CN102333818A - Inorganic microparticle-dispersed paste composition - Google Patents
Inorganic microparticle-dispersed paste composition Download PDFInfo
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- CN102333818A CN102333818A CN2010800092766A CN201080009276A CN102333818A CN 102333818 A CN102333818 A CN 102333818A CN 2010800092766 A CN2010800092766 A CN 2010800092766A CN 201080009276 A CN201080009276 A CN 201080009276A CN 102333818 A CN102333818 A CN 102333818A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
Abstract
Disclosed is an inorganic microparticle-dispersed paste composition which can be defatted at low temperature and has excellent dispersibility and storage stability. The inorganic microparticle-dispersed paste composition comprises a (meth)acrylic resin, inorganic microparticles, and an organic solvent. The (meth)acrylic resin has an amino group or an amide group at a molecular end and has a weight average molecular weight in terms of polystyrene of 5000 to 100000.
Description
Technical field
The present invention relates to can be low-temperature defatted, and the inorganic particles dispersed, that storage stability is excellent disperses paste composition.
Background technology
In recent years, making the inorganic particles of electroconductive powder, ceramic powder etc. be scattered in the inorganic particles that adhesive resin forms disperses paste composition to be used to obtain the body that burns till of different shape.The glass paste that especially will be scattered in phosphor paste composition that adhesive resin forms as the fluor of inorganic particles, make low melting glass disperse to form is used in the plasma display etc., and needs in recent years constantly raise.
Adhesive resin as using in the inorganic particles dispersion paste composition uses cellulose-based resins such as having thixotropic TKK 021 usually.; After considering to make inorganic particles to disperse and pattern being printed with silk screen printing; Carry out degreasing, burn till, when obtaining the such technology of layer with inorganic particles, because the pyrolytic of cellulose-based resin is poor; So must carry out degreasing at high temperature more, need a large amount of problems such as the energy in the production process thereby exist in.
To such problem, studied the method that pyrolytic is good, can carry out the acrylic resin of degreasing at low temperature of using, for example, in the patent documentation 1, disclose the inorganic particles that has used acrylic resin and disperseed paste composition.Used the inorganic particles of TKK 021 to disperse paste composition and used and when the inorganic particles dispersion paste composition of low-temperature defatted acrylic resin is compared, to have used the inorganic particles of TKK 021 to disperse the aspect of paste composition to be difficult to cause the sedimentation of inorganic particles.Its reason is that the hydroxyl in the cellulosic molecule is influential to dispersion stabilization.Therefore, in the time of can imagining on the monomeric ester substituting group in vinyl resin the polar group that imports with the hydroxyl of TKK 021 equal extent etc., the dispersed raising, but in fact pyrolytic becomes the degree that does not almost have difference with TKK 021.
Therefore, studied in the patent documentation 2 on the ester substituting group of vinyl resin and almost do not imported polar group, but, improved the method for the storage stability of paste composition through a small amount of dispersion agent that adds in paste composition.At this moment; Glass powder, ceramic powder, fluor etc. have through interpolation and have the tendency that amino dispersion agent improves dispersion stabilization, and at the reverse side of this tendency, used dispersion agent is poor more than the pyrolytic of TKK 021; Even if a small amount of, also become the residue behind the sintering easily.
On the other hand; Also attempted importing in the ester substituting group in vinyl resin amino method, even if but under the situation of the amino of importing minute quantity, the pyrolytic of vinyl resin also significantly worsens; In addition; Through between amino and the Acrylic Acid Monomer Michael reaction takes place, the tendency of giant moleculeization is arranged, it is difficult adjusting to the molecular weight of vinyl resin less.
The look-ahead technique document
Patent documentation
Patent documentation 1: TOHKEMY 2004-002164 communique
Patent documentation 2: No. 3832177 communiques of Japanese Patent
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide and to disperse paste composition at the inorganic particles low-temperature defatted, dispersed, that storage stability is excellent.
The means that are used to deal with problems
The present invention is that a kind of inorganic particles disperses paste composition; Said compsn contains (methyl) vinyl resin, inorganic particles and organic solvent; Said (methyl) vinyl resin has amino or carboxamido-group in molecular end, and to utilize the weight-average molecular weight of polystyrene conversion be 5000～100000.
Below the present invention is detailed.
The result that the inventor etc. study intensively finds; Molecular end through at (methyl) vinyl resin imports amino or carboxamido-group; Thereby the pyrolytic of vinyl resin is worsened, compare, dispersiveness, storage stability are significantly improved with the situation that does not import amino or carboxamido-group.In addition, also find to import amino or carboxamido-group, weight-average molecular weight is adjusted, in being suitable for the scope of printing so that accomplished the present invention through molecular end at (methyl) vinyl resin.
Inorganic particles of the present invention disperses paste composition to contain (methyl) vinyl resin as adhesive resin.
As above-mentioned (methyl) vinyl resin so long as the material that under the low temperature about 350～400 ℃, decomposes; Just there is not special qualification; For example, the preferred use by being selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) NSC 20949, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid Octadecane alcohol ester, (methyl) vinylformic acid benzyl ester and having at least a kind of polymkeric substance that forms in the group that (methyl) Acrylic Acid Monomer of polyoxyalkylene structure forms.Here, for example (methyl) propenoate is meant propenoate or methacrylic ester.
Wherein, owing to can obtain high viscosity with less amount of resin, thus preferred glass transition temperature (Tg) height, and the excellent Polymerization of Methyl thing of low-temperature defatted property is polymethylmethacrylate (Tg105 a ℃).
Inorganic particles of the present invention disperses in the paste composition, and when using phosphor particles as inorganic particles, above-mentioned (methyl) vinyl resin preferably uses the polymkeric substance that is formed by TEB 3K.Through using the polymkeric substance that forms by above-mentioned TEB 3K, can reduce the organic detritus behind the sintering, can improve the light characteristic of phosphor particles.
Above-mentioned (methyl) vinyl resin has amino or carboxamido-group in molecular end.
When on the ester substituting group of above-mentioned (methyl) Acrylic Acid Monomer, importing the high functional group of such interaction property such as amino or carboxamido-group; In firing process; The depolymerization of (methyl) vinyl resin is hindered, and the thermolysis end temp increases, and pyrolytic extremely worsens.
For example, the carbon fiber material that in fishing rod, golf club, uses is the material after the acrylic-amino ester polymer is burnt till, and when burning till, has promoted charing owing to amino existence.
But, when molecular end imports amino or carboxamido-group, do not hinder depolymerization, almost do not have influence on the temperature that thermolysis finishes yet.
In addition; Glass powder, ceramic powder, fluor etc. are high with amino or carboxamido-group interaction property; With above-mentioned (methyl) vinyl resin and when carrying out paste; A molecular end is adsorbed on microparticle surfaces such as pottery, and another becomes the form that extends to the organic solvent side, improves so can prevent the dispersion stabilization that reassociates, makes of particulate.Explain that inorganic particles disperses the dispersiveness of inorganic particles in the paste composition to depend on the terminal number of molecular chain.
In addition, amino or carboxamido-group are present in molecular end, thereby (methyl) vinyl resin and organic solvent are incompatible; Be separated (microphase-separated) that shows appropriateness; Have that bounding force descends under the state of sufficient viscosity (thixotropy), so do not produce wire drawing, the raising of silk screen printing property.And then, reduce through the weight-average molecular weight appropriateness that makes molecular end have (methyl) vinyl resin of amino or carboxamido-group, can suppress microphase-separated property, only improve dispersiveness, can also make the paste that shows newtonian viscous.
Above-mentioned (methyl) vinyl resin is the material that has amino or carboxamido-group in molecular end, but in the scope of not damaging effect of the present invention, can have a kind of imidazolinyl as above-mentioned amino, carboxamido-group, pyrrolidyl etc.Thus, the affinity with glass powder, ceramic powder, fluor etc. increases.
Above-mentioned (methyl) vinyl resin based on the weight-average molecular weight of polystyrene conversion following be limited to 5000, on be limited to 100000.Above-mentioned weight-average molecular weight can't show sufficient viscosity less than 5000 o'clock, used paste so be not suitable for printing; Above 100000 o'clock; Inorganic particles of the present invention disperses the binding property of paste composition to increase, and produces wire drawing, perhaps is difficult to be used in the silk screen printing property etc.Above-mentioned weight-average molecular weight is limited to 50000 on preferably, is limited to 40000 on preferred.Particularly weight-average molecular weight is 10000～20000 o'clock, obtains distinct image during silk screen printing, so preferred.
Explain, based on the mensuration of the weight-average molecular weight of polystyrene conversion can use post for example post LF-804 (clear with electrician's corporate system) carry out GPC and measure and obtain.
Explain; As the adhesive resin that uses in the inorganic particles dispersion paste composition of the present invention; Directly under the situation of the reaction soln after use (methyl) vinyl resin polyreaction, preferably do not comprise low molecular weight compositions such as monomer, oligopolymer in the polymeric solution.
(weight-average molecular weight/number-average molecular weight=Mw/Mn) be preferably below 3 is more preferably below 2.5 for the MWD of above-mentioned (methyl) vinyl resin.
