 identical ground, made phosphor paste composition.
(comparative example 7～11)
Use the described chain-transfer agent of table 3, made the Diethylene Glycol single-butyl ether solution of polymethylmethacrylate identically with embodiment 13.Then, each composition is regulated on the ratio of components ground that becomes table 3, in addition, with embodiment 13 identical ground, has made adhesive resin composition, has reached phosphor paste composition.
At this, be tensio-active agent as nonionic, use polyoxyethylene lauryl ether (daylight pharmaceutical chemicals corporate system " NIKKOL BL-25 "), as dispersion agent, used the described material of table 3.
< evaluation >
About adhesive resin composition and the phosphor paste composition that obtains in embodiment 13～18 and the comparative example 7～11, the evaluation below having carried out.The result is illustrated in the table 4.
(1) viscosity evaluation
Use Brookfield viscometer (BROOK FIELD corporate system " DVII+Pro "), under the condition of 23 ℃ of temperature, rotating speed 10rpm,, measured the viscosities il of phosphor paste composition for the phosphor paste composition that obtains 10rpm(Pas).
(2) screen printing property
The phosphor paste composition that obtains was taken care of one month under the environment of 23 ℃ of temperature, humidity 50%.Then; For the phosphor paste composition that obtains; Use screen printer (Mike's enlightening gram corporate system " MT-320TV "), web plate plate-making (Tokyo technology service company system " SX230 ° of B " (emulsion 20 μ m, web plate frame 320mm * 320mm)), printed base plate (soda glass 150mm * 150mm, thickness 15mm); Under the environment of 23 ℃ of temperature, humidity 50%, under the condition of following screen printer, carried out screen printing:
Gap: 2.0mm
Squeegee speed: 50mm/s
Scraper velocity: 50mm/s
Squeegee pressure: 0.25MPa
Scraper plate pressure: 0.17MPa
Back pressure: 0.10MPa
By following benchmark, estimated screen printing property.
Zero: formed clean and tidy printed patterns.
*: printed patterns has cotton-shaped (か The れ) part, maybe can not print.
(3) package stability
23 ℃ of down keepings after month, having or not of the sedimentation of be separated (liquid object separation), fluor through Visual Confirmation solution etc. estimated by following benchmark with the phosphor paste composition that obtains.
Zero: do not confirm to sedimentation of be separated (liquid object separation), the fluor of solution etc.
*: phosphor paste composition fully is separated, and observes the sedimentation of fluor, and the viscosity of supernatant reduces.Perhaps, fluor is deposited in the bottom of container, has formed particle layer.
(4) decomposition temperature is measured (TG-DTA estimates (evaluation of degreasing property))
To the adhesive resin composition that obtains; Use thermal decomposer (TA instrument company system " simultaneous SDT2960 "); Under air atmosphere; Be heated to 600 ℃ for 10 ℃/minute with the intensification temperature, measured the temperature that the thermolysis of 99.5 weight % of the initial weight of adhesive resin composition finishes.The pyrolysated end temp is judged as degreasing property zero less than 400 ℃ adhesive resin composition, with the adhesive resin composition more than 400 ℃ be judged as degreasing property *.
Figure G2008800191270D00281
[table 4]
Viscosity (10rpm) (Pas) Screen printing property Package stability Degreasing property
Embodiment 13 8 ○ ○ ○
Embodiment 14 38 ○ ○ ○
Embodiment 15 15 ○ ○ ○
Embodiment 16 20 ○ ○ ○
Embodiment 17 10 ○ ○ ○
Embodiment 18 37 ○ ○ ○
Comparative example 7 15 × * (liquid object separation) ○
Comparative example 8 19 × * (fluor sedimentation) ○
Comparative example 9 25 × * (fluor sedimentation) ×
Comparative example 10 23 × * (fluor sedimentation) ×
Comparative example 11 22 × * (fluor sedimentation) ×
(embodiment 19)
Possess whisking appliance, water cooler, TM, hot water bath, and the 2L of nitrogen inlet links mixed methyl methacrylate monomers (MMA) 100 weight parts in the flask, as the mercapto-propanediol of chain-transfer agent, as Diethylene Glycol single-butyl ether 100 weight parts of organic solvent, obtained monomer mixed solution.
Use nitrogen, to the monomer mixed solution bubbling that obtains 20 minutes, remove dissolved oxygen thus after, link in the flask with nitrogen replacement, when stirring, be warming up to the hot water bath boiling.The vinyl acetic monomer solution that adds polymerization starter, and then, in polymerization, add repeatedly the vinyl acetic monomer solution of polymerization starter.
