CN1720294A

CN1720294A - Paste composition and use thereof

Info

Publication number: CN1720294A
Application number: CN 200480001676
Authority: CN
Inventors: 种市大树; 鹤田学; 三塚雅彦
Original assignee: Mitsui Takeda Chemicals Inc
Current assignee: Mitsui Chemicals Polyurethanes Inc
Priority date: 2003-10-27
Filing date: 2004-10-27
Publication date: 2006-01-11
Anticipated expiration: 2024-10-27
Also published as: CN100404620C

Abstract

The paste composition of the present invention is a paste composition comprising (i) a polyurethane resin which comprises (a) a recurring unit represented by the formula (1) and (b) a recurring unit represented by the formula (2), a molar fraction of said recurring unit (a) being in the range of 0.35 to 0.99, a molar fraction of said recurring unit (b) being in the range of 0.01 to 0.65, the total of both the molar fractions being 1, (ii) a solvent and (iii) a powder. By the use of the paste composition, dielectric layers, sealing products, barrier ribs, phosphors, etc. can be favorably formed.

Description

Paste composition and uses thereof

Technical field

The present invention relates to a kind of paste composition, relate in particular to the paste composition that is used to make PDP (plasma display panel) as dielectric medium paste, isolation rib (barrier ribs) material paste and fluor paste, and the paste composition that is used as the sealing glass paste, be used in particular for sealing PDP (plasma display panel), cathodic discharge conduit, fluorescence sign typotron and FED (field-emitter display) or sealing IC package.

In addition, the invention still further relates to dielectric layer, sealing prod, isolation rib and fluor that uses the paste composition manufacturing and the method for making them.

Background technology

PDP (plasma display panel) most possibly can be used as follow-on large-scale TV indicating meter.At " Technical Trends of PDP Materials (technological trend of PDP material) " (Yasuo Katsuya, Hitachi Chemical Technical Report No.33 (7), 9-16,1999) in, the method for making PDP and the main raw that is used for this each step of method there is detailed description (non-patent literature 1).

In the structure of common PDP, the electrode of plasma discharge is formed on the front glass substrate, and forms dielectric layer (isolator) on electrode.This dielectric layer needs high pressure resistant and to the transparency of visible light.

In the method for production common dielectric layer, on the front glass substrate, form electrode, then the dielectric medium paste of proper viscosity is coated with machine etc. and evenly is coated with by silk screen printing or by using bar to be coated with machine, roller coating machine, seam, dryly then remove solvent and under 500 ℃～600 ℃, calcine to decompose the adhesive resin in the dielectric medium paste.

As the adhesive resin in the dielectric medium paste, use ethyl cellulose up to now without peer, because it has the superior printing characteristics energy always.Yet, because ethyl cellulose is a rigid resin, so in existing problems as checking or contraction in drying step aspect the workability.After this, in Japanese Patent Laid publication number 246236/1999 (patent documentation 1) etc., add as the softening agent raising workability of phthalic ester, but softening agent and solvent are different on drying rate.Therefore, in drying step, need stricter temperature control, thereby make production method become more complicated, that is, also have the leeway that to improve.

The sealing glass paste that is used for PDP is mainly by low-melting glass powder, mineral filler, adhesive resin and solvent composition.In the method for the common PDP substrate of sealing, by silk screen printing or divider sealing glass paste (being also referred to as " glass for bonding paste ", " seal glass paste " or " frit glass paste (frit glass paste) ") is filled in the space between rear end substrate and the front end substrate, drying is removed solvent and is calcined in the time of 400 ℃～500 ℃ to decompose adhesive resin then.As adhesive resin, ethyl cellulose is because it has good viscosity characteristics thereby is used up to now always.Yet, because ethyl cellulose easy carbonization when thermolysis, make the often insufficient degradation that causes sealing glass of thermolysis degree, cause the lost of life of PDP.

Have preferably that the acrylic resin of thermal decomposition performance is used as tackiness agent research, although thermal decomposition performance is improved, the paste that obtains has too high flowability and insufficient viscosity.After this, as in Japanese Patent Laid publication number 255587/2002 (patent documentation 2), the acrylic resin that viscosity performance improves has been proposed.Yet these acrylic resins have high molecular weight, so produce the problem of spinning property (linear) in the silk screen printing between silk screen and print surface, thereby also have the leeway that can improve printing performance.

In PDP, generally front glass substrate and rear end glass substrate are set, and the space between these glass substrates is isolated rib and is separated in their modes in opposite directions.Isolating rib forms by blasting method usually.In the method, barrier ribs strip material paste is coated on the glass substrate of rear end by silk screen printing or by using roller coating machine, seam to be coated with machine etc., and dry then removing desolvated, thereby just obtains having the isolation rib layer of uniform thickness.Subsequently, laminating film protective layer (DFR) thereon is then with its exposure imaging.After this, thus the method by sandblast remove the barrier ribs strip material that does not scribble this protective layer and form in the place of needs and isolate rib.The method that rib is isolated in other formation comprises that will isolate rib by silk screen printing directly is printed on method on the glass substrate of rear end, and by silk screen printing or by using roller coating machine, seam to be coated with machine etc. the barrier ribs strip material is coated on the surface of whole rear end glass substrate, and will except with isolate corresponding extra-regional other the regional barrier ribs strip materials of rib and scrape off the method for isolating rib with comb to form.

The isolation rib of calcining formation thus under 500 ℃～600 ℃ is to decompose adhesive resin.As adhesive resin, use ethyl cellulose up to now, because it has the superior printing characteristics energy always.Yet because ethyl cellulose is a rigidity, so paste is relatively poor aspect processibility such as sandblast, unless add softening agent to reduce rigidity in this paste.By adding softening agent, can improve processibility, but have another problem, promptly this isolation rib is in the defective that has easily under the influence of softening agent as checking in drying step or calcining step.

In order to improve workability, proposed to use the mixture of the acrylic resin of ethyl cellulose and hydroxyl to be used as tackiness agent (Japanese Patent Laid publication number 54992/2003 (patent documentation 3)).Yet, when using the mixture of two kinds of tackiness agents, more complicated problems that the preparation method that can produce paste becomes more complicated and quality control paste becomes, so this respect still leaves some room for improvement.

The fluor of PDP uses the fluor paste that mainly contains fluorophor powder, adhesive resin and solvent to generate.By using methods such as silk screen printing that the fluor paste is filled between the rib, drying is removed solvent then, and calcines under 400 ℃～500 ℃ to decompose adhesive resin.As adhesive resin, so ethyl cellulose is because it has the superior printing characteristics energy and is used up to now always.Yet because ethyl cellulose carbonization when thermolysis, carbon remains in the phosphorus and has reduced the brightness of fluorescence.

Have preferably that the acrylic resin of pyrolytic is used as tackiness agent research, but the paste that obtains have too high flowability and insufficient printing performance.After this, as in Japanese Patent Laid publication number 329256/2001 (patent documentation 4), the acrylic resin that printing performance improves has been proposed.Yet these acrylic resins have the higher weight-average molecular weight of 600000～2000000 scopes, therefore, produce the problem of spinning property between silk screen in silk screen printing and the print surface, thereby also have the leeway of improving on the printing performance.

On the other hand, in Japanese Patent Laid publication number 355618/2000 (patent documentation 5), the present inventor has disclosed the urethane resin that uses among the present invention and has had good pyrolytic, but this does not cause printing the invention of paste.

In the Embodiment C-17～C-19 of U.S. Patent number 6646093 (patent documentation 6), the cement paste that contains thickening material, cement and water is disclosed, wherein thickening material is made of the urethane resin that uses among the present invention.Prepare this cement paste according to its feature that solidification delay does not take place basically when using this thickening material.Water in cement and the paste react (hydration reaction) make the cement paste solidify, thereby when use cement paste, do not need to be used for solidifying the calcining step of paste.Therefore, the cement paste is different from aforesaid dielectric medium paste etc. in this.

In patent documentation 5 and patent documentation 6, the printing performance to the paste that contains urethane resin is not described, and do not have to disclose the paste that contains urethane resin and can be used to printing, more specifically, if use a kind of paste that contains urethane resin, thereby silk screen printing can be carried out and the spinning property problem that produces paste hardly can obtain slick print.

Patent documentation 1: Japanese Patent Laid publication number 246236/1999

Patent documentation 2: Japanese Patent Laid publication number 255587/2002

Patent documentation 3: Japanese Patent Laid publication number 54992/2003

Patent documentation 4: Japanese Patent Laid publication number 329256/2001

Patent documentation 5: Japanese Patent Laid publication number 355618/2000

Patent documentation 6: U.S. Patent number 6,646,093

Non-patent literature 1: " Technical Trends ofPDP Materials (technological trend of PDP material) " (Yasuo Katsuya, Hitachi Chemical Technical Report No.33 (7), 9-16,1999)

Summary of the invention

One of purpose of the present invention provides a kind of use, and it can carry out silk screen printing, thereby and produces the paste composition that the spinning property problem can obtain slick print hardly.