MWD was above 3 o'clock; The low molecular weight compositions of the oligopolymer in the polymeric solution etc. becomes softening agent; Inorganic particles disperses can't obtain sufficient viscosity in the paste composition, silk screen printing property possible deviation, and high molecular weight components has the situation that stringiness is worsened in addition.
As not special qualification of content that inorganic particles of the present invention disperses (methyl) vinyl resin in the paste composition, preferably be limited to 5 weight % down, be limited to 25 weight % on preferably.The content of above-mentioned (methyl) vinyl resin is during less than 5 weight %; Inorganic particles disperses paste composition can't obtain sufficient viscosity, and silk screen printing property meeting variation is when surpassing 25 weight %; Inorganic particles disperses viscosity, the binding property of paste composition to become too high, and silk screen printing property can variation.
As the method for making above-mentioned (methyl) vinyl resin; For example can enumerate; On the basis of polymerization starter, make above-mentioned (methyl) acrylic monomer shift the known method method of carrying out copolymerization in the past such as polymerization, anionic polymerization, active anionic polymerization method that stops with radical polymerization, living radical polymerization, initiation with amino or carboxamido-group; On the basis of chain-transfer agent, make above-mentioned (methyl) acrylic monomer shift the known method method etc. of carrying out copolymerization in the past such as polymerization, anionic polymerization, active anionic polymerization method that stops with radical polymerization method, living radical polymerization, initiation with amino or carboxamido-group.Explain that these methods also can and be used.
But,, preferably use polymerization starter as radical polymerization initiator with amino or carboxamido-group in order to import amino or carboxamido-group in more molecular end.
In addition, only can for example utilize at the molecular end importing amino of (methyl) vinyl resin or the situation of carboxamido-group
13C-NMR confirms.
Make in the method for above-mentioned (methyl) vinyl resin, the situation of using radical polymerization is described.
Common radical polymerization is made up of the primitive reaction that following (1)～(4) illustrate.In the formula, I be radical (polymerization) initiator, M be monomer, P be monomer polymerization obtain polymkeric substance.
Shown in following formula (1)～(4), at the molecular end addition radical initiator of the polymkeric substance that utilizes the radical polymerization preparation.Therefore, through the selected radical initiator that imports to the molecular end of (methyl) vinyl resin, can import desirable amino or carboxamido-group in the molecular end of (methyl) vinyl resin with amino or carboxamido-group.
I
2→ 2I (1): radical formation reaction
I+M → I-M (as P) (2): initiation reaction
P+M → P-M (as Pn) (3): reaction of propagation
Pn+Pn → Pn-Pn (4): termination reaction
Prepare in the method for above-mentioned (methyl) vinyl resin, the situation of on the basis of chain-transfer agent, carrying out radical polymerization is described.
For example, the chain-transfer agent that will have sulfydryl imports under the situation in the reaction system, and the chain transfer reaction shown in the following formula (5) takes place.Through such chain transfer reaction, can prolong polymkeric substance by chain-transfer agent.Therefore, through the selected chain-transfer agent that imports to the molecular end of (methyl) vinyl resin, can import needed amino or carboxamido-group in the molecular end of (methyl) vinyl resin with amino or carboxamido-group and sulfydryl.
Explain, when using above-mentioned chain-transfer agent owing in reaction system, also there is the polymkeric substance of growing up by radical initiator, thus with the situation of using above-mentioned radical initiator to carry out radical polymerization relatively, the sense radix that can import reduces.Therefore, more preferably use the method for radical polymerization initiator with amino or carboxamido-group.
P+SH → P+S (5): chain transfer reaction
It is the material that polymerization starter and terpenic series solvent polymeric form that above-mentioned (methyl) vinyl resin especially preferably uses the azo that does not have cyanic acid.
Though have the azo of cyanic acid is that polymerization starter is no problem in the security of compound itself, and the decomposition radical that utilizes thermal degradation to produce is captured Wasserstoffatoms from other material, during stabilization, becomes the very high chemical substance of toxicity.Using the above-mentioned azo that does not have cyanic acid is polymerization starter when carrying out polymerization, such problem can not take place.
In addition; For to use azo be polymerization starter (methyl) vinyl resin of weight-average molecular weight 5000～100000 is carried out polymerization; Through in the toluene equal solvent, regulating azo is that the addition of polymerization starter is adjusted molecular weight; But, be polymerization starter and need to drop into more substantial azo for polymerization more low-molecular-weight (methyl) vinyl resin.Yet; Azo with above-mentioned amino or carboxamido-group is in the dissolving of polymerization starter (methyl) vinyl resin of being not dissolved in toluene etc. and so in the preferred solvent; Therefore azo is between the radical of polymerization starter bonding again to take place; Be easy to generate the reaction (cage effect of solvent) that becomes stable impurity; In addition, because two key generation Michael reactions of amino or carboxamido-group and (methyl) Acrylic Acid Monomer, so be that polymerization starter also exists and is difficult to make low-molecular-weight resin polymeric situation even if add a large amount of azos.
Relative therewith, found use terpenic series solvent, can suppress the polymerization of Michael reaction.Though being polymerization starter, azo is not dissolved in the terpenic series solvent; But making azo in advance is that polymerization starter is scattered in the terpenic series solvent; And make an addition in the polymerization system; Can make azo thus is that polymerization starter is dispersed in the reaction system apace, and the contained unsaturated double-bond of terpenic series solvent hinders Michael reaction, in addition; Because can to suppress by azo reposefully is the Raolical polymerizable that polymerization starter causes, thus can not produce azo be polymerization starter impurity make low-molecular-weight (methyl) vinyl resin carry out polymerization.
As the above-mentioned azo that does not have cyanic acid is polymerization starter; Then do not have special qualification so long as have the material of above-mentioned amino or carboxamido-group, for example can enumerate 2; Two [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides, 2 of 2 '-azo; Two [2-(2-tetrahydroglyoxaline-2-yl) propane] the dithionate dihydroxide, 2 of 2 '-azo, two (the 2-methyl-prop amidine) dihydrochlorides, 2 of 2 '-azo, two [N-(2-the carboxy ethyl)-2-methyl-prop amidine] oxyhydroxide, 2 of 2 '-azo; Two { 2-[1-(2-the hydroxyethyl)-2-tetrahydroglyoxaline-2-yl] propane } dihydrochlorides, 2 of 2 '-azo; 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], 2, two (1-imino--1-tetramethyleneimine-2-methylpropane) dihydrochlorides, 2 of 2 '-azo, the two { 2-methyl-N-[1 of 2 '-azo; Two (the hydroxymethyl)-2-hydroxyethyls of 1-] propionic acid amide, 2, the two azos such as [2-methyl-N-(2-hydroxyethyl) propionic acid amides] of 2 '-azo are polymerization starter etc.
As above-mentioned chain-transfer agent, just there is not special qualification so long as have the material of above-mentioned amino or carboxamido-group, for example can enumerate, have amino sulfydryl sulfur alcohol, ammonium mercaptoacetate, Thiovanic acid thanomin, dimercapto acetate two ammoniums etc.
As hindering above-mentioned Michael reaction and the stable solvent that suppresses Raolical polymerizable, preferably use the terpenic series solvent that has unsaturated double-bond in the polymer solvent and have the viscosity of appropriateness.As terpenic series solvent, for example can enumerate α-terpinol, β-terpinol, γ-terpinol, PC 560, terpinolene, γ-terpinene, α-terpinene, d-PC 560, α-terpinol acetic ester etc. with unsaturated double-bond.
In the paste composition of the present invention,, the same material of polymer solvent with (methyl) vinyl resin can be used, also different materials can be used as above-mentioned organic solvent.
As above-mentioned organic solvent, preferred above-mentioned terpenic series solvent.In addition, in the inorganic particles paste composition of the present invention, can also be also with the solvent beyond the above-mentioned terpenic series.
As can and with above-mentioned terpenic series solvent organic solvent in addition; 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 monobutyl ether, acetate of butyl carbitol, 2; 2; 4-trimethylammonium-1,3 pentanediol mono isobutyrate (Texanol), isophorone, n-Butyl lactate, phthalic acid dioctyl ester, hexanodioic acid dioctyl ester, benzylalcohol, phenyl Ucar 35, cresols etc.Wherein, from the aspect that be separated of easy demonstration with the appropriateness of (methyl) vinyl resin, preferred TC, diethylene glycol monomethyl ether, Diethylene Glycol list isobutyl ether, diethylene glycol monobutyl ether, acetate of butyl carbitol, 2; 2; 4-trimethylammonium-1,3 pentanediol mono isobutyrate is explained; These organic solvents can use separately, also can be also with more than 2 kinds.
In addition, because the temperature in the polyreaction is kept constant, so also can add lower boiling organic solvent.
Do not limit as above-mentioned lower boiling organic solvent is special, for example, can enumerate ETHYLE ACETATE, propyl acetate, butylacetate, methyl alcohol, ethanol, Virahol, toluene, methylethylketone, acetone etc.Above-mentioned lower boiling organic solvent carries out vacuum-treat, and removes monomer and the low boiling point organic solvent of not seized by force by polymkeric substance after when finishing polymerization, adding the high boiling organic solvent that uses in the inorganic particles dispersion paste composition.