After polymerization begins 7 hours, be cooled to room temperature, polymerization is through with.Thus, obtained having endways the Diethylene Glycol single-butyl ether solution of the polymethylmethacrylate (PMMA) of hydroxyl.About (methyl) vinyl resin that obtains, as post, use SHOKO corporate system post LF-804, carry out result based on the analysis of GPC, as shown in table 5 based on the weight-average molecular weight of polystyrene conversion.
For the Diethylene Glycol single-butyl ether solution of the polymethylmethacrylate that obtains like this, become table 5 described ratio of components ground and then add the Diethylene Glycol single-butyl ether, disperse with the high speed dispersion agent, made adhesive resin composition.
For the adhesive resin composition that obtains; To become 0.2 weight % as the polyoxyethylene sorbitol acid anhydride stearate (day oily corporate system " Nuo Niang ST221 ") of tensio-active agent, will become 0.3 weight % ground as 2-(8-17 the thiazolinyls)-2-tetrahydroglyoxaline-1-ethanol of dispersion agent and add.Become the described ratio of components of table 5 ground and add (Y, Gd) BO as fluor 3: Eu (red-emitting phosphors), use high-speed stirring apparatus, mixing fully, handle to reaching lubricious state with three roller mills, made phosphor paste composition.
(embodiment 20,21, comparative example 12～17)
Become the described ratio of components of table 5 or table 6 ground and regulate each composition, in addition,, made adhesive resin composition, reached phosphor paste composition with embodiment 19 identical ground.
(evaluation)
About the phosphor paste composition of embodiment 19～21 and comparative example 12～17 making, estimate through following method.
(1) package stability (viscosity velocity of variation (%))
Put into the 250ml polythene container with just having disperseed the phosphor paste composition behind the fluor; Use Brookfield viscometer (BROOK FIELD corporate system " DVII+Pro "); Under the condition of 23 ℃ of temperature, rotating speed 10rpm, measured the viscosities il of phosphor paste composition A 10rpm(Pas).Then; Under the environment of 23 ℃ of temperature, humidity 50%, keeping reused Brookfield viscometer after one month with the phosphor paste composition of putting into polythene container; Under the condition of 23 ℃ of temperature, rotating speed 10rpm, measured the viscosities il of phosphor paste composition B 10rpm(Pas), calculated viscosity velocity of variation (%).
Through following formula, calculated viscosity velocity of variation (%)
Viscosity velocity of variation (%)=((η A 10rpm-η B 10rpm)/η A 10rpm) * 100
(2) package stability (sedimentary having or not)
With just having disperseed the phosphor paste composition behind the fluor to put into the 250ml polythene container, whether there is throw out in the bottom of container through visual observation.Then, with the phosphor paste composition of putting into polythene container under the environment of 23 ℃ of temperature, humidity 50%, the keeping one month after, once more through visual observation whether have throw out in the bottom of container.
Through following benchmark, estimate whether there is throw out in the bottom of container.
Zero: throw out is not observed in the bottom at container.
*: throw out is observed in the bottom at container.
(3) screen printing property
With just having disperseed the phosphor paste composition behind the fluor to put into the 250ml polythene container, under the environment of 23 ℃ of temperature, humidity 50%, took care of one month.Secondly, use the phosphor paste composition of keeping under the environment of 23 ℃ of temperature, humidity 50%, carried out screen printing.
In screen printing; (Tokyo technology service company system " SX230 ° of B " (emulsion 20 μ m, web plate frame 320mm * 320mm)), printed base plate (soda glass 150mm * 150mm, thickness 15mm) have carried out screen printing under the condition of following screen printer to use screen printer (Mike's enlightening gram corporate system " MT-320TV "), web plate plate-making
Gap: 2.0mm
Squeegee speed: 50mm/s
Scraper velocity: 50mm/s
Squeegee pressure: 0.25MPa
Scraper plate pressure: 0.17MPa
Back pressure: 0.10MPa
The appearance of screen printing shown in Fig. 1.Printed patterns 1 shown in Figure 1 is the travel direction with respect to squeegee, the printed patterns that along continuous straight runs forms.Printed patterns 2 shown in Figure 1 is the travel directions with respect to squeegee, with the printed patterns of the 45 ° of directions formation of tilting.
About printed patterns shown in Figure 11 and printed patterns 2,, estimated screen printing property by following benchmark.
Zero: on printed patterns, do not find cotton-shaped part.
*: found that on printed patterns cotton-shaped part maybe can not print.