Another object of the present invention provides a kind of dielectric paste paste composite, and it is to use the surrogate of ethyl cellulose as the paste composition of the routine of adhesive resin, thereby has better workability.

Another purpose of the present invention provides a kind of sealing glass paste composition, and it can carbonization in when calcining, thereby does not cause the problem etc. of spinning property when carrying out silk screen printing.

Another purpose of the present invention provides a kind of barrier ribs strip material paste composition, and it is to use the surrogate of ethyl cellulose as the paste composition of the routine of adhesive resin, thereby has better workability.

Another purpose of the present invention provides a kind of phosphor slurry paste composite, thereby it can carbonization cause the problem etc. of spinning property in when calcining when carrying out silk screen printing.

The inventor addresses the above problem to have carried out conscientious research, found that and use urethane resin to show the superior printing characteristics energy that wherein urethane resin contains special pectination glycol and as the polyoxyalkylene glycol of diol component as the paste composition of adhesive resin.Based on these discoveries, finished the present invention.

That is, the present invention has following characteristics.

Paste composition of the present invention contains:

(i) urethane resin, it comprises

(a) repeating unit of following general formula (1) expression:

Wherein A is the group (divalent group) that obtains behind the OH group of removing among polyoxyalkylene glycol (compd A) HO-A-OH that two ends have hydroxyl, B for remove the group (divalent group) that obtains behind the NCO group among vulcabond (compd B) OCN-B-NCO and

(b) repeating unit of following general formula (2) expression:

Wherein D removes the group (divalent group) that obtains behind the OH group among the pectination glycol HO-D-OH, wherein have two carbonatomss in the pectination glycol molecules at least and are 4～21 hydrocarbyl group (monoradical), B is for removing the group (divalent group) that obtains behind the NCO group among vulcabond (compound) OCN-B-NCO

The molar fraction of repeating unit in the described urethane resin (a) is 0.35～0.99, and the molar fraction of repeating unit (b) is 0.01～0.65, and its prerequisite is to be 1 with the two whole molar fraction;

(ii) solvent; With

(iii) powder.

As pectination glycol HO-D-OH, can use the pectination glycol (Compound D) of following general formula (3) expression:

R wherein ¹Be alkyl with 1～20 carbon atom or nitrogenous alkyl, R ²And R ³Respectively doing for oneself has the alkyl of 4～21 carbon atoms, at R ¹, R ²And R ³In part or all of hydrogen atom can be by fluorine, chlorine, smell or iodine replaces and R ²And R ³Can be the same or different.

Y and Y ' respectively do for oneself hydrogen, methyl or CH ₂The Cl base, and Y and Y ' can be the same or different.

Z and Z ' respectively do for oneself oxygen, sulphur or CH ₂Base, and Z and Z ' can be the same or different.

When Z was oxygen, n was 0～15 integer, and when Z be sulphur or CH ₂During base, n is 0, and

When Z ' was oxygen, n ' was 0～15 integer, and to work as Z ' be sulphur or CH ₂When base, n ' is 0, and n and n ' can be the same or different;

Perhaps

The pectination glycol (Compound D ') represent with following general formula (4):

R wherein ⁵For having the alkyl of 1～20 carbon atom, R ²And R ³Respectively doing for oneself has the alkyl of 4～21 carbon atoms, at R ⁵, R ²And R ³In part or all of hydrogen atom can be replaced and R by fluorine, chlorine, bromine or iodine ²And R ³Can be the same or different.

Y, Y ' and Y " be hydrogen, methyl or CH ₂The Cl base, and Y and Y ' can be the same or different.

Z and Z ' respectively do for oneself oxygen, sulphur or CH ₂Base, and Z and Z ' can be the same or different,

R ⁴For total has the alkylene of 2～4 carbon atoms,

K is 0～15 integer,

When Z ' was oxygen, n ' was 0～15 integer, and to work as Z ' be sulphur or CH ₂When base, n ' is 0, and n and n ' can be the same or different.

Powder (iii) is preferably low-melting glass powder or phosphor powder.

Paste composition also contains mineral filler (except that low-melting glass powder) as powder (iii).Low-melting glass powder is preferably dielectric medium powder, sealing glass powder or barrier ribs strip material glass powder.

All passing through above-mentioned paste composition with the corresponding dielectric layer of the present invention, sealing prod, isolation rib and fluor forms.

The method of production and the corresponding dielectric layer of the present invention, sealing prod, isolation rib and fluor comprises above-mentioned paste composition coating or is printed on the substrate, calcines this paste composition then.

The paste composition of the application of the invention can carry out carrying out well that silk screen is peeled off and the silk screen printing of the spinning property of paste takes place hardly between print surface and silk screen.In addition, also can form slick print surface.In addition, to the printing paste composition calcine after, the amount of residue is quite little.

When paste composition of the present invention was used as the dielectric paste paste composite, advantage was: even when not containing or containing a spot of softening agent, be full of cracks as taking place and shrinking in the defective that also can avoid dielectric layer in drying step.

When paste composition of the present invention is used as sealing during paste composition, advantage is: because when calcining, not carbonization of paste composition and decomposing fully reduces so the sealing glass performance can not take place, and problems such as spinning property do not take place in silk screen printing.

When paste composition of the present invention was used as barrier ribs strip material paste composition, advantage was: rare in the sandblast process " excessively sandblast ".In the sandblast process, sandblast is carried out from figuratum photo-resist upper end, and only removes the barrier ribs strip material paste composition of having peeled off photo-resist from it on the direction perpendicular to the coatingsurface of barrier ribs strip material paste composition.Barrier ribs strip material paste composition is removed in term " excessively sandblast " expression too much, in addition remove small part do not peel off from it photo-resist barrier ribs strip material paste composition.Another advantage is: because barrier ribs strip material paste composition of the present invention do not contain softening agent or contains a spot of softening agent, so can not produce isolate rib in drying step or calcining step owing to added the caused defective of a large amount of softening agent.

When paste composition of the present invention was used as the phosphor slurry paste composite, advantage was: because paste composition the time does not have carbonization in calcining, thus the fluorescent brightness height, and problem such as spinning property does not take place in silk screen printing yet.

Embodiment

To be described in detail paste composition of the present invention below.

(i) urethane resin

Being used for urethane resin of the present invention (i) is the urethane resin that comprises following repeating unit:

(a) the represented repeating unit of following general formula (1):

Wherein A is the group (divalent group) that obtains behind the OH group of removing among polyoxyalkylene glycol (compd A) HO-A-OH that its two end has hydroxyl, B is the group (divalent group) that obtains behind the NCO group of removing among vulcabond (compd B) OCN-B-NCO, and

(b) the represented repeating unit of following general formula (2):

Wherein D is the group (divalent group) that obtains behind the OH group of removing among the pectination glycol HO-D-OH, wherein have two carbonatomss in the pectination glycol molecules at least and are 4～21 hydrocarbyl group (monoradical), B is for removing the group (divalent group) that obtains behind the NCO group among vulcabond (compd B) OCN-B-NCO

The molar fraction of repeating unit in the described urethane resin (a) is 0.35～0.99, and the molar fraction of repeating unit (b) is 0.01～0.65, and its prerequisite is that the molar fraction summation of the two is 1.

In the repeating unit (a) of general formula (1) expression, A is for removing the group (divalent group) that obtains behind the OH group among water-soluble or hydrophilic polyoxyalkylene glycol (compd A) HO-A-OH.As polyoxyalkylene glycol (compd A), especially preferably use the polyoxyalkylene glycol that has 2～6 carbon atoms in the alkylidene group.The example of this polyoxyalkylene glycol comprises the adducts of polyoxyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether diol (PTMEG), polyhexamethylene ether glycol and PPG and oxyethane.

The number-average molecular weight that compd A has (Mn) is preferably 400～100,000, and more preferably 400～20,000, be preferably 900～9,000 especially.When number-average molecular weight is not less than 400, can obtain having the urethane resin (i) of the weight-average molecular weight that is enough to obtain even print surface.When number-average molecular weight is not higher than at 100,000 o'clock, can carry out sufficient polyreaction, thereby obtain not existing substantially the resin of spinning property problem.

As polyoxyalkylene glycol (compd A), can be used in combination two or more polyoxyalkylene glycols.For example, can be used in combination polyoxyethylene glycol, polypropylene glycol, polytetramethylene ether diol.

As compd A, also can be used in combination low-molecular-weight glycol and replace polyoxyalkylene glycol, as ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, tetramethylene glycol or 1,6-hexylidene glycol, its prerequisite are 20% of the amount of the low-molecular-weight glycol gross weights that are no more than entire compound A.