When these residual monomers, low boiling point organic solvent remained in the resin solution composition, the reason of the viscosity stability deterioration when becoming viscosity degradation, printing etc. was so the residual quantity in the resin solution preferably is made as below the 100ppm.
When disperseing paste composition to disperse paste composition as phosphor particles inorganic particles of the present invention, as above-mentioned organic solvent, the preferred use contained the different material of solvent more than 2 kinds of molecular weight.
As the adhesive resin of phosphor particles dispersion paste composition, when using (methyl) vinyl resin, produce skinning during solvent seasoning, form the resin skin on dry paste surface, organic solvent can take place be difficult to the evaporable phenomenon.Therefore, in the next door of plasma display, fill phosphor particles and disperse paste composition, make its drying; When forming luminescent coating along lateral next door; The preferred high solvent of volatility that uses, but through using the different solvent of vapour pressure, the phosphor particles when low-molecular-weight solvent can make drying disperses the rate of drying of paste composition to improve; And the high-molecular weight solvent can be controlled the solvability of (methyl) vinyl resin; Institute can make fluor surface shape optimizing so that lateral top, next door can make phosphor particles disperse paste composition to adhere to.
In addition, preferably to contain the vapour pressure under the normal temperature be the above solvent of 0.1mmHg to above-mentioned organic solvent.
And then, preferably contain vapour pressure under the normal temperature and be above solvent of 0.1mmHg and the vapour pressure under the normal temperature solvent less than 0.01mmHg.Through containing 2 kinds of different solvents of such vapour pressure; Vapour pressure is that the phosphor particles of the above solvent of 0.1mmHg can make drying the time disperses the rate of drying of paste composition to improve; Vapour pressure under the normal temperature can be controlled the solvability of (methyl) vinyl resin less than the solvent of 0.01mmHg; Therefore the lateral top to the next door can make phosphor particles disperse paste composition to adhere to, and can make fluor surface shape optimizing.
As the vapour pressure under the above-mentioned normal temperature is the solvent more than the 0.1mmHg; For example can enumerate terpinol, terpinol acetic ester, diethylene glycol monomethyl ether, TC, benzylalcohol, Trivalin SF acetic ester, ethylene glycol mono hexyl ether, TC, n-Butyl lactate, 2-butoxyethyl group acetic ester, glycol diacetate, octanol, isophorone etc.
As the solvent of the vapour pressure under the above-mentioned normal temperature less than 0.01mmHg; For example can enumerate Diethylene Glycol single-butyl ether acetic ester, neopentyl glycol mono isobutyrate, Diethylene Glycol single-butyl ether, glycol monomethyl isobutyl ether, phenyl glycol, phenyl Ucar 35 etc.
Above-mentioned organic solvent plays important effect in silk screen printing.The needed effect of such organic solvent is 3 kinds when roughly dividing, and the 1st act as the dissolved adhesive resin; The 2nd act as the dispersiveness of guaranteeing phosphor particles, and the 3rd act as silk screen printing property excellence.Therefore, in order effectively to realize these 3 kinds of effects, the organic solvent that preferably combination is suitable uses.
Among the present invention, use as (methyl) vinyl resin under the situation of polymethylmethacrylate, when using weight-average molecular weight, do not dissolve basically in the high solvent of the polarity as terpinol, diethylene glycol monobutyl ether etc. than higher polymethylmethacrylate.Yet the solvent that polarity is high is that phosphor particles is disperseed the necessary solvent of paste composition, in order to make the top of fluor attached to the PDP next door, needs high, the good solvent of vapo(u)rability of combination vapour pressure.Therefore, realize that in order to make the 1st effect preferably a small amount of interpolation does not have hydroxyl and makes polymethylmethacrylate dissolved solvent well in terpinol or diethylene glycol monobutyl ether etc.
In addition; Because by the solvent of the many compound formation of the hydroxyl quantity in the molecule good dispersibility to phosphor particles; So in order to realize the 2nd effect; Interpolation has the solvent of the compound formation of 2 hydroxyls as 2-ethyl-1 in the molecule of that kind such as 3-pinakon, the dispersiveness of phosphor particles becomes well thus.Also can enumerate the 3-methyl isophthalic acid as such solvent, 5-pentanediol, 2-ethyl-1,3-pinakon etc.
Yet; At this moment; The vapo(u)rability variation of organic solvent, the solvability of polymethylmethacrylate reduces, so as the high solvent of the vapour pressure under the normal temperature; Use the terpinyl acetate equal solvent that does not have hydroxyl, preferably use with it and by the solvent combinations of the compound formation that has 2 hydroxyls in the molecule.
And then; Disperse the operation of paste to use silk screen printing, apportion design to carry out usually though in the next door of PDP backplate, fill phosphor particles; But the stainless steel mesh that especially mesh is thin in the silk screen printing is used for the silk screen version; Therefore the solvent that polarity is high is high to the coating of the parts of stainless steel of printing press, and misplacing of stencil property variation might phosphor particles disperse the loading level of paste to become insufficient.Therefore, preferably add acetate of butyl carbitol etc. such do not have hydroxyl and a low solvent of polarity.Explain, about polarity size, in the chemical constitution of solvent with respect to the quantity (carbon/hydroxyl) of the hydroxyl of carbon number, the solubleness of water etc. is become standard.Wherein, preferably use the high material of molecular weight.For example; Molecular weight is that (carbon/hydroxyl: 4) solvability to water is ∞ for 162 diethylene glycol monobutyl ether; Molecular weight is Texanol (carbon/hydroxyl: 12) though have the solvability less than 0.9% of hydroxyl to water of 216; Constitute the molecular weight of the compound of solvent through adjustment, can take into account the above-mentioned the 1st～3 effect.
In above-mentioned, the optimized solvent of the structure in the stiffening web that can make fluor is described, on the other hand, among the present invention,, also can contain the good resin of solvent seasoning property on a small quantity except above-mentioned (methyl) vinyl resin.Especially cellulose-based resin do not have molecular chain mutual winding, utilize the interaction that hydrogen bond causes and show viscosifying action, so the such skinning of (methyl) vinyl resin does not take place during solvent seasoning, rate of drying is also fast.Explain, when containing cellulose-based resin, hope the Tg of (methyl) vinyl resin is adjusted to less than 80 ℃, and the composition that (methyl) vinylformic acid 2-hydroxy methacrylate etc. has a hydroxyl is imported in the polymkeric substance.
As the cellulose-based resin that except above-mentioned (methyl) vinyl resin, is contained, preferred, ethyl.Do not limit as the grade of above-mentioned TKK 021 is special, from the preferred STD4 of reason～20 of viscosity stability excellence etc.
The preferred lower limit of the addition of above-mentioned cellulose-based resin is 0.5 weight part with respect to (methyl) vinyl resin 100 weight parts, is limited to 100 weight parts on preferred.
The addition of above-mentioned cellulose-based resin can not be brought into play the effect to drying property during less than 0.5 weight part sometimes, when surpassing 100 weight parts, and coking property variation sometimes.Be limited to 10 weight parts under above-mentioned addition is preferred, be limited to 70 weight parts on preferred.
Inorganic particles of the present invention disperses paste composition to contain inorganic particles.
Do not limit as above-mentioned inorganic particles is special, can enumerate glass powder, ceramic powder, phosphor particles, Si oxide etc.
Above-mentioned glass powder is not special to be limited, and for example can enumerate frit, CaO-Al such as bismuth oxide glass, silicate glass, lead glass, zinc glass, boron glass
2O
3-SiO
2System, MgO-Al
2O
3-SiO
2System, LiO
2-Al
2O
3-SiO
2The frit of various silicic acid oxide compounds such as system etc.In addition, except these, can also use PbO-B
2O
3-SiO
2Mixture, BaO-ZnO-B
2O
3-SiO
2Mixture, ZnO-Bi
2O
3-B
2O
3-SiO
2Mixture, Bi
2O
3-B
2O
3-BaO-CuO mixture, Bi
2O
3-ZnO-B
2O
3-Al
2O
3-SrO mixture, ZnO-Bi
2O
3-B
2O
3Mixture, Bi
2O
3-SiO
2Mixture, P
2O
5-Na
2O-CaO-BaO-Al
2O
3-B
2O
3Mixture, P
2O
5-SnO mixture, P
2O
5-SnO-B
2O
3Mixture, P
2O
5-SnO-SiO
2Mixture, CuO-P
2O
5-RO mixture, SiO
2-B
2O
3-ZnO-Na
2O-Li
2O-NaF-V
2O
5Mixture, P
2O
5-ZnO-SnO-R
2O-RO mixture, B
2O
3-SiO
2-ZnO mixture, B
2O
3-SiO
2-Al
2O
3-ZrO
2Mixture, SiO
2-B
2O
3-ZnO-R
2O-RO mixture, SiO
2-B
2O
3-Al
2O
3-RO-R
2O mixture, SrO-ZnO-P
2O
5Mixture, SrO-ZnO-P
2O
5Mixture, BaO-ZnO-B
2O
3-SiO
2Glass powders such as mixture (explaining that R is the element that is selected from the group of being made up of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe and Mn).
