CN1438667A - Optical-solidifying composition and plasma displaying board using same to form black pattern - Google Patents

Optical-solidifying composition and plasma displaying board using same to form black pattern Download PDF

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Publication number
CN1438667A
CN1438667A CN03104467A CN03104467A CN1438667A CN 1438667 A CN1438667 A CN 1438667A CN 03104467 A CN03104467 A CN 03104467A CN 03104467 A CN03104467 A CN 03104467A CN 1438667 A CN1438667 A CN 1438667A
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mass parts
photocurable composition
black
mentioned
thermal endurance
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CN100433228C (en
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伊藤秀之
东海裕之
高木幸一
福岛和信
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G3/00—Scaffolds essentially supported by building constructions, e.g. adjustable in height
    • E04G3/28—Mobile scaffolds; Scaffolds with mobile platforms
    • E04G3/30—Mobile scaffolds; Scaffolds with mobile platforms suspended by