In the repeating unit (b) of general formula (2) expression, D is for removing the group (divalent group) that obtains behind the OH group among the pectination glycol HO-D-OH (Compound D).Pectination glycol HO-D-OH has the glycol that two carbonatomss are 4～21 univalence hydrocarbyl at least in the molecule.A plurality of univalence hydrocarbyls are grafted on the side chain of glycol molecules skeleton, and on shape, Compound D is called as " pectination glycol ".

The example of univalence hydrocarbyl comprises alkyl, alkenyl, aralkyl and aryl.

Univalence hydrocarbyl is connected on the skeleton of pectination glycol by methylene radical, ether, thioether group, polyether-based etc.

Although the skeleton of pectination glycol can only be made of hydrocarbon, the preferred use on the skeleton has polar group such as ether (O-), polyether-based (the pectination glycol of O-or uncle's amino (N (R)-).

As the pectination glycol, the glycol that has uncle's amino on the skeleton as above-mentioned general formula (3) or (4) expression can use.

Be considered to because the univalence hydrocarbyl in the pectination glycol has lower polarity, they interact in polar solvent and produce hydrophobic interaction between the polymer chain that causes urethane, therefore, in addition the urethane with relatively low molecular weight also can obtain the viscosity that the printshop needs.

Usually, contain weight-average molecular weight and surpass 1,000, the paste composition of 000 polymers soln, using bar to be coated with in the silk screen printing step or application step of machine, roller coating machine etc., be coated with between machine, the roller coating machine etc. with silk screen, bar easily and the spinning property problem occurs, and there is the problem of slickness reduction in the paste surface of using such polymers soln to make on the surface of paste.Especially in silk screen printing,, thereby sometimes make printing to carry out because the silk screen that spinning property can influence between the surface of silk screen and printing peels off.The surperficial automatic isolating phenomenon that term used herein " silk screen discharges and peels off " expression utilizes silk screen tension force to make silk screen and printing.In addition, under the situation of using the divider coating, occur the spinning property problem between the tip of divider and the paste, thereby reduced the accuracy of processing.

In paste composition, the polymer chain formation viscosity of tangling mutually in polymers soln, this entanglement between polymer chain is considered to cause the reason of spinning property.In order to form the viscosity that processing needs as the printshop by tangling, polymkeric substance required weight-average molecular weight usually is not less than 500,000, more preferably is not less than 1,000,000.

On the other hand, in paste composition of the present invention,, thereby also, the hydrophobic interaction of pectination glycol makes the polymeric solution retrogradation because making polymer chain in the solution mutually combine even the polymer chain of urethane resin (i) does not tangle.Therefore, though urethane resin (i) even weight-average molecular weight be no more than 1,000,000, also can give the viscosity of processing of this paste composition as printshop need, thereby the spinning property problem can not occur.

In addition, the pectination glycol is considered to serve as the softening agent (internal plasticizer) in the polymer backbone that is fixed on urethane.

The method for preparing the pectination glycol has a detailed description in the patent of Japan's special permission publication number 343328/1999, Japanese Patent Laid publication number 297133/2000 etc.

In the repeating unit (b) that the repeating unit (a) and the general formula (2) of general formula (1) expression are represented, B is for removing the group (divalent group) that obtains behind the NCO group among vulcabond (compd B) OCN-B-NCO.

Vulcabond (compd B) is the vulcabond that is selected from chain aliphatic diisocyanate, ring-shaped fat (cyclo) aliphatic diisocyanates and aromatic diisocyanate.

Be more preferably to use to add up to and contain the vulcabond of 3～18 carbon atoms (comprising the carbon atom in the NCO group) as diisocyanate cpd (compd B).

The chain aliphatic diisocyanate is the diisocyanate cpd with structure that NCO group wherein connects by the straight or branched alkylene, the example of these compounds comprises methylene diisocyanate, ethylidene diisocyanate, trimethylene diisocyanate, 1-methyl ethylidene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1, the 4-vulcabond, hexamethylene diisocyanate (being abbreviated as HMDI (popular name)), the heptamethylene vulcabond, 2,2 '-dimethylpentane-1, the 5-vulcabond, lysinediisocyanate methyl ester (being abbreviated as LDI (popular name)), eight methylene diisocyanates, 2,5-dimethylhexane-1, the 6-vulcabond, 2,2,4-trimethylpentane-1, the 5-vulcabond, the ninth of the ten Heavenly Stems methylene diisocyanate, 2,4,4-trimethyl cyclohexane-1, the 6-vulcabond, the decamethylene vulcabond, 11 methylene diisocyanates, ten dimethylene diisocyanates, ten trimethylene diisocyanate, ten tetramethylene diisocyanate, ten pentamethylene diisocyanate, ten hexamethylene diisocyanates and trimethyl hexamethylene diisocyanate.

The ring-shaped fat (cyclo) aliphatic diisocyanates is for wherein being connected to the polyisocyanate compound that the alkylene on the NCO group has ring texture, the example of this compound comprises hexanaphthene-1, the 2-vulcabond, hexanaphthene-1, the 3-vulcabond, hexanaphthene-1, the 4-vulcabond, 1-methylcyclohexane-2, the 4-vulcabond, 1-methylcyclohexane-2, the 6-vulcabond, 1-ethylcyclohexane-2, the 4-vulcabond, 4,5-dimethyl cyclohexane-1, the 3-vulcabond, 1,2-dimethyl cyclohexane-ω, ω '-vulcabond, 1,4-dimethyl cyclohexane-ω, ω '-vulcabond, isophorone vulcabond (being abbreviated as IPDI (popular name)), dicyclohexyl methyl hydride-4,4 '-vulcabond, dicyclohexyl methylmethane-4,4 '-vulcabond, dicyclohexyl dimethylmethane-4,4 '-vulcabond, 2,2 '-dimethyl dicyclohexyl methyl hydride-4,4 '-vulcabond, 3,3 '-dimethyl dicyclohexyl methyl hydride-4,4 '-vulcabond, 4,4 '-methylene radical-two (isocyanato cyclohexanes), two (4-cyclohexyl isocyanate) (being abbreviated as IPCI (popular name)) of isopropylidene, 1, two (isocyanatomethyl) hexanaphthenes of 3-, hydrogenation benzylidene vulcabond (being abbreviated as H-TDI (popular name)), hydrogenation 4,4 '-diphenylmethanediisocyanate (being abbreviated as H-MDI (popular name)), hydrogenation eylylene diisocyanate (being abbreviated as H-XDI (popular name)) and norcamphane vulcabond (being abbreviated as NBDI (popular name)).

Aromatic diisocyanate is the polyisocyanate compound that connects by aromatic group of NCO group wherein, aromatic group such as phenylene, phenylene or inferior aralkyl that alkyl replaces, or contain the alkyl of aromatic base, the example of these compounds comprises: 1,3-or 1, the 4-phenylene vulcabond, 1-methyl-2,4-phenylene vulcabond (2,4-TDI), 1-methyl-2,6-phenylene vulcabond (2,6-TDI), 1-methyl-2, the 5-phenylene vulcabond, 1-methyl-3, the 5-phenylene vulcabond, 1-ethyl-2, the 4-phenylene vulcabond, 1-sec.-propyl-2, the 4-phenylene vulcabond, 1,3-dimethyl-2, the 4-phenylene vulcabond, 1,3-dimethyl-4, the 6-phenylene vulcabond, 1,4-dimethyl-2, the 5-phenylene vulcabond, the m-Xylene Diisocyanate, the diethylbenzene vulcabond, the di-isopropyl phenylene diisocyanate, 1-methyl-3,5-diethylbenzene-2, the 4-vulcabond, the 3-methyl isophthalic acid, 5-diethylbenzene-2, the 4-vulcabond, 1,3,5-triethylbenzene-2, the 4-vulcabond, naphthalene-1, the 4-vulcabond, naphthalene-1, the 5-vulcabond, 1-methylnaphthalene-1, the 5-vulcabond, naphthalene-2, the 6-vulcabond, naphthalene-2, the 7-vulcabond, 1,1-dinaphthyl-2,2 '-vulcabond, biphenyl-2,4 '-vulcabond, biphenyl-4,4 '-vulcabond, 1, two (1-isocyanic acid-1-methylethyl ester) benzene of 3-, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond, ditan-4,4 '-vulcabond (MDI), ditan-2,2 '-vulcabond, ditan-2,4 '-vulcabond and eylylene diisocyanate (XDI).

By can suitably preparing urethane resin (i) with reference to the preparation method in the patent that is described in detail in Japan's special permission publication number 343328/1999, Japan's special permission publication number 297133/2000 etc.

(ii) solvent

The solvent that uses among the present invention is (ii) had no particular limits, and any solvent that can dissolve the urethane resin (i) as tackiness agent can use.Solvent example (ii) comprises the mixture of N-Methyl pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), phenylcarbinol, Terpineol 350, ester acetoacetic ester, N-BUTYL ACETATE, diethylene glycol monobutyl ether acetic ester, diethylene glycol monobutyl ether, toluene, dimethylbenzene, tetrahydrofuran (THF), methyl alcohol, ethanol, Virahol, butanols, water and these solvents.Especially preferred the use has high polar solvent.