In addition, also can use fusing point is the low melting glass powder below 600 ℃.As above-mentioned ceramic powder, for example can enumerate aluminum oxide, zirconium white, titanium oxide, barium titanate, aluminium nitride AlN, silicon nitride, SP 1 etc.As above-mentioned phosphor particles, for example can enumerate BaMgAl
10O
17: Eu, Zn
2SiO
4: Mn, (Y, Gd) BO
3: Eu etc.
Except above-mentioned inorganic particles, can also preferred use copper, iron etc. and so on amino or the carboxamido-group characterization of adsorption is good and oxidized metal easily.
In addition, because inorganic particles of the present invention disperses be separated (microphase-separated) of paste composition for the stabilization appropriateness, the nonionic that preferably contains the HLB value and be more than 10 is a tensio-active agent.Here; The HLB value is meant that method of calculation have proposed several, for example as the wetting ability of presentation surface promoting agent, the employed parameter of oil loving index; To nonionic is tensio-active agent; Saponification value is made as S, and when the acid value of the lipid acid of formation tensio-active agent was made as A, the HLB value defined with 20 (1-S/A).
As above-mentioned HLB value is that nonionic more than 10 is a tensio-active agent, does not have special qualification, alkylene ether is added be formed in the material of aliphatic chain, particularly for example, and preferred polyoxyethylene lauryl ether, polyoxyethylene cetyl ether etc.Explain that though that above-mentioned nonionic is the tensio-active agent pyrolytic is good, during heavy addition, inorganic particles disperses the pyrolytic of paste composition to reduce, so be limited to 5 weight % on content preferred.
Inorganic particles of the present invention disperses that paste composition contains further preferably that second-order transition temperature is below 0 ℃, weight-average molecular weight is 1000～30000 organic cpds.
Inorganic particles of the present invention disperses paste composition to use technologies such as die head coating, roller coat cloth, silk screen printing, apportion design, hectograph to apply usually, and the bubble that is involved in during coating, during misplacing of stencil can become pin hole etc. and produce bad situation after burning till.
Especially in the fluor printing process of plasma display, owing to print paste in the narrow space in the glass stiffening web, so can be involved in bubble in high-accuracy ground.Therefore, hope to have in the phosphor paste from being printed onto the character that bubble is vanished fast between the drying process.
Among the present invention, because above-mentioned organic cpds has defoaming effect, so contain above-mentioned organic cpds, the undesirable condition when bubble is sneaked in the time of can effectively preventing to apply or during misplacing of stencil.
Above-mentioned organic cpds hopes it is low polar compound.(methyl) that inorganic particles of the present invention disperses to use in the paste composition is though the polar group of vinyl resin because of having endways; Its polarity is than higher; But through adding low polar compound as organic cpds; Utilize the polar difference that the surface tension of bubble surface is descended, the result can make the bubble-break after being involved in.
As above-mentioned organic cpds; For example can enumerate; The compound of polyolefine, polyethers etc. particularly for example, can be enumerated Vestolen PP 7052-polyethylene and ethylene copolymers, polybutylenes, W 166, polytetramethylene glycol, W 166-polytetramethylene glycol multipolymer etc.
The second-order transition temperature of above-mentioned organic cpds (Tg) is preferably below 0 ℃.Through Tg is below 0 ℃; Disperse vehicle contained in the paste composition immiscible with inorganic particles of the present invention; Vehicle is freely moved around to a certain degree, so can play a role effectively as the broken basic point that steeps with respect to the surface of the bubble that is involved in.When Tg surpasses 0 ℃, good excessively with the intermiscibility of (methyl) vinyl resin, can't obtain defoaming effect sometimes.
The preferred of the weight-average molecular weight of above-mentioned organic cpds is limited to 1000 down, is limited to 30000 on preferably.The weight-average molecular weight of above-mentioned organic cpds was less than 1000 o'clock, and good excessively with the intermiscibility of (methyl) vinyl resin, defoaming effect is insufficient sometimes, surpassed at 30000 o'clock, and vehicle is moved freely, and defoaming effect descends sometimes.
The preferred lower limit of the content of above-mentioned organic cpds is 0.1 weight part with respect to (methyl) vinyl resin 100 weight parts, is limited to 10 weight parts on preferred.The content of above-mentioned organic cpds can't be brought into play sufficient defoaming effect during less than 0.1 weight part sometimes, when surpassing 10 weight parts, can bring bad influence to coking property.
The organic materials that inorganic particles of the present invention disperses paste composition preferably to contain to have the surface modulation effect (below be also referred to as surface conditioner).In addition, the high polar organic compound that has hydroxyl in the preferred molecule of above-mentioned surface conditioner.
Through using high polar organic compound as above-mentioned surface conditioner, can improve the intermiscibility with inorganic particles, can be difficult to bubble is rolled in the paste.
And then aforesaid high polar organic compound can further improve the polarity that inorganic particles disperses paste composition.Its result can make the polarity difference of itself and above-mentioned organic cpds bigger, and the effect of bubble is further improved.
As above-mentioned surface conditioner, for example can enumerate, diol compound, three alkylol cpds, particularly for example; Can enumerate Ucar 35, trimethylene, 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 2; 2-dimethyl--1, ammediol, 2,2-diethylammonium-1, ammediol, 2-butyl-2-ethyl glycol, 2-Rutgers 612,2; 4-diethylammonium-1,5-pentanediol, 2-methyl-2,4-pentanediol, glycerine, monoglyceride class, acetylene hydroxyl are given thing etc.
The boiling point of above-mentioned surface conditioner is preferably below 300 ℃.When the boiling point of above-mentioned surface conditioner surpasses 300 ℃, have bad influence during sintering.
The preferred lower limit of the content of above-mentioned surface conditioner is 1 weight % with respect to the content of (methyl) vinyl resin, is limited to 100 weight % on preferred.The content of above-mentioned surface conditioner is during less than 1 weight %, and the effect that can't obtain expecting sometimes is when surpassing 100 weight %, too poor sometimes with the intermiscibility of (methyl) vinyl resin.
Disperse the preparation method of paste composition to have no particular limits as inorganic particles of the present invention, can enumerate known in the past stirring means, particularly for example, can enumerate each material with 3 stirring method such as roller etc.
Inorganic particles of the present invention disperses paste composition; Particularly preferably be the glass paste composition when using glass powder, the ceramic paste compsn when using ceramic powder, the phosphor paste composition when using fluorophor powder, the conductive paste compsn when using electroconductive powder, the raw cook when using glass powder or ceramic powder as inorganic particles as inorganic particles as inorganic particles as inorganic particles as inorganic particles.
Printing process when disperseing paste composition to print to inorganic particles of the present invention does not have special qualification, but preferably uses the whole bag of tricks such as silk screen printing, apportion design, die head coating, roller coat cloth, offset printing.
To inorganic particles of the present invention disperse paste composition use the die head coating, when apportion design is printed, preferably with the low situation of viscosity of the low state estimating of velocity of shear.Particularly, preferred inorganic particles of the present invention disperses 2 (l/s) that velocity of shear is made as of paste composition to survey periodic viscosity is below 50 (Pas).When above-mentioned viscosity surpasses 50 (Pas), make inorganic particles disperse paste composition when die orifice is extruded, to need high pressure, inorganic particles to disperse paste composition to disperse, or it is uneven to produce glue spread.
Inorganic particles of the present invention disperses paste composition owing to use at the organic solvent that evaporates below 280 ℃, at (methyl) vinyl resin of separating the coalescence decomposition below 400 ℃, therefore the low-temperature defatted possibility that becomes.Here, the low-temperature defatted skimming temp that is meant that adhesive resin loses 99.5% weight of initial stage weight is a low temperature, will be that 250～400 ℃ situation is defined as low-temperature defatted not carrying out skimming temp under the common air atmosphere such as nitrogen displacement in this specification sheets.
The invention effect
According to the present invention, can provide can be low-temperature defatted, and the inorganic particles dispersed, that storage stability is excellent disperses paste composition.
Embodiment
Below enumerate embodiment the present invention is more specified, but the present invention is limited by these embodiment not only.
(embodiment 1)
To have stirrer, water cooler, TM, hot water bath and, mixed methyl methyl acrylate (MMA) 100 weight parts in the removable flask of 2L of nitrogen inlet, as terpinol 100 weight parts of organic solvent, obtain monomer mixed solution.