Figure G2008800191270D00321
Figure G2008800191270D00331
[table 7]
Figure G2008800191270D00341
(embodiment 22)
Possess whisking appliance, water cooler, TM, hot water bath, and the 2L of nitrogen inlet links mixed methyl methacrylic ester (Mitsubishi's Leiyang corporate system) 100 weight parts in the flask, as mercaptosuccinic acid (with the pure medicine corporate system of light) 1.5 weight parts of chain-transfer agent, as film coalescence aid (republicanism fermentation chemistry drug company system) 100 weight parts of organic solvent, obtained monomer mixed solution.
Use nitrogen, to the monomer mixed solution bubbling that obtains 20 minutes, remove dissolved oxygen thus after, link in the flask with nitrogen replacement, when stirring, being warming up to solution temperature becomes 95 ℃.After reaching temperature, add the solution that has diluted polymerization starter with vinyl acetic monomer.In addition, in polymerization, add the vinyl acetic monomer solution that repeatedly contains polymerization starter.
After polymerization begins 10 hours, be cooled to room temperature, polymerization is through with.Thus, as (methyl) vinyl resin, obtained the film coalescence aid solution of polymethylmethacrylate (PMMA).
(methyl) vinyl resin about obtaining carries out the result based on the analysis of GPC, is 5000 based on the weight-average molecular weight of polystyrene conversion.Also have, in the mensuration of polystyrene conversion weight-average molecular weight,, used SHOKO corporate system post LF-804 as post.
To polymethyl methacrylate solution that obtains and then interpolation film coalescence aid, use the high speed dispersion agent to make its dispersion, obtained thus containing the adhesive resin composition of film coalescence aid 39.7 weight % with respect to polymethylmethacrylate 25 weight %.
For the adhesive resin composition that obtains, add T 46155 (POE) (20) sorbitan monolaurate (KAO. Corp. SA's system " Lyons Dorr TW-L120 ") 0.2 weight %, as poly carboxylic acid (nanmu originally changes into corporate system, " this compels dragon 2150 enlightening ") 0.1 weight % and green-emitting phosphor powder (Ri Ya chemical company system, the Zn of dispersion agent as tensio-active agent 2SiO 4: Mn) 35 weight %, with the processing of fully mixing of three roller mills, made phosphor paste composition thus.
(embodiment 23～25)
Become the described ratio of components of table 8 ground and regulate each composition, in addition,, made adhesive resin composition, reached phosphor paste composition with embodiment 22 identical ground.
(comparative example 18,19)
Become the described ratio of components of table 8 ground and regulate each composition, in addition,, made adhesive resin composition, reached phosphor paste composition with embodiment 22 identical ground.
< evaluation >
About the phosphor paste composition that in embodiment 22～25, comparative example 18,19, obtains, the evaluation below having carried out.The result is illustrated in the table 9.
(1) viscosimetric analysis
Use Brookfield viscometer (BROOK FIELD corporate system " DVII+Pro "); Under the condition of 23 ℃ of temperature, rotating speed 10rpm; For the phosphor paste composition that obtains, under the condition of 23 ℃ of temperature, rotating speed 10rpm, measured the viscosities il of phosphor paste composition 10rpm(Pas).
(2) surfaceness evaluation
The phosphor paste composition that obtains is coated on sliding glass (2cm * 5cm) with becoming thickness 12.5 μ m.The sliding glass that has applied phosphor paste composition after under 120 ℃ dry 10 minutes, has been measured the surface of the phosphor paste composition that applies with surfaceness meter (little slope institute's corporate system " Sa Fu Coud SE-30D ").By following benchmark, estimated surface roughness Ra.
Zero: Ra=is less than 1.0 μ m
*: more than the Ra=1.0 μ m
(3) the dispersed evaluation
With mesh-of-grind appearance (Sven-Gan Eriksson corporate system, 0～15 μ m), for the phosphor paste composition that obtains, measure the distribution density of fluor, observed the scale at the position that the fluor of cohesion manifests.Wherein, carry out 5 times and measure, estimated the graduated MV at the position that the fluor that condense manifest with 10 row.By following benchmark, estimated dispersiveness.
Zero: less than 10 μ m
*: more than the 10 μ m
(4) screen printing
Under the environment of 23 ℃ of temperature, 50 ℃ of humidity,, carried out screen printing to the phosphor paste composition that obtains.
In screen printing; (Tokyo technology service company system " SX230 ° of B " (emulsion 20 μ m, web plate frame 320mm * 320mm)), printed base plate (soda glass 150mm * 150mm, thickness 15mm) have carried out screen printing under the condition of following screen printer to use screen printer (Mike's enlightening gram corporate system " MT-320TV "), web plate plate-making.