(iii) powder

The powder that uses among the present invention (iii) can suitably be selected according to the purposes of paste composition of the present invention.Powder (iii) for example is low-melting glass powder or fluorophor powder.Low melting glass is illustrated under the temperature that thermal distortion does not take place base plate glass and can carries out the glass of fusion bonding or can carry out fusion bonding under the temperature of the heat resisting temperature that is lower than base plate glass.The Tg that low melting glass has is not higher than 600 ℃, preferably is not higher than 400 ℃, more preferably no higher than 350 ℃ and be not less than 250 ℃.This low-melting glass is often used as sealing glass, seal glass, glass for bonding etc.The maximum particle dia (Dmax) that powder (iii) has is no more than 100 μ m, more preferably between 1～50 μ m.When the particle diameter of maximum is no more than 100 μ m, use the paste composition that obtains fully to carry out silk screen printing.

For example, under the situation of using paste composition of the present invention as for example dielectric paste paste composite, use the dielectric glass powder (iii), use mineral filler in case of necessity (iii) as powder.

Then it is not done special restriction as long as the dielectric glass powder is the powder of above-mentioned low melting glass, any dielectric glass powder as PDP can use easily.Dielectric glass is the glass that is used to form the dielectric layer of PDP, and the glass that can form the film that does not have defective, and shows higher withstand voltage properties down in the calcining temperature (be generally 400～600 ℃, be preferably 530～580 ℃) of dielectric layer.The Tg that dielectric glass has is not higher than 600 ℃ and be not less than 300 ℃ usually, is preferably not to be higher than 500 ℃ of C and to be not less than 390 ℃.The example of the preferred dielectric glass that uses comprises PbO-B ₂O ₃-SiO ₂Glass, PbO-B ₂O ₃-SiO ₂-ZnO-CaO glass, PbO-B ₂O ₃-SiO ₂-ZnO-BaO-CaO-Bi ₂O ₃Glass and Bi ₂O ₃-B ₂O ₃-CaO-SrO-BaO glass.

Although not necessarily must use mineral filler, can add flowability and the thermal expansivity of controlling paste in right amount.Type to mineral filler has no particular limits, and any dielectric filler as PDP can use easily.For example, can use aluminum oxide, alpha-quartz, titanium oxide and zirconium white.

When paste composition of the present invention is used as the sealing glass paste composition, use the sealing glass powder (iii) as powder, use mineral filler in case of necessity (iii) as powder.Sealing glass also is known as " glass for bonding ", " seal glass " or " frit glass ".This glass is the glass of the opening of finally sealed PDP, FED, cathode tube etc., and considers that from performance perspective this glass is to carry out sealed glass under seal temperature (for example, 410～480 ℃).The Tg that sealing glass has usually is not higher than 400 ℃, preferably is not higher than 350 ℃, more preferably no higher than 330 ℃ and be not less than 250 ℃.

The example of the preferred sealing glass that uses comprises B ₂O ₃-PbO glass, B ₂O ₃-PbO-SiO glass, B ₂O ₃-PbO-ZnO glass, Cu ₂O-P ₂O ₅Glass, P ₂O ₅-SnO glass, P ₂O ₅-SnO-B ₂O ₃Glass and PbO-B ₂O ₃Glass.Its concrete example comprises that frit glass AFS1304M, ASF1200M and IWF2300M are (available from Asahi Glass Co., LTD.).

When needing,, can in paste, add above-mentioned mineral filler in order to control thermal expansivity.Mineral filler is had no particular limits, and any mineral filler that is used for the sealing glass paste composition can be used.For example, preferably use trichroite, zircon, stannic oxide, niobium oxides, zirconium phosphate, willemite and mullite.

When paste composition of the present invention is used as barrier ribs strip material paste composition, use the mineral filler (aluminum oxide, quartz etc.) in addition of glass powder and glass powder (iii) as powder.

Glass powder is not so long as above-mentioned low melting glass powder then limits especially to it, and any barrier ribs strip material glass powder as PDP can use.Be also referred to as " barrier ribs strip material glass " below as the powder glass powder (iii) in the barrier ribs strip material paste composition.The softening temperature of barrier ribs strip material glass is not less than 450 ℃ and be not higher than 650 ℃.The thermal expansivity that barrier ribs strip material glass preferably has is about 60 * 10 ^-7～90 * 10 ^-7(1/ ℃).The median size (D50) that barrier ribs strip material glass preferably has is 1～7 μ m, and maximum particle diameter (Dmax) is 5～30 μ m.The example of the preferred barrier ribs strip material glass that uses comprises PbO-B ₂O ₃-SiO ₂Glass, BaO-ZnO-B ₂O ₃-SiO ₂Glass and ZnO-Bi ₂O ₃-B ₂O ₃-SiO ₂Glass.

Mineral filler except that glass is also had no particular limits, and any filler that is used as the barrier ribs strip material of PDP can use.For example, can use aluminum oxide, alpha-quartz, titanium oxide and zirconium white.

When paste composition of the present invention was used as the phosphor slurry paste composite, fluorophor powder was used as powder (iii).

Employed fluorophor powder is had no particular limits, and any fluorophor powder as PDP can use.The example of the preferred fluorophor powder that uses comprises the BaMgAl as blue emitting phophor ₁₄O ₂₄: Eu, BaMgAl ₁₀O ₁₇: Eu and SrMg (SiO ₄) ₂: Eu; (Y, Gd) BO as red-emitting phosphors ₃: Eu, Y ₂O ₃: Eu, Y (P, V) O ₄: Eu and (Y, Gd) ₂O ₃: Eu; Zn as green-emitting phosphor ₂SiO ₄, BaAl ₁₂O ₁₉: Mn and YBO ₃: Tb.

Paste composition of the present invention (ii) also can contain softening agent, dispersion agent, defoamer etc. with powder (iii) except that containing urethane resin (i), solvent.

Paste composition

Weight in the paste composition among the present invention is 100%, and powder weight content (iii) is 30～95%, and the weight content of the binder resin solution that (ii) is made of urethane resin (i) and solvent is 5～70%.

Weight in binder resin solution is 100%, and the weight content of urethane resin (i) is 1～30%, and solvent weight content (ii) is 70～99%, and prerequisite is that the gross weight of adhesive resin and solvent is 100%.The viscosity that binder resin solution has in the time of 20 ℃ is generally 20～50Pas.

The urethane resin as adhesive resin that paste composition of the present invention uses (i) is TPU(Thermoplastic polyurethanes), and its weight-average molecular weight that has is 10,000～1,000,000, more preferably 50,000～500,000.

When the weight-average molecular weight of urethane resin (i) was not less than, can improve the viscosity of paste at 10,000 o'clock.When its weight-average molecular weight is no more than 1,000,, the spinning property problem of paste seldom appears at 000 o'clock when silk screen printing.When weight-average molecular weight 50,000～500, in the time of in 000 scope, have extremely excellent printing performance.

The viscosity of paste composition is as follows.When paste composition for using dielectric glass as (iii) dielectric paste paste composite of powder, when using sealing glass to isolate rib glass as (iii) barrier ribs strip material glass paste paste composite of powder as powder sealing glass paste composition or use (iii), its range of viscosities in the time of 20 ℃ is generally 1～1000Pas, more preferably in 5～50Pas scope.When paste composition when using fluorophor powder as (iii) phosphor slurry paste composite of powder, its range of viscosities in the time of 20 ℃ is generally 1～1000Pas, more preferably 10～150Pas.The viscosity of utilization in this scope, paste composition of the present invention is applicable to printing as silk screen printing.

The paste composition of the application of the invention, it also is feasible forming pattern.

Paste composition of the present invention is the inertia paste composition, and promptly in paste composition, urethane resin (i), the solvent of forming paste composition (ii) with powder chemical reaction do not take place each other basically (iii).

Method to the paste composition among preparation the present invention has no particular limits.For example, in separable flask, add solvent (ii) and urethane resin (i), stir them and be heated to about 40～80 ℃ simultaneously in about 1 hour, obtain binder resin solution.Binder resin solution, powder (iii) mix by three roller runner millings etc. with filler, thereby obtain paste composition.

The dielectric paste paste composite

When paste composition of the present invention is used as the dielectric paste paste composite, weight in the dielectric paste paste composite is 100%, then the weight content of dielectric glass powder is 40～80%, the weight content of the mineral filler except that dielectric glass (aluminum oxide, quartz etc.) is 0～10%, and the weight content of binder resin solution is 20～60%.