To the bubbling that the monomer mixed solution that obtains uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with use nitrogen replacement in the removable flask, and the limit stirring, the limit is warmed up to 130 ℃ with oil groove.Having added will be as 2 of polymerization starter, the solution after 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide] dilutes with terpinol.In addition, in polymerization, add the terpinol solution that contains polymerization starter for several times, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
Polymerization begins 7 hours postcooling makes finishing polymerization to room temperature.Thus, obtain the terpinol solution that molecular end has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as described in Table 1 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that obtains for operation like this further adds as the terpinol of the ratio of components of table 1 record, makes it disperse to prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will as nonionic be tensio-active agent BL-9EX (day Optical Chemical Company system), (contain SiO as the glass granules of the median size 2.0 μ m of inorganic particles
232.5%, B
2O
320.5%, ZnO 18%, Al
2O
310%, BaO 3.5%, Li
2O 9%, Na
2O 6%, SnO
20.5%) after the ratio of components of pressing table 1 record added, it was fully mixing to use high-speed stirring apparatus to carry out, and uses 3 roller mills to handle to level and smooth state, has prepared inorganic particles and has disperseed paste composition.
(embodiment 2)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet, mixed methyl methyl acrylate (MMA) 100 weight parts, as toluene 100 weight parts of organic solvent obtain monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Adding will be as 2 of polymerization starter, the solution after 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] dilutes with terpinol.In polymerization, add the terpinol solution that contains polymerization starter in addition for several times, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtained toluene/terpinol solution that molecular end has amino (methyl) vinyl resin.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 1 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained further adds terpinol, utilize the vaporizer decompression to remove toluene, has obtained the terpinol solution that molecular end has amino (methyl) acryloid cement.Behind solvent seasoning method affirmation resin solid composition, further add terpinol according to the mode of the ratio of components that becomes table 1 record, make its dispersion with high speed dispersor, prepared the vehicle compsn.
To the vehicle compsn that obtains, will as nonionic be tensio-active agent BL-9EX (day Optical Chemical Company system), (contain SiO as the glass granules of the median size 2.0 μ m of inorganic particles
232.5%, B
2O
320.5%, ZnO 18%, Al
2O
310%, BaO 3.5%, Li
2O 9%, Na
2O 6%, SnO
20.5%), after adding according to the mode of the ratio of components that becomes table 1 record, use high-speed stirring apparatus carry out fully mixing, handle to level and smooth state with 3 roller mills, prepared inorganic particles dispersion paste composition thus.
(embodiment 3)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet, mixed methyl methyl acrylate (MMA) 100 weight parts, as terpinol 200 weight parts of organic solvent have obtained monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Adding will be as 2 of polymerization starter, the solution after 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] dilutes with terpinol.In polymerization, add the terpinol solution that contains polymerization starter in addition for several times, amount to the polymerization starter that has added 10 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtained the terpinol solution that molecular end has amino (methyl) vinyl resin.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 1 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained utilizes vaporizer that the part of terpinol is reduced pressure and removes, and regulates the resin solid composition.Behind solvent seasoning method affirmation resin solid composition, further add terpinol according to the mode of the ratio of components that becomes table 1 record, use high speed dispersor to make its dispersion, prepared the vehicle compsn.
To the vehicle compsn that obtains, will as nonionic be tensio-active agent BL-9EX (day Optical Chemical Company system), (contain SiO as the glass granules of the median size 2.0 μ m of inorganic particles
232.5%, B
2O
320.5%, ZnO 18%, Al
2O
310%, BaO 3.5%, Li
2O 9%, Na
2O 6%, SnO
20.5%), after adding according to the mode of the ratio of components that becomes table 1 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition thus.
(embodiment 4)
In the molecular end with embodiment 1 preparation has the terpinol solution of carboxamido-group, further add terpinol, make its dispersion, prepared the vehicle compsn with high speed dispersor according to the mode of the ratio of components that becomes table 1 record.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors (Ri Ya chemical industrial company system, (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 1 record, carry out fully mixingly with high-speed stirring apparatus, handle to level and smooth state, prepared inorganic particles dispersion paste composition thus with 3 roller mills.
(embodiment 5)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet mixed methyl methyl acrylate (MMA) 100 weight parts, as terpinol 100 weight parts of organic solvent; And add aminoothyl mercaptan 0.8 weight part as chain-transfer agent, obtained monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Adding will be as 2 of polymerization starter, the solution after 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide] dilutes with terpinol.In polymerization, add the terpinol solution that contains polymerization starter in addition for several times, amount to the polymerization starter that adds 2.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the terpinol solution that molecular end has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 1 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained further adds terpinol according to the mode of the ratio of components that becomes table 1 record, makes its dispersion prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors (Ri Ya chemical industrial company system, (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 1 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
(comparative example 1)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet; Mixed methyl methyl acrylate (MMA) 100 weight parts, as acetate of butyl carbitol 100 weight parts of organic solvent; Interpolation has obtained monomer mixed solution as aminoothyl mercaptan 0.8 weight part of chain-transfer agent.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Adding is the solution after PERHEXA TMH (day oily corporate system) dilutes with acetate of butyl carbitol as the ketal peroxide of polymerization starter.In polymerization, repeatedly add the acetate of butyl carbitol solution that contains polymerization starter in addition, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtained the acetate of butyl carbitol solution that molecular end has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is the HMW body more than 3 times with respect to estimated molecular weight originally.Weight-average molecular weight based on polystyrene conversion is as shown in table 1.
The solution of (methyl) vinyl resin that operation like this is obtained further adds acetate of butyl carbitol according to the mode of the ratio of components that becomes table 1 record, makes its dispersion prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will as nonionic be tensio-active agent BL-9EX (day Optical Chemical Company system), (contain SiO as the glass granules of the median size 2.0 μ m of inorganic particles
232.5%, B
2O
320.5%, ZnO 18%, Al
2O
310%, BaO 3.5%, Li
2O 9%, Na
2O 6%, SnO
20.5%), after adding according to the mode of the ratio of components that becomes table 1 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
(comparative example 2)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet mixed methyl methyl acrylate (MMA) 90 weight parts, USAF RH-1 (MAA) 10 weight parts, as acetate of butyl carbitol 100 weight parts of organic solvent; Interpolation has obtained monomer mixed solution as lauryl mercaptan 1.2 weight parts of chain-transfer agent.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Solution after adding will be diluted with acetate of butyl carbitol as the PERHEXA TMH (day oily corporate system) of polymerization starter.In polymerization, repeatedly add the acetate of butyl carbitol solution that contains polymerization starter in addition, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After beginning 3 hours from polymerization, the methacrylic resin that molecular side chain has carboxamido-group can not be used for gelation, pasteization.
(comparative example 3)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet; Mixed methyl methyl acrylate (MMA) 90 weight parts, n-sec.-propyl acid amides methacrylic ester (NIPAM) 10 weight parts, as acetate of butyl carbitol 100 weight parts of organic solvent; Interpolation has obtained monomer mixed solution as lauryl mercaptan 1.2 weight parts of chain-transfer agent.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with in the removable flask with nitrogen replacement and while stirring oil groove is warmed up to 130 ℃.Added the solution after diluting with acetate of butyl carbitol as the PERHEXA TMH (day oily corporate system) of polymerization starter.In polymerization, repeatedly add the acetate of butyl carbitol solution that contains polymerization starter in addition, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the acetate of butyl carbitol solution that molecular side chain has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear with electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is the HMW body more than 2 times with respect to originally estimated molecular weight.Weight-average molecular weight based on polystyrene conversion is as shown in table 1.
The solution of (methyl) vinyl resin that operation like this is obtained further adds acetate of butyl carbitol according to the mode of the ratio of components that becomes table 1 record, makes its dispersion prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will as nonionic be tensio-active agent BL-9EX (day Optical Chemical Company system), (contain SiO as the glass granules of the median size 2.0 μ m of inorganic particles
232.5%, B
2O
320.5%, ZnO 18%, Al
2O
310%, BaO 3.5%, Li
2O 9%, Na
2O 6%, SnO
20.5%), after adding according to the mode of the ratio of components that becomes table 1 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition thus.
(comparative example 4)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet, mixed methyl methyl acrylate (MMA) 100 weight parts, as acetate of butyl carbitol 100 weight parts of organic solvent have obtained monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Added the solution after diluting with acetate of butyl carbitol as the azobis isobutyronitrile (AIBN) of polymerization starter.In addition, in polymerization, repeatedly add the acetate of butyl carbitol solution that contains polymerization starter, amount to the polymerization starter that has added 3 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtained the acetate of butyl carbitol solution that molecular end has (methyl) vinyl resin of isopropyl cyanide.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 1 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained further adds acetate of butyl carbitol according to the mode of the ratio of components that becomes table 1 record, makes its dispersion prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors (Ri Ya chemical industrial company system, (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 1 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition thus.
< evaluation >
Disperse paste composition to carry out following evaluation to embodiment 1～5 with the inorganic particles that comparative example 1～4 obtains.The result is shown in table 2.
(1) transparency of adhesive resin composition (impurity generative nature)
With ETHYLE ACETATE the vehicle compsn that embodiment 1～5 and comparative example 1～4 obtain is diluted to 50 times, has confirmed the transparency.When the impurity that produces because of the cage effect of polymerization starter generates in a large number owing to can see muddiness, so can see muddy situation conduct *, can not see muddy situation as zero.