Gap: 2.0mm
Squeegee speed: 50mm/s
Scraper velocity: 50mm/s
Squeegee pressure: 0.25MPa
Scraper plate pressure: 0.17MPa
Back pressure: 0.10MPa
Utilize stereomicroscope, the printing picture that obtains with visual observation evaluation.
◎: do not have inequality on the rugosity of printing picture, the printing picture is thick fully, and density is high
Zero: do not have inequality on the rugosity of printing picture
△: the printing picture rugosity on do not have inequality but the printing as extremely thin
*: the printing as on inequality is arranged
Figure G2008800191270D00371
[table 9]
Figure G2008800191270D00381
Utilizability on the industry
Can know that according to the present invention can provide and can utilize screen printing printing, the good dispersibility and the package stability of fluor are superior, and the phosphor paste composition of degreasing at low temperatures.

Claims (13)

1. phosphor paste composition; It is characterized in that; It is that to contain (methyl) vinyl resin, fluor, organic solvent, HLB value be the phosphor paste composition of the polyoxyethylene sorbitan fatty acid ester more than 9; Said (methyl) vinyl resin is to have (methyl) vinyl resin of polar group in degreasing below 400 ℃ and at molecule chain end, and said HLB value is a value of utilizing the formula of following Griffin to calculate
[(molecular weight of hydrophilic segment) ÷ (whole molecular weight) * 100]/5,
Using down Brookfield viscometers at 23 ℃, is that the viscosity that 10rpm surveys periodic compsn is 8～40Pas with the detector speed setting.
2. phosphor paste composition according to claim 1 is characterized in that,
Polyoxyethylene sorbitan fatty acid ester is by the compound of following chemical formula (1) expression and/or by the compound of following chemical formula (2) expression or the compound of being represented by following chemical formula (3),
[changing 1]
Figure FDA00001788940200011
[changing 2]
Figure FDA00001788940200012
[changing 3]
Figure FDA00001788940200021
R 1, R 2And R 3Be C nH 2n-1Or C nH 2n+1, a+b+c=20, d+e+f=20, g+h+i+j=20, wherein, n is the integer more than 5.
3. phosphor paste composition according to claim 1 and 2 is characterized in that,
The weight-average molecular weight based on polystyrene conversion of (methyl) vinyl resin is 5000～50,000.
4. phosphor paste composition according to claim 1 is characterized in that,
Polar group is a hydrogen bond property functional group.
5. phosphor paste composition according to claim 1 and 2 is characterized in that,
(methyl) vinyl resin is a polymethylmethacrylate.
6. phosphor paste composition according to claim 1 and 2 is characterized in that,
The content of (methyl) vinyl resin is 5～25 weight %.
7. phosphor paste composition according to claim 1 and 2 is characterized in that,
And then contain organic cpds as dispersion agent with three above hydroxyls.
8. phosphor paste composition according to claim 7 is characterized in that,
Organic cpds with three above hydroxyls is a glycerine.
9. phosphor paste composition according to claim 1 and 2 is characterized in that,
And then contain organic cpds as dispersion agent with three above carboxyls.
10. phosphor paste composition according to claim 1 and 2 is characterized in that,
And then contain the polyether ester amine acid salt as dispersion agent.
11. phosphor paste composition according to claim 7 is characterized in that,
The content of dispersion agent is 0.1～5 weight %.
12. phosphor paste composition according to claim 1 and 2 is characterized in that,
And then to contain the HLB value be the Voranol EP 2001 more than 11, and said HLB value is a value of utilizing the formula of following Griffin to calculate,
[(molecular weight of hydrophilic segment) ÷ (whole molecular weight) * 100]/5.
13. phosphor paste composition according to claim 1 and 2 is characterized in that, and then contains the imidazolium compounds by following chemical formula (6) or following chemical formula (7) expression,
[changing 4]
Figure FDA00001788940200031
R 4Expression C nH 2n+1Or C nH 2n-1, wherein n is the integer more than 5, R 5Expression H, C nH 2n+1Or C nH 2nOH, wherein n is 1～5 integer, R 6Expression H, C nH 2 N+1Or C nH 2nOH, wherein n is 1～5 integer, R 7Expression H or C nH 2n+1, wherein n is 1～5 integer,
[changing 5]
Figure FDA00001788940200032
R 8Expression C nH 2n+1Or C nH 2n-1, wherein n is the integer more than 5, R 9Expression H, C nH 2n+1Or C nH 2nOH, wherein n is 1～5 integer, R 10Expression H, C nH 2 N+1Or C nH 2nOH, wherein n is 1～5 integer, R 11Expression H or C nH 2n+1, wherein n is 1～5 integer.
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