If the weight of dielectric glass powder is less than 40%, then can not obtain the sufficient insulativity and the transparency in some cases.If the weight of dielectric glass powder surpasses 80%, then the flowability of paste can reduce, and difficulty becomes when evenly being coated with.

Weight in paste composition is 100%, then more preferably the weight content scope of dielectric glass powder is 55～65%, the weight content scope of the mineral filler except that dielectric glass (aluminum oxide, quartz etc.) is 0～5%, and the weight content scope of binder resin solution is 35～45%.

Weight in binder resin solution is 100%, and the weight content of adhesive resin is 1～30%, and the weight content of solvent is 70～99%, and prerequisite is that the gross weight of adhesive resin and solvent is 100%.

As adhesive resin, use above-mentioned urethane resin (I), it is a TPU(Thermoplastic polyurethanes), its weight-average molecular weight is 10,000～1,000,000, more preferably 50,000～500,000.

When the weight-average molecular weight of urethane resin (i) was not less than, can improve the viscosity of paste at 10,000 o'clock.When its weight-average molecular weight is no more than 1,000,, the spinning property problem of paste seldom appears at 000 o'clock when carrying out silk screen printing.When weight-average molecular weight 50,000～500, during 000 scope, demonstrate extremely excellent printing performance.

When paste composition of the present invention is used as the dielectric paste paste composite, the preparation method of paste composition is had no particular limits.For example, in separable flask, add solvent (ii) and urethane resin (i), stir them and be heated to about 40～80 ℃ about 1 hour the time, obtain binder resin solution.Binder resin solution, dielectric glass powder and filler mix by three roller runner millings etc., thereby obtain the dielectric paste paste composite.

The sealing glass paste composition

When paste composition of the present invention is used as the sealing glass paste composition, weight in the sealing glass paste composition is 100%, the weight content of sealing glass powder is 35～95%, and the weight content of mineral filler is 0～50%, and the weight content of binder resin solution is 5～30%.

In binder resin solution, the weight content of adhesive resin is 1～30%, and the weight content of solvent is 70～99%, and prerequisite is that the gross weight of adhesive resin and solvent is 100%.

If the sealing glass powder weigh less than 30%, in Mi Feng the product a lot of defectives can appear then, insufficient when being sealed with.If the weight of sealing glass powder is higher than 95%, thereby then the flowability of paste just reduces the feasible difficulty that becomes of processing sometimes.

When the weight-average molecular weight of urethane resin (i) was not less than, can improve the viscosity of paste at 10,000 o'clock.When its weight-average molecular weight is no more than 1,000,, the spinning property problem of paste seldom appears at 000 o'clock when carrying out silk screen printing.When weight-average molecular weight 50,000～500, in the time of in 000 scope, have extremely superior printing characteristics energy.

When paste composition of the present invention is used as the sealing glass paste composition, the preparation method of paste composition is had no particular limits.For example, in separable flask, add solvent (ii) and urethane resin (i), stir them and be heated to about 40～80 ℃ simultaneously in about 1 hour, obtain binder resin solution.Binder resin solution, sealing glass powder and filler mix by three roller runner millings etc., thereby obtain the sealing glass paste composition.

Barrier ribs strip material paste composition

When paste composition of the present invention is used as barrier ribs strip material paste composition, weight in barrier ribs strip material paste composition is 100%, the weight content of barrier ribs strip material glass powder is 30～80%, the weight content of the mineral filler except that barrier ribs strip material glass powder (aluminum oxide, quartz etc.) is 1～40%, and the weight content of binder resin solution is 5～30%.

In binder resin solution weight is 100%, and the weight content of adhesive resin is 1～30%, and the weight content of solvent is 70～99%, and prerequisite is that the gross weight of adhesive resin and solvent is 100%.

As adhesive resin, use above-mentioned urethane resin (i), it is a TPU(Thermoplastic polyurethanes), its weight-average molecular weight that has is 10,000～1,000,000, more preferably 50,000～500,000.

When the weight-average molecular weight of urethane resin (i) was not less than, can improve the viscosity of paste at 10,000 o'clock.When its weight-average molecular weight is no more than 1,000,, the spinning property problem of paste seldom appears at 000 o'clock when carrying out silk screen printing.When weight-average molecular weight 50,000～500, during 000 scope, have extremely excellent printing performance.

When paste composition of the present invention is used as barrier ribs strip material paste composition, the preparation method of paste composition is had no particular limits.For example, in separable flask, add solvent (ii) and urethane resin (i), stir them and be heated to about 40～80 ℃ about 1 hour the time, obtain binder resin solution.Binder resin solution, glass powder and filler mix by three roller runner millings etc., thereby obtain barrier ribs strip material paste composition.

The phosphor slurry paste composite

When paste composition of the present invention is used as the phosphor slurry paste composite, be 100% in the weight of phosphor slurry paste composite, the weight content of fluorophor powder is 30～70%, the weight content of binder resin solution is 30～70%.

In binder resin solution, the weight content of adhesive resin is 2～20%, and the weight content of solvent is 80～98%, and prerequisite is that the gross weight of adhesive resin and solvent is 100%.

As adhesive resin, use above-mentioned urethane resin (i), it is a TPU(Thermoplastic polyurethanes), its weight-average molecular weight that has is 10,000～1,000,000, more preferably 50,000～500,000, further be preferably 100,000～500,000.

When the weight-average molecular weight of urethane resin (i) was not less than, can improve the viscosity of paste at 10,000 o'clock.When its weight-average molecular weight is no more than 1,000,, the spinning property problem of paste seldom appears at 000 o'clock when carrying out silk screen printing.When weight-average molecular weight 100,000～500, during 000 scope, have extremely excellent printing performance.

When paste composition of the present invention is used as the phosphor slurry paste composite, the preparation method of paste composition is had no particular limits.For example, in separable flask, add solvent (ii) and urethane resin (i), stir them and be heated to about 40～80 ℃ about 1 hour the time, obtain binder resin solution.Binder resin solution and fluorophor powder mix by three roller runner millings etc., thereby obtain the phosphor slurry paste composite.

Dielectric layer and preparation method thereof

Dielectric layer of the present invention can be by with the paste composition coating that contains the dielectric glass powder of the present invention or be printed on the substrate, calcines this paste composition then and prepares.More specifically, dielectric layer can be by method preparation as described below.

Formed thereon on the whole surface of rear end glass substrate of electrode, use screen process press, spreader, bar to be coated with the paste composition of the present invention as the dielectric paste paste composite of coating preparations such as machine, roller coating machine, then dry paste composition is to remove solvent.Suitable thickness range is 30～500 μ m.Using hot-air drier etc. that paste composition is being carried out drying with after removing solvent under 80～150 ℃ the temperature,, be about the dielectric layer of 20～100 μ m with formation thickness 500～600 ℃ of calcinings 5～15 minutes down.

Sealing prod and preparation method thereof

(being used to seal the method for PDP substrate)

The product of sealing of the present invention can be by with the paste composition coating that contains the sealing glass powder of the present invention or be printed on the substrate, calcines paste composition then and makes.More specifically, the product of sealing can be by method preparation as described below.

Slit between rear end glass substrate that is used for PDP and front glass substrate uses screen process press, divider etc. to fill the paste composition as the sealing glass paste composition of preparation.Then paste composition is carried out drying removing solvent, and under 400 ℃～500 ℃, calcine decomposing adhesive resin, thereby realize sealing the substrate that is used for PDP.Therefore, the product of the present invention sealing is to form between the substrate of PDP being used for.Calcining can be carried out in air or nitrogen.Subsequently, charging into the low pressure Ne gas that contains Xe waits and makes PDP.

Isolate rib and preparation method thereof

The present invention isolates rib can be by with the paste composition coating that contains barrier ribs strip material glass powder of the present invention or be printed on the substrate, calcines paste composition then and makes.More specifically, isolating rib can make by method as described below.

Isolate rib in order to use paste composition of the present invention to form, many methods are arranged, will the method that (a) contains sandblast be described below.Formed thereon on the whole surface of glass rear end substrate of electrode and dielectric layer, the paste composition of the present invention as barrier ribs strip material paste composition of coating preparation carries out paste composition drying subsequently with the removal solvent.Suitable thickness range is 50～200 μ m.On the paste composition layer, lamination exsiccant resist film carries out pattern exposure and development subsequently.Then, remove unnecessary portions, thereby lingering section is calcined formation isolation rib on glass substrate under 500～600 ℃ by sandblast.

Other method of form isolating rib comprises: thus thereby (b) comprise that repeatedly repeating silk screen printing is directly forming the method for patterning of isolating rib and (c) comprising on the surface that the barrier ribs strip material is coated on whole base plate by silk screen printing etc. and remove unnecessary barrier ribs strip material by comb and form the pattern of isolating rib on the substrate.Paste composition of the present invention also can be used in other barrier ribs bar formation method except that the method that contains sandblast.