(2) coking property
Use is set at the applicator of 5 mils, disperses paste coating on glass substrate inorganic particles, makes its drying after 30 minutes with 150 ℃ air-supply baking ovens, burns till 30 minutes with 500 ℃ electric furnaces.Utilize the hole field to make made analysis of carbon and sulfur device and measure residual carbon (ppm).In addition, utilize Visual Confirmation to burn look, and the evaluation that is described below.
Zero: residual carbon is below the 150ppm.
*: residual carbon is more than the 150ppm.
(3) storage stability (sediment-free is arranged)
To put into the 250ml polythene container with the paste composition that embodiment 1～5, comparative example 1～4 are made, whether have throw out with the visual observation container bottom.Then, whether the phosphor paste composition that is placed in polythene container is existed throw out with the visual observation container bottom in keeping under the environment of 23 ℃ of temperature, humidity 50% after 1 month again.
According to following benchmark, whether container bottom is existed throw out evaluation.
Zero: do not observe throw out in container bottom.
*: observed throw out in container bottom.
[table 2]
(embodiment 6)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet, mixed methyl methyl acrylate (MMA) 100 weight parts, as terpinol 100 weight parts of organic solvent have obtained monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Interpolation will be as 2 of polymerization starter, the solution after 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide] dilutes with terpinol.In addition, in polymerization, add the terpinol solution that contains polymerization starter for several times, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the terpinol solution that molecular end has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 3 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained further adds terpinyl acetate according to the mode of the ratio of components that becomes table 3 record, makes its dispersion prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will be the BC-30 (day Optical Chemical Company system) of tensio-active agent as nonionic, as the PDP of inorganic particles with fluor inorganic particles (Ri Ya chemical industrial company system, red-emitting phosphors (Y, Gd) BO
3: Eu), after adding according to the mode of the ratio of components that becomes table 3 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
(embodiment 7)
In the polymerization process, except using 2 as polymerization starter, 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], organic solvent etc. are beyond the prescription of table 3 record, disperse paste composition with embodiment 6 same operation preparation inorganic particles.
(embodiment 8)
In the polymerization process; Except using terpinyl acetate as polymer solvent, using 2 as polymerization starter; 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] beyond the prescription of table 3 record, disperses paste composition with embodiment 6 same operation preparation inorganic particles.
(embodiment 9)
In the polymerization process,, beyond the prescription of table 3 record, disperse paste composition with embodiment 6 same operation preparation inorganic particles except reducing the addition of polymerization starter.
(embodiment 10)
Except using the molecular end that in embodiment 5, obtains to have the terpinol solution of (methyl) vinyl resin of carboxamido-group, beyond the prescription of table 3 record, disperse paste composition with embodiment 6 same operation preparation inorganic particles.
(comparative example 5)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet, mixed methyl methyl acrylate (MMA) 100 weight parts, as ETHYLE ACETATE 30 weight parts of organic solvent obtain monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with use nitrogen replacement in the removable flask, and the mixing solutions backflow is stirred and is warmed up on the limit.Having added will be the solution after PERHEXA TMH (day oily corporate system) dilutes with ETHYLE ACETATE as the ketal peroxide of polymerization starter.In addition, in polymerization, repeatedly add the ethyl acetate solution that contains polymerization starter, amount to the polymerization starter that has added 0.5 weight part with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the ethyl acetate solution of polymethylmethacrylate.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 3 based on the weight-average molecular weight of polystyrene conversion.Make ETHYLE ACETATE dry, it is dissolved again with terpinol.
But, even if the high-molecular weight plexiglass at high temperature also is not dissolved in terpinol, become the resin solution of sensation as gelation, the evaluation after can not carrying out.
(comparative example 6)
Ethyl acetate solution to using the polymethylmethacrylate that obtains with comparative example 5 same methods carries out drying, and it is dissolved in the acetate of butyl carbitol again.
The acetate of butyl carbitol solution of the polymethylmethacrylate that operation like this is obtained further adds acetate of butyl carbitol according to the mode of the ratio of components that becomes table 3 record, makes its dispersion prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will be the BC-30 (day Optical Chemical Company system) of tensio-active agent as nonionic, as the PDP of inorganic particles with fluor inorganic particles (Ri Ya chemical industrial company system, red-emitting phosphors (Y, Gd) BO
3: Eu), after adding according to the mode of the ratio of components that becomes table 3 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition thus.
< evaluation >
Inorganic particles to obtaining with embodiment 6～10 and comparative example 5,6 disperses paste composition, except the evaluation of carrying out above-mentioned (1)～(3), and the evaluation of (4)～(5) below having carried out.The result is shown in table 4.
(estimating preparation) with substrate
(the SigmaAldrich corporate system STD100) is dissolved in the terpinol solution, has prepared the vehicle compsn to make TKK 021.Then; After softening temperature being about 550 ℃ frit and mixing with the mode of frit 50 weight %, vehicle compsn 50 weight % with the vehicle compsn that contains TKK 021; Carry out mixing with impeller; Use 3 roller mills to handle, prepared the glass paste composition thus to smooth state.Use applicator that the setting of the glass paste composition that obtains with 5 mils is coated on the soda-lime glass substrate of 15cm * 15cm, make its drying 30 minutes, then,, prepared the substrate A that is formed with glass coating with 550 ℃ of sintering 20 minutes with 120 ℃ of baking ovens.
The glass granules of median size 2.0 μ m (is contained SiO
235%, B
2O
320%, ZnO 18%, Al
2O
312%, BaO 5%, Li
2O 7%, Na
2O 2.5%, SnO
20.5%) mix with the terpinol solution that has dissolved TKK 021, and it is fully mixing to use high-speed stirring apparatus to carry out, and handles to smooth state with 3 roller mills, makes the glass paste composition.Use applicator to be coated on the substrate A this glass paste composition with the setting of 5 mils, with baking oven 150 ℃, make its drying 60 minutes, obtain substrate B.
On the glass coating of the substrate B that obtains, use sandblast machine (society of only making institute system, ニ ユ one マ Block ラ ス タ one SMC-1ADE-401) to carry out sandblasting, formed the next door thus.Explain that use PDP with blast media (society of only making institute system, S9#1200) as abrasive, the pressure under the sandblasting is that 0.04MPa, emitted dose are 200g/min.Then, the substrate that forms behind the next door was burnt till 10 minutes under 550 ℃ of top temperatures, preparation has the evaluation in next door and uses substrate.
(4) viscosity evaluation
Use rheometer VAR100 (REOLOGICA society system), the viscosity that the inorganic particles when the mensuration velocity of shear is 2 (1/s) disperses paste composition.Explain, use the parallel plate of diameter 10mm during mensuration, be spaced apart 0.5mm.
50 (Pas) when following are zero, when surpassing 50 (Pas) for *.
(5) fluor shape evaluation
Use divider, disperse paste composition to be filled in the next door of estimating substrate the inorganic particles that obtains after, with the blast type baking oven 150 ℃, drying 10 minutes.Then, in retort furnace, burnt till under 500 ℃ 10 minutes, the section of the substrate that obtains is observed with stereomicroscope, confirm the shape of luminescent coating thus.Luminescent coating is not biased to the top in next door and the situation of adhering to is zero, sink to the bottom, next door or partially the part in the next door situation for *.
(embodiment 11)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet; Mixed methyl methyl acrylate (MMA) 100 weight parts, as ammonium mercaptoacetate 0.8 weight part of chain-transfer agent, as terpinol 50 weight parts of organic solvent, obtain monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and make hot water bath be warmed up to boiling while stirring.Adding will be the solution after PERHEXA TMH (day oily corporate system) dilutes with ETHYLE ACETATE as the ketal peroxide of polymerization starter.In addition, in polymerization, repeatedly add the ethyl acetate solution that contains polymerization starter, amounted to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the terpinol solution of polymethylmethacrylate.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 5 based on the weight-average molecular weight of polystyrene conversion.
In the terpinol solution of the polymethylmethacrylate that obtains, further add solvent, tensio-active agent according to table 5, preparation vehicle compsn.After stirring with high-speed stirring apparatus, add PDP as inorganic particles with fluor inorganic particles (Ri Ya chemical industrial company system, red-emitting phosphors (Y, Gd) BO
3: Eu), use 3 roller mills to handle, prepared inorganic particles and disperseed paste composition to level and smooth state.
(embodiment 12)
Except replacing ammonium mercaptoacetate, use beyond Thiovanic acid monoethanolamine 1 weight part, with embodiment 11 same operation preparation polymkeric substance.Then, use the polymkeric substance that obtains, use with composition shown in the table 5 and embodiment 11 same operations to have prepared the inorganic particles paste composition.
(embodiment 13)
Except replacing ammonium mercaptoacetate to use dimercapto acetate two ammoniums 0.7 weight part, with embodiment 11 same operation preparation polymkeric substance.Then, use the polymkeric substance that obtains, prepared the inorganic particles paste composition with composition shown in the table 5 and embodiment 11 same operations.
(embodiment 14)
Except replacing ammonium mercaptoacetate to use propane thioic acid ammonium 0.8 weight part, with embodiment 11 same operation preparation polymkeric substance.Then, use the polymkeric substance that obtains, prepared the inorganic particles paste composition equally with composition shown in the table 5 and embodiment 11.
(embodiment 15)
Except replacing ammonium mercaptoacetate to use propane thioic acid monoethanolamine 1.1 weight parts, with embodiment 11 same operation preparation polymkeric substance.Then, use the polymkeric substance that obtains, with composition shown in the table 5 and embodiment 11 same operation preparation inorganic particles paste compositions.
(comparative example 7)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet; Mixed methyl methyl acrylate (MMA) 100 weight parts, as ammonium mercaptoacetate 0.8 weight part of chain-transfer agent, as acetate of butyl carbitol 50 weight parts of organic solvent, obtain monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with use nitrogen replacement in the removable flask, and limit stirring and make hot water bath be warmed up to boiling.Adding will be the solution after PERHEXA TMH (day oily corporate system) dilutes with ETHYLE ACETATE as the ketal peroxide of polymerization starter.In addition, in polymerization, repeatedly add the ethyl acetate solution that contains polymerization starter, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtained the acetate of butyl carbitol solution of polymethylmethacrylate.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 5 based on the weight-average molecular weight of polystyrene conversion.
In the terpinol solution of the polymethylmethacrylate that obtains, further add solvent, tensio-active agent according to table 5, preparation vehicle compsn.After stirring with high-speed stirring apparatus, add PDP as inorganic particles with fluor inorganic particles (Ri Ya chemical industrial company system, red-emitting phosphors (Y, Gd) BO
3: Eu), handle level and smooth state, prepared inorganic particles and disperseed paste composition with 3 roller mills.
(comparative example 8)
Except replacing ammonium mercaptoacetate to use propane thioic acid ammonium 0.8 weight part, prepared the inorganic particles paste composition with comparative example 7 same operations.
(embodiment 16)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet; Mixed methyl methyl acrylate (MMA) 50 weight parts, methylacrylic acid butyl ester (BMA) 50 weight parts; Terpinol 100 weight parts as organic solvent obtain monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Adding will be as 2 of polymerization starter, the solution after 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide] dilutes with terpinol.In addition, in polymerization, add the terpinol solution that contains polymerization starter for several times, amount to the polymerization starter that adds 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the terpinol solution that molecular end has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 7 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained; Will be in advance in Texanol the dissolved TKK 021 (with the pure medicine corporate system of light, STD10, weight-average molecular weight: 65000); Mode according to the ratio of components that becomes table 7 record; Further add terpinol and Texanol, make its dispersion, prepared the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors particulate (Ri Ya chemical industrial company system, red-emitting phosphors (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 7 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
(embodiment 17)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet; Mixed methyl methyl acrylate (MMA) 50 weight parts, Propenoic acid, 2-methyl, isobutyl ester (IBMA) 50 weight parts, as terpinol 100 weight parts of organic solvent, obtain monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Having added will be as 2 of polymerization starter, the solution after 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] dilutes with terpinol.In addition, add the terpinol solution that contains polymerization starter in the polymerization for several times, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the terpinol solution that molecular end has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 7 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained; Will be in advance in Texanol the dissolved TKK 021 (with the pure medicine corporate system of light, STD4, weight-average molecular weight: 50000); Mode according to the ratio of components that becomes table 7 record; Further add terpinol and Texanol, make its dispersion prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors particulate (Ri Ya chemical industrial company system, red-emitting phosphors (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 7 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
(comparative example 9)
Make TKK 021 (with the pure medicine corporate system of light, STD4, weight-average molecular weight: 60000) be dissolved in the terpinol; And the mode according to the ratio of components that becomes table 7 record is further added terpinol and Texanol, makes its dispersion prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors particulate (Ri Ya chemical industrial company system, red-emitting phosphors (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 7 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
< evaluation >
To disperseing paste composition with the inorganic particles that comparative example 7～9 obtains with embodiment 11～17, except the evaluation of carrying out above-mentioned (1)～(3), the evaluation of (4)～(5) below also having carried out.The result is shown in table 6,8.
(estimating preparation) with substrate
TKK 021 (Sigma Aldrich corporate system, STD100) is dissolved in the terpinol solution, has prepared the vehicle compsn.Then; Mode according to frit 50 weight %, vehicle compsn 50 weight % is mixed the vehicle compsn that softening temperature is about 550 ℃ frit and contains TKK 021; Carry out mixing with impeller then; Use 3 roller mills to handle, prepared the glass paste composition to smooth state.Use applicator with the glass paste composition that obtains, be coated on the soda-lime glass substrate of 15cm * 15cm, make its drying 30 minutes, then,, prepared the substrate A that is formed with glass coating 550 ℃ of sintering 20 minutes with 120 ℃ of baking ovens with the setting of 5 mils.
The glass granules of median size 2.0 μ m (is contained SiO
235%, B
2O
320%, ZnO 18%, Al
2O
312%, BaO5%, Li
2O 7%, Na
2O 2.5%, SnO
20.5%) mix with the terpinol solution that has dissolved TKK 021, it is fully mixing to use high-speed stirring apparatus to carry out, and handles smooth state with 3 roller mills, makes the glass paste composition.This glass paste composition is used applicator, is coated on the substrate A with the setting of 5 mils, with baking oven 150 ℃, make its drying obtain substrate B in 60 minutes.
Use sandblast machine (society of only making institute system, ニ ユ one マ Block ラ ス タ one SMC-1ADE-401) to carry out sandblasting to the glass coating of the substrate B that obtains, formed the next door thus.Explain that use PDP with blast media (society of only making institute system, S9#1200) as abrasive, the pressure during sandblasting is that 0.04MPa, emitted dose are 200g/min.Then, the substrate that formed the next door was burnt till 10 minutes under 550 ℃ of top temperatures, prepared evaluation and used substrate with next door.
(4) viscosity evaluation
Use rheometer VAR100 (REOLOGICA corporate system), the viscosity that the inorganic particles when the mensuration velocity of shear is 2 (1/s) disperses paste composition.Explain, use the parallel plate of diameter 10mm during mensuration, be spaced apart 0.5mm.
With the situation below 50 (Pas) is zero, the situation that surpasses 50 (Pas) is *.
(5) fluor shape evaluation
Use divider, disperse paste composition to be filled in the next door of estimating substrate the inorganic particles that obtains, use the blast type baking oven then at 150 ℃, dry 10 minutes.Then, with retort furnace 500 ℃, burnt till 10 minutes, the section of the substrate that obtains is observed with stereomicroscope, confirm the shape of luminescent coating.Luminescent coating is not biased to the top in next door and the situation of adhering to is zero, sink to the bottom, next door or partially the part in the next door situation for *.
(embodiment 18)
To the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet, mixed methyl methyl acrylate (MMA) 100 weight parts, as terpinol 100 weight parts of organic solvent obtain monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with in the removable flask with nitrogen replacement and while stirring oil groove is warmed up to 130 ℃.Adding will be as 2 of polymerization starter, the solution after 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide] dilutes with terpinol.In addition, in polymerization, add the terpinol solution that contains polymerization starter for several times, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the terpinol solution that molecular end has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 9 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained further adds terpinol, organic cpds, surface conditioner according to the mode of the ratio of components that becomes table 9 record, makes its dispersion prepare the vehicle compsn with high speed dispersor.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors (Ri Ya chemical industrial company system, (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 9 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
Explain,, use ニ Star サ Application Port リ Block テ Application (grade 200N, day oily corporate system, second-order transition temperature-24 ℃, weight-average molecular weight 5500) as above-mentioned organic cpds.
(embodiment 19)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet; Mixed methyl methyl acrylate (MMA) 50 weight parts, Propenoic acid, 2-methyl, isobutyl ester (IBMA) 50 weight parts, as terpinol 100 weight parts of organic solvent, obtain monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Interpolation will be as 2 of polymerization starter, the solution after 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] dilutes with terpinol.In addition, in polymerization, add the terpinol solution that contains polymerization starter for several times, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the terpinol solution that molecular end has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 9 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained further adds terpinol, organic cpds according to the mode of the ratio of components that becomes table 9 record, makes its dispersion with high speed dispersor, has prepared the vehicle compsn.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors (Ri Ya chemical industrial company system, (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 9 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
(embodiment 20)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet; Mixed methyl methyl acrylate (MMA) 50 weight parts, Propenoic acid, 2-methyl, isobutyl ester (IBMA) 50 weight parts, as terpinol 100 weight parts of organic solvent, obtained monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and while stirring oil groove is warmed up to 130 ℃.Adding will be as 2 of polymerization starter, the solution after 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide] dilutes with terpinol.In addition, add the terpinol solution that contains polymerization starter in the polymerization for several times, amount to the polymerization starter that has added 1.5 weight parts with respect to monomer 100 weight parts.
After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtain the terpinol solution that molecular end has (methyl) vinyl resin of carboxamido-group.To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 9 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained further adds terpinol, surface conditioner according to the mode of the ratio of components that becomes table 9 record, makes its dispersion with high speed dispersor, has prepared the vehicle compsn.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors (Ri Ya chemical industrial company system, (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 9 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
(comparative example 10)
In the removable flask of the 2L with stirrer, water cooler, TM, hot water bath and nitrogen inlet; Mixed methyl methyl acrylate (MMA) 100 weight parts, as lauryl mercaptan 1 weight part of chain-transfer agent, as terpinol 100 weight parts of organic solvent, obtained monomer mixed solution.