Fluor and preparation method thereof

(preparation is used for the method for the rear end flat-panel component of PDP)

Fluor of the present invention can be by will containing fluorophor powder paste composition of the present invention coating or be printed on the substrate, calcine paste composition then and make.More specifically, fluor can make by method as described below.

Between the isolation rib that the rear end glass substrate that is used for PDP forms, use screen process press, divider etc. to fill the paste composition of the present invention as the phosphor slurry paste composite of preparation.Then paste composition is carried out drying with the removal solvent, and under 400 ℃～500 ℃, calcine, thereby make the rear end flat-panel component that is used for PDP with the decomposition adhesive resin.Thereby form fluor of the present invention.

Subsequently, adopt sealing material (low melting glass) that the front glass substrate and the rear end flat-panel component of independent preparation are sealed, and charge into the low pressure Ne gas that contains Xe and make PDP.

Embodiment

Quote the following examples the present invention is further described, but it is to be noted that the present invention is not limited to these embodiment.

The dielectric glass paste composition

Embodiment A 1

Synthetic (1) of pectination glycol

On the round flask of 500ml, be equipped with magnetic stirrer, thermometer and dropping funnel.In flask, add the 2 ethyl hexylamine (available from Kanto Kagaku) of 64.6g, and flask is cleaned with nitrogen.Flask is heated to 60 ℃ in oil bath, in 40 minutes, adopts dropping funnel to drip the 2-ethylhexyl glycidyl ether (available from Asahi Denka Co., Ltd., AdekaGlycirol ED518, epoxy several 220) of 220.0g in the flask while stirring.After dropwise operation is finished, oil bath temperature is elevated to 80 ℃, with flask heating 10 hours.After this, oil bath temperature is elevated to 120 ℃, uses vacuum pump under the vacuum tightness of 3mmHg, to carry out vacuum distilling and remove a small amount of unreacted matters.Make productive rate and be 90% pectination glycol (the 1) (molecular-weight average that obtains by the OH value: 532),, add 2-ethylhexyl glycidyl ether with the ratio of 2mol wherein based on the 2 ethyl hexylamine of 1mol.

Synthetic (1) of urethane resin

In the separable flask of the SUS of 1000ml, add 200g commercial PEG#6000 (available from Sanyo Chemical Industries, Ltd., number-average molecular weight: 8,630), with under the nitrogen purge with it 150 ℃ of following fusions.Stir on one side, Yi Bian (3mmHg) drying and melting body 3 hours under reduced pressure.Surplus water content is 200ppm.Temperature is reduced to 70 ℃, in flask, charges into an atmospheric nitrogen then.Add BHT (di-tert-butyl hydroxy toluene) with the amount of 300ppm then as oxidation inhibitor.When the material in the flask was stirred, the hexamethylene vulcabond (available from Tokyo Kasei Kogyo Co.Ltd.) of the pectination glycol (1) of adding 1.90g and 4.41g (NCO/OH=0.98mol/mol) in flask.Add the DBTDL of 0.05g as catalyzer, the result makes the rapid retrogradation of material in the flask in about 10 minutes.Then, stop to stir, reacted 2 hours down at 70 ℃.Then temperature is elevated to 120 ℃ and kept constant 30 minutes.Then, reactor product is taken out from flask.The weight-average molecular weight that product has is 470,000.

The product that takes out cut into pieces make its cooling then.Section is used liquid nitrogen to cool off and is adopted the small-sized electric runner milling that section is pulverized.Obtain the powder that particle diameter is no more than 600m thereby abrasive material is carried out sieving, with it as urethane resin (1).The median size that powder has is 400 μ m.

The preparation of binder resin solution (1)

In the separable flask of the glass of 200ml, add the urethane resin (1) of 10g and as the N-Methyl pyrrolidone (available from Kanto Kagaku) of the 90g of solvent, when being stirred 1 hour, they are heated to 60 ℃, with with resin dissolves in solvent, thereby obtain binder resin solution (1).

The preparation of dielectric paste paste composite (1)

Dielectric glass powder (the PbO-B that in the binder resin solution of 35g, adds 65g ₂O ₃-SiO ₂-CaO glass), obtain dielectric paste paste composite (1) after using three-roll grinder that they are mixed then.

The formation of dielectric layer

Using bar to be coated with machine is coated on dielectric layer paste composition (1) on the whole surface of alkali glass plate (soda glassplate), adopt hot air dryer under 120 ℃, to carry out drying then with the removal solvent, thereby and at 550 ℃ of following dielectric layers that obtained 50 μ m thickness in 10 minutes of calcining.

Use tracer needle surfagauge measure surface roughness Ra, found that this layer has slick surface, its surfaceness is 0.15 μ m.

Embodiment A 2

Dielectric glass powder (the PbO-B that in the binder resin solution (1) of 45g, adds 50g ₂O ₃-SiO ₂-CaO glass) and the quartz powder of 5g, obtain dielectric paste paste composite (2) after using three-roll grinder to mix.

Use bar to be coated with machine dielectric paste paste composite (2) is coated on the whole surface of alkali glass plate, adopt hot air dryer under 120 ℃, to carry out drying then with the removal solvent, thereby and at 550 ℃ of following dielectric layers that obtained 30 μ m thickness in 10 minutes of calcining.

Use tracer needle surfagauge measure surface roughness Ra, found that this layer has slick surface, its surfaceness is 0.10 μ m.

Comparative Examples A 1

In the separable flask of 200ml, add the ethyl cellulose of 10g and, stir and also be heated to 60 ℃ simultaneously in 1 hour as the N-Methyl pyrrolidone (available from Kanto Kagaku) of the 90g of solvent, with resin dissolves in solvent.Therefore, obtain binder resin solution (2).

Dielectric glass powder (the PbO-B that in the binder resin solution (2) of 40g, adds 60g ₂O ₃-SiO ₂-CaO glass), obtain dielectric paste paste composite (3) after the use three-roll grinder mixes.

Use bar to be coated with machine dielectric paste paste composite (3) is coated on the whole surface of alkali glass plate, adopt hot air dryer under 120 ℃, to carry out drying removing solvent then, thereby and calcine the dielectric layers that obtained 50 μ m thickness in 10 minutes down at 550 ℃.

Use tracer needle surfagauge measure surface roughness Ra, found that this layer has a lot of irregular surfaces, its surfaceness is 1.0 μ m.Because its unfairness, thereby damaged the transparency.Crackle occurs on the surface, make resistance to pressure reduce.

As mentioned above, under the situation of the paste that uses ethyl cellulose, a lot of unfairnesses can appear in the product surface when not using softening agent.On the contrary, although use urethane resin of the present invention not use softening agent also can obtain slick surface.

The sealing glass paste composition

Embodiment B 1

The preparation of binder resin solution (3)

In the separable flask of 200ml, add the urethane resin (1) of 6g and, stir and be heated to 60 ℃ simultaneously in 30 minutes as the N-Methyl pyrrolidone (available from Kanto Kagaku) of the 94g of solvent, with resin dissolves in solvent.Thereby obtain binder resin solution (3).

The preparation of sealing glass paste composition (1)

The P that in the binder resin solution (3) of 10g, adds 70g ₂O ₅-SnO-B ₂O ₃Glass and as the 20g stannic oxide powder of mineral filler obtains sealing glass paste composition (1) after using three-roll grinder to mix.

Silk screen printing

Use silk screen that sealing glass paste composition (1) is printed on the alkali glass plate.Its thickness is 100 μ m.The spinning property problem do not occur, obtain slick print surface.With the paste composition of printing thus 150 ℃ air drying 10 minutes, calcining 10 minutes in 450 ℃ air then.

The sealing glass glossiness

After calcining, the glossiness on sealing glass surface is by visual inspection.Found that glass surface is glossiness, glossiness variation phenomenon does not take place.

Embodiment B 2

Use silk screen will with the identical sealing glass paste composition (1) that uses in the Embodiment B 1 with Embodiment B 1 in identical mode be printed on the surface of alkali glass plate.With the paste composition of printing thus 150 ℃ air drying 10 minutes, calcining 10 minutes in 480 ℃ air then.

Embodiment B 3

The preparation of sealing glass paste composition (2)

The P that in the binder resin solution (3) of 20g, adds 40g ₂O ₅-SnO-B ₂O ₃Glass and as the 40g stannic oxide powder of mineral filler obtains sealing glass paste composition (2) after using three-roll grinder to mix.

Silk screen printing

Use silk screen that sealing glass paste composition (2) is printed on the alkali glass plate.Its thickness is 80 μ m.The spinning property problem do not occur, obtain slick print surface.With the paste composition of printing thus 150 ℃ air drying 10 minutes, calcining 10 minutes in 450 ℃ air then.

The sealing glass glossiness

Comparative example B1

In the N-Methyl pyrrolidone of 95g, the ethyl cellulose of dissolving 5g.The P that in the resulting binder resin solution of 10g, adds 70g ₂O ₅-SnO-B ₂O ₃Glass and as the 20g stannic oxide powder of mineral filler obtains sealing glass paste composition (3) after using three-roll grinder to mix.

Use silk screen that sealing glass paste composition (3) is printed on the alkali glass plate.Its thickness is 110 μ m.The spinning property problem do not occur, obtain slick print surface.With the paste composition of printing thus 150 ℃ air drying 10 minutes, calcining 10 minutes in 480 ℃ air then.After calcining, the glossiness on sealing glass surface is by visual inspection.Found that glass surface is brightless, gloss variation phenomenon takes place.

Comparative example B2

In the N-Methyl pyrrolidone of 95g, the acrylic resin of dissolving 5g (poly-(butyl methyl acrylate)).The P that in the resulting binder resin solution of 10g, adds 70g ₂O ₅-SnO-B ₂O ₃Glass and as the 20g stannic oxide powder of mineral filler obtains sealing glass paste composition (4) after using three-roll grinder to mix.

Use silk screen that sealing glass paste composition (4) is printed on the alkali glass plate.Its thickness is average 90 μ m.The spinning property problem occurs, and find unfairness at print surface.With the paste composition that obtains thus 150 ℃ air drying 10 minutes, calcining 10 minutes in 480 ℃ air then.

After calcining, the glossiness on sealing glass surface is by visual inspection.Found that glass surface is glossiness, glossiness variation phenomenon does not take place.Yet, still show unfairness in the calcining rear surface.

Under the situation of the paste that uses ethyl cellulose, find to cause vitreous luster degree variation owing in air, calcining.In contrast, under the situation of using sealing glass paste composition of the present invention, do not have to find owing in air, calcining the vitreous luster degree variation that causes.In addition, even to calcine in nitrogen also be feasible.Even this shows sealing glass paste composition of the present invention at low temperatures or calcine also and decompose easily in air, thereby make sealing glass be difficult to take place the glossiness variation.

Paste composition of the present invention has superior printing characteristics and pyrolytic, and paste composition also can be used as the glass paste paste composite of IC encapsulation usefulness.

Barrier ribs strip material paste composition

Embodiment C 1

Synthesizing of urethane resin (2)

In the separable flask of the SUS of 1000ml, the commercial PEG#6000 that adds 160g is (available from Sanyo Chemical Industries, Ltd., number-average molecular weight: 8,630) and the commercial PTMEG#1000 of 40g (available from Hodogaya Chemical Co., Ltd., number-average molecular weight: 1,039), with under the nitrogen purge with it 150 ℃ of following fusions.When stirring, with molten mass under reduced pressure (3mmHg) dry 3 hours.Surplus water content is 200ppm.Temperature is reduced to 70 ℃, in flask, charges into 1 atmospheric nitrogen then.As oxidation inhibitor, add the BHT (di-tert-butyl hydroxy toluene) of 300ppm.When the material in the flask was stirred, the pectination glycol (1) of adding 2.00g and the hexamethylene vulcabond of 5.07g were (available from Tokyo Kasei Kogyo Co., Ltd.) (NCO/OH=0.99mol/mol).Add the DBTDL of 0.05g, make the rapid retrogradation of material in the flask in 10 minutes as a result as catalyzer.Then, stop to stir, reacted 2 hours down at 70 ℃.Then temperature is elevated to 120 ℃ and kept constant temperature 30 minutes.Then, reactor product is taken out from flask.The weight-average molecular weight that product has is 300,000.

The product that takes out cut into pieces then cool off.Section is used liquid nitrogen to cool off and is adopted the small-sized electric runner milling that section is pulverized.Obtain the powder that particle diameter is no more than 600 μ m thereby abrasive material is carried out sieving, with it as adhesive resin (urethane resin (2)).The median size that powder has is 400 μ m.

The preparation of binder resin solution (4)

In the separable flask of 200ml, add the urethane resin (2) of 20g and, stir and be heated to 60 ℃ simultaneously in 1 hour as the N-Methyl pyrrolidone (available from Kanto Kagaku) of the 80g of solvent, with resin dissolves in solvent.Therefore, obtain binder resin solution (4).

The preparation of barrier ribs strip material paste composition (1)

Glass powder (the PbO-B that in the binder resin solution (4) of 20g, adds 60g ₂O ₃-SiO ₂) and as the 20g alumina powder of mineral filler, obtain barrier ribs strip material paste composition (1) after using three-roll grinder to mix.

Isolate the formation of rib

Use spreader that barrier ribs strip material paste composition (1) is coated on the whole surface of alkali glass plate, adopt the hot air dryer drying removing solvent then, thereby obtain the barrier ribs web bed of material of 180 μ m thickness.Press the exsiccant resist film on this layer upper strata, and then cover one deck optical screen film in the above, expose subsequently and develop.Use 1% soda lye removal unexposed portion.Then, the sandblast operation of using calcium carbonate powders to carry out 90 seconds by sand spraying device.The degree of depth after the sandblast is measured, and it is 110 μ m, and it is a proper depth.When shape of cross section is observed, find that the outside surface of isolation rib almost is flat, and do not find excessive sandblast phenomenon.

Comparative example C1

In the separable flask of the glass of 200ml, add the ethyl cellulose of 20g and, stir and be heated to 60 ℃ simultaneously in 1 hour as the N-Methyl pyrrolidone (available from Kanto Kagaku) of the 80g of solvent, with resin dissolves in solvent.Thereby obtain binder resin solution (5).

Glass powder (the PbO-B that in the binder resin solution (5) of 20g, adds 60g ₂O ₃-SiO ₂) and the 20g aluminum oxide, after mixing, the use three-roll grinder obtains barrier ribs strip material paste composition (2).

Use spreader that barrier ribs strip material paste composition (2) is coated on the whole surface of alkali glass plate, adopt the hot air dryer drying removing solvent then, thereby obtain the barrier ribs web bed of material of 180 μ m thickness.Press the exsiccant resist film on this layer upper strata, and then cover one deck optical screen film in the above, expose subsequently and develop.Use 1% soda lye removal unexposed portion.Then, by sand spraying device and the sandblast operation of using calcium carbonate powders to carry out 90 seconds.When the degree of depth after the sandblast was measured, it was 100 μ m, is suitable thickness.When shape of cross section was observed, discovery was isolated too many (excessively sandblast) phenomenon of outside surface centre sandblast of rib and is formed concave surface.

When use has utilized the paste of ethyl cellulose that sandblast is proceeded to enough degree of depth, find that excessive sandblast appears in the side surface of isolating rib, promptly this paste has problems aspect sandblast.On the other hand, although use barrier ribs strip material paste composition of the present invention that sandblast is proceeded to much at one the degree of depth, the side surface of isolating rib is not by excessive sandblast, thereby paste composition has good sandblast.

The phosphor slurry paste composite

Embodiment D1

Synthesizing of urethane resin (3)

In the separable flask of the SUS of 1000ml (separable flask), add 200g commercial PEG#6000 (available from Sanyo Chemical Industries, Ltd., number-average molecular weight: 8,630), with under the nitrogen purge with it 150 ℃ of following fusions.Follow stirring, under decompression (3mmHg) with dry 3 hours of molten mass.Remainder water content is 200ppm.Temperature is reduced to 70 ℃, in flask, charges into 1 atmospheric nitrogen then.Add BHT (di-tert-butyl hydroxy toluene) then as the 300ppm of oxidation inhibitor.When the material in the flask was stirred, the pectination glycol (1) of adding 1.90g and the hexamethylene vulcabond of 4.28g were (available from Tokyo Kasei Kogyo Co., Ltd.) (NCO/OH=0.95mol/mol).Add the DBTDL of 0.05g, make the rapid retrogradation of material in the flask in 10 minutes as a result as catalyzer.Then, stop to stir, reacted 2 hours down at 70 ℃.Then temperature is elevated to 120 ℃ and kept constant 30 minutes.Then, reactor product is taken out from flask.The weight-average molecular weight that product has is 290,000.

The product that takes out cut into pieces make its cooling then.Section is used liquid nitrogen to cool off and is adopted the small-sized electric runner milling that section is pulverized.Obtain the powder that particle diameter is no more than 600 μ m thereby abrasive material is carried out sieving, with it as adhesive resin (urethane resin (3)).The median size that powder has is 400 μ m.

The preparation of binder resin solution (6)

In the separable flask of the glass of 200ml, add the urethane resin (3) of 9g and, stir and be heated to 60 ℃ simultaneously in 30 minutes as the N-Methyl pyrrolidone (available from Kanto Kagaku) of the 91g of solvent, with resin dissolves in solvent.Thereby obtain binder resin solution (6).

The preparation of phosphor slurry paste composite (1)

Blue emitting phophor powder (the BaMgAl that in the binder resin solution (6) of 50g, adds 50g ₁₀O ₁₇: Eu), after mixing, the use three-roll grinder obtains blue emitting phophor paste composition (1).

Silk screen printing

Use silk screen that phosphor slurry paste composite (1) is printed on the alkali glass plate.Thickness is 30 μ m.The spinning property problem do not occur, obtain slick print surface.With the paste composition that obtains thus 150 ℃ dry 10 minutes down, then 450 ℃ of calcinings 10 minutes down.

The brightness of fluor

Fluor after peeling off, sheet glass is reverted to fluorophor powder.This powder is shone to measure the luminous intensity of fluor with UV-light (146nm).When the luminous intensity without the incinerating fluorophor powder was 100%, the luminous intensity of the fluor after obtaining calcining was 96%.

Embodiment D2

Synthesizing of urethane resin (4)

In the separable flask of the SUS of 1000ml, add 200g commercial PEG#6000 (available from Sanyo Chemical Industries, Ltd., number-average molecular weight: 8,630), with under the nitrogen purge with it 150 ℃ of following fusions.Follow stirring, molten mass was decompression (3mmHg) dry 3 hours down.Surplus water content is 200ppm.Temperature is reduced to 70 ℃, in flask, charges into 1 atmospheric nitrogen then.Add BHT (di-tert-butyl hydroxy toluene) then as the 300ppm of oxidation inhibitor.When the material in the flask was stirred, the pectination glycol (1) of adding 1.90g and the hexamethylene vulcabond of 4.41g were (available from Tokyo Kasei Kogyo Co., Ltd.) (NCO/OH=0.98mol/mol).Add the DBTDL of 0.05g, make the rapid retrogradation of material in the flask in 10 minutes as a result as catalyzer.Then, stop to stir, reacted 2 hours down at 70 ℃.Then temperature is elevated to 120 ℃ and kept constant 30 minutes.Then, reactor product is taken out from flask.The weight-average molecular weight that product has is 470,000.

The product that takes out cut into pieces make its cooling then.Section is used liquid nitrogen to cool off and is adopted the small-sized electric runner milling that section is pulverized.Obtain the powder that particle diameter is no more than 600 μ m thereby abrasive material is carried out sieving, with it as adhesive resin (urethane resin (4)).The median size that powder has is 400 μ m.

The preparation of binder resin solution (7)

In the separable flask of the glass of 200ml, add the urethane resin (4) of 6g and, stir and be heated to 60 ℃ simultaneously in 30 minutes as the N-Methyl pyrrolidone (available from Kanto Kagaku) of the 94g of solvent, with resin dissolves in solvent.Thereby obtain binder resin solution (7).

The preparation of phosphor slurry paste composite (2)

The red-emitting phosphors powder ((Y, Gd) BO that in the binder resin solution (7) of 50g, add 50g ₃: Eu), after mixing, the use three-roll grinder obtains red-emitting phosphors paste composition (2).

Silk screen printing

Use silk screen that phosphor slurry paste composite (2) is printed on the alkali glass plate.Thickness is 30 μ m.The spinning property problem do not occur, obtain slick print surface.With the paste composition that obtains thus 150 ℃ dry 10 minutes down, then 450 ℃ of calcinings 10 minutes down.

The brightness of fluor

Fluor after peeling off, sheet glass is reverted to fluorophor powder.This powder is shone to measure the luminous intensity of fluor with UV-light (146nm).When the luminous intensity without the incinerating fluorophor powder was 100%, the luminous intensity of the fluor after obtaining calcining was 95%.

Comparative example D1

The ethyl cellulose of 5g is dissolved in the N monomethyl pyrrolidone of 95g.Blue emitting phophor powder (the BaMgAl that in the solution of 50g gained, adds 50g then ₁₀O ₁₇: Eu), after mixing, the use three-roll grinder obtains blue emitting phophor paste composition (3).

Use silk screen that phosphor slurry paste composite (3) is printed on the alkali glass plate.Thickness is 30 μ m.The spinning property problem do not occur, obtain slick print surface.With the paste composition that obtains thus 150 ℃ of dryings 10 minutes, then 500 ℃ of calcinings 10 minutes.Fluor after peeling off, sheet glass is reverted to fluorophor powder.This powder is shone to measure the luminous intensity of fluor with UV-light (146nm).When the luminous intensity without the incinerating fluorophor powder was 100%, the luminous intensity of the fluor after obtaining calcining was 80%.

Under the situation of the paste that uses ethyl cellulose, be 80% through relative luminous intensity after 500 ℃ of calcinings.In contrast, under the situation of using phosphor slurry paste composite of the present invention, be not less than 95% through relative luminous intensity after 450 ℃ of calcinings.Even this shows carbonization takes place hardly also when phosphor slurry paste composite of the present invention is calcined at low temperatures, thereby the brightness of fluor is reduced.

Industrial applicibility

Paste composition of the present invention can be used for forming dielectric layer, the PDP of PDP (plasma display panel) Seal glass layer, the barrier ribs web bed of material of PDP and the luminescent coating of PDP. Paste of the present invention Composition is very useful as the paste composition that is used for display.

Claims

1. paste composition, it comprises:

(i) urethane resin, it comprises:

(a) the represented repeating unit of general formula (1) below:

Wherein, A is the group (divalent group) that obtains behind the OH group of removing among polyoxyalkylene glycol (compd A) HO-A-OH that there is hydroxyl at two ends, B is the group (divalent group) that obtains behind the NCO group of removing among vulcabond (compd B) OCN-B-NCO, and

(b) the represented repeating unit of general formula (2) below:

Wherein, D is the group (divalent group) that obtains behind the OH group of removing among the pectination glycol HO-D-OH, wherein have two carbonatomss in the pectination glycol molecules at least and are 4～21 alkyl (monoradical), B is for removing the group (divalent group) that obtains behind the NCO group among vulcabond (compd B) OCN-B-NCO

The molar fraction of repeating unit in the described urethane resin (a) is 0.35～0.99, and the molar fraction of repeating unit (b) is 0.01～0.65, and prerequisite is to be 1 with the two total molar fraction;

(ii) solvent; And

(iii) powder.

2. paste composition according to claim 1, wherein, pectination glycol HO-D-OH is the pectination glycol (Compound D) of following general formula (3) expression or the pectination glycol of following general formula (4) expression (Compound D '):

Wherein, R ¹Be alkyl or the nitrogenous alkyl with 1～20 carbon atom, R ²And R ³Respectively doing for oneself has the alkyl of 4～21 carbon atoms, at R ¹, R ²And R ³In part or all of hydrogen atom can be replaced and R by fluorine, chlorine, bromine or iodine ²And R ³Can be the same or different,

Y and Y ' respectively do for oneself hydrogen, methyl or CH ₂The Cl base, and Y and Y ' can be the same or different,

Wherein, R ⁵For having the alkyl of 1～20 carbon atom, R ²And R ³Respectively doing for oneself has the alkyl of 4～21 carbon atoms, at R ⁵, R ²And R ³In part or all of hydrogen atom can be replaced and R by fluorine, chlorine, bromine or iodine ²And R ³Can be the same or different,

Y, Y ' and Y " hydrogen, methyl or CH respectively do for oneself ₂The Cl base, and Y and Y ' can be the same or different.

R ⁴For total has the alkylene of 2～4 carbon atoms,

K is 0～15 integer,

3. paste composition according to claim 1 and 2, wherein, powder (iii) is the low melting glass powder.

4. according to each described paste composition in the claim 1～3, wherein, also comprise as powder mineral filler (except that the low melting glass powder) (iii).

5. paste composition according to claim 1 and 2, wherein, powder (iii) is a fluorophor powder.

6. according to each described paste composition in the claim 1～4, wherein, the low melting glass powder is a dielectric medium powder.

7. according to each described paste composition in the claim 1～4, wherein, the low melting glass powder is the sealing glass powder.

8. according to each described paste composition in the claim 1～4, wherein, the low melting glass powder is a barrier ribs strip material glass powder.

9. dielectric layer, it is formed by each described paste composition in claim 1～4 and 6.

10. sealing prod, it is formed by each described paste composition in claim 1～4 and 7.

11. isolate rib for one kind, it is formed by each described paste composition in claim 1～4 and 8.

12. a fluor, it is formed by each described paste composition in the claim 1,2 and 5.

13. a method for preparing dielectric layer, it comprises each described paste composition coating in claim 1～4 and 6 or is printed on the step of calcining paste composition on the substrate then.

14. a method for preparing sealing prod, it comprises each described paste composition coating in claim 1～4 and 7 or is printed on the step of calcining paste composition on the substrate then.

15. one kind prepares the method for isolating rib, it comprises each described paste composition coating in claim 1～4 and 8 or is printed on the step of calcining paste composition on the substrate then.

16. a method for preparing fluor, it comprises each described paste composition coating in the claim 1,2 and 5 or is printed on the step of calcining paste composition on the substrate then.