To the monomer mixed solution that obtains, the bubbling that uses nitrogen to carry out 20 minutes, remove thus dissolve deposit oxygen after, with using nitrogen replacement in the removable flask, and make hot water bath be warming up to boiling while stirring.Adding will be the solution after PERHEXA TMH (day oily corporate system) dilutes with ETHYLE ACETATE as the ketal peroxide of polymerization starter.In polymerization, repeatedly add the ethyl acetate solution that contains polymerization starter in addition.After polymerization began 7 hours, cool to room temperature made finishing polymerization.Thus, obtained terminal terpinol solution with poly methyl methacrylate polymer of methyl.
To the polymkeric substance that obtains, use post LF-804 (clear and electrician's corporate system) as post, utilize gel permeation chromatography analysis, the result is as shown in table 9 based on the weight-average molecular weight of polystyrene conversion.
The solution of (methyl) vinyl resin that operation like this is obtained further adds terpinol according to the mode of the ratio of components that becomes table 9 record, makes its dispersion with high speed dispersor, has prepared the vehicle compsn.
To the vehicle compsn that obtains, will be the BL-9EX (day Optical Chemical Company system) of tensio-active agent as nonionic, as red-emitting phosphors (Ri Ya chemical industrial company system, (Y, Gd) BO of inorganic particles
3: Eu), after adding according to the mode of the ratio of components that becomes table 9 record, it is fully mixing to use high-speed stirring apparatus to carry out, and handles to level and smooth state with 3 roller mills, has prepared inorganic particles dispersion paste composition.
< evaluation >
Inorganic particles to obtaining with embodiment 18～20, comparative example 10 disperses paste composition, except the evaluation of carrying out above-mentioned (1)～(5), has also advanced the evaluation of (6) and (7) of following record.The result is shown in table 10.
(6) defoaming
The vehicle compsn that obtains is scraped mixed 30 seconds with spatula (spatula) fierceness, leave standstill then.30 minutes products with interior broken bubble are made as ◎, 1 hour product with interior broken bubble is made as zero, even if the also not broken product that steeps is made as more than 1 hour with leaving standstill *.
(7) defoaming (applying the back)
Use screen process press, disperse paste composition to be filled in the next door of estimating substrate the inorganic particles that obtains after, leave standstill in room temperature, with visual observation the situation of follicular rupture.10 minutes is zero with interior follicular rupture, the product that becomes level and smooth condition of surface, even if leave standstill that bubble does not break yet more than 10 minutes, or the surface for the convexo-concave product be *.
Utilizability on the industry
According to the present invention, can provide can be low-temperature defatted, and the inorganic particles dispersed, that storage stability is excellent disperses paste composition.
Claims (9)
1. an inorganic particles disperses paste composition, it is characterized in that,
Said inorganic particles disperses paste composition to contain (methyl) vinyl resin, inorganic particles and organic solvent,
Said (methyl) vinyl resin has amino or carboxamido-group in molecular end, and to utilize the weight-average molecular weight of polystyrene conversion be 5000～100000.
2. inorganic particles according to claim 1 disperses paste composition, it is characterized in that,
The vapour pressure that organic solvent contains under the normal temperature is the above solvent of 0.1mmHg.
3. inorganic particles according to claim 1 disperses paste composition, it is characterized in that,
It is the above solvent of 0.1mmHg and the vapour pressure under the normal temperature solvent less than 0.01mmHg that organic solvent contains vapour pressure under the normal temperature.
4. disperse paste composition according to claim 1,2 or 3 described inorganic particles, it is characterized in that,
It is that polymerization starter is polymerized that (methyl) vinyl resin is to use the azo with cyanic acid.
5. disperse paste composition according to claim 1,2,3 or 4 described inorganic particles, it is characterized in that,
Also contain cellulose-based resin.
6. disperse paste composition according to claim 1,2,3,4 or 5 described inorganic particles, it is characterized in that,
(methyl) vinyl resin is to form with the solvent polymeric that contains the terpenic series solvent.
7. disperse paste composition according to claim 1,2,3,4,5 or 6 described inorganic particles, it is characterized in that,
Velocity of shear is that the viscosity of measuring in 2 o'clock is below the 50Pas, and the unit of velocity of shear is 1/s.
8. disperse paste composition according to claim 1,2,3,4,5,6 or 7 described inorganic particles, it is characterized in that,
Inorganic particles is low melting glass powder, ceramic powder, phosphor particles or Si oxide.
9. disperse paste composition according to claim 1,2,3,4,5,6,7 or 8 described inorganic particles, it is characterized in that,
Also contain second-order transition temperature and be below 0 ℃, weight-average molecular weight is 1000～30000 organic cpds.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
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| JP2009064784 | 2009-03-17 | ||
| JP2009-064784 | 2009-03-17 | ||
| JP2009103365 | 2009-04-21 | ||
| JP2009-103365 | 2009-04-21 | ||
| JP2009-141023 | 2009-06-12 | ||
| JP2009141023 | 2009-06-12 | ||
| JP2009-187430 | 2009-08-12 | ||
| JP2009187430 | 2009-08-12 | ||
| JP2009228724 | 2009-09-30 | ||
| JP2009-228724 | 2009-09-30 | ||
| PCT/JP2010/054225 WO2010106980A1 (en) | 2009-03-17 | 2010-03-12 | Inorganic microparticle-dispersed paste composition |
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| JP (1) | JP4937411B2 (en) |
| KR (1) | KR20110131283A (en) |
| CN (1) | CN102333818A (en) |
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| CN114605764A (en) * | 2018-08-30 | 2022-06-10 | 积水化学工业株式会社 | Carrier composition for inorganic fine particle dispersion, inorganic fine particle dispersion slurry composition, and method for producing inorganic fine particle dispersible tablet |
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| JP5940790B2 (en) * | 2010-10-26 | 2016-06-29 | 株式会社ダイセル | Solvent for printing or solvent composition |
| KR20130018619A (en) * | 2011-08-09 | 2013-02-25 | 가부시끼가이샤 다이셀 | Solvent for printing and paste composition |
| JP6091014B2 (en) * | 2014-11-07 | 2017-03-08 | 楠本化成株式会社 | Method of forming a pattern by screen printing |
| JP6754366B2 (en) * | 2015-09-28 | 2020-09-09 | 綜研化学株式会社 | Plasticizer for polylactic acid resin, polylactic acid resin composition using the plasticizer, and polylactic acid resin molded product |
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- 2010-03-12 JP JP2010511004A patent/JP4937411B2/en not_active Expired - Fee Related
- 2010-03-12 WO PCT/JP2010/054225 patent/WO2010106980A1/en active Application Filing
- 2010-03-12 KR KR1020117024072A patent/KR20110131283A/en not_active Application Discontinuation
- 2010-03-12 CN CN2010800092766A patent/CN102333818A/en active Pending
- 2010-03-16 TW TW099107537A patent/TW201035223A/en unknown
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| JP2001163918A (en) * | 1999-12-13 | 2001-06-19 | Sekisui Chem Co Ltd | Vinyl polymer having functional groups at ends, method for manufacturing the same, and curable composition containing the vinyl polymer having functional groups at ends |
| CN101137712A (en) * | 2005-03-31 | 2008-03-05 | 积水化学工业株式会社 | Binder resin composition and inorgnaic fine particle-dispersed paste composition |
| JP2007224363A (en) * | 2006-02-23 | 2007-09-06 | Sekisui Chem Co Ltd | Sinterable paste composition containing dispersed inorganic fine particles |
| JP2009001646A (en) * | 2007-06-20 | 2009-01-08 | Sekisui Chem Co Ltd | Binder resin, and paste composition having inorganic fine particle dispersed therein |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105108162A (en) * | 2015-08-21 | 2015-12-02 | 中国科学院理化技术研究所 | Method for dispersing liquid metal to micro nano-particles |
| CN105108162B (en) * | 2015-08-21 | 2017-11-24 | 中国科学院理化技术研究所 | A kind of method that liquid metal is dispersed into micro-nano granules |
| CN114605764A (en) * | 2018-08-30 | 2022-06-10 | 积水化学工业株式会社 | Carrier composition for inorganic fine particle dispersion, inorganic fine particle dispersion slurry composition, and method for producing inorganic fine particle dispersible tablet |
| CN114605764B (en) * | 2018-08-30 | 2024-01-19 | 积水化学工业株式会社 | Carrier composition for inorganic microparticle dispersion, slurry composition for inorganic microparticle dispersion, and method for producing inorganic microparticle-dispersed sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010106980A1 (en) | 2010-09-23 |
| JP4937411B2 (en) | 2012-05-23 |
| KR20110131283A (en) | 2011-12-06 |
| JPWO2010106980A1 (en) | 2012-09-20 |
| TW201035223A (en) | 2010-10-01 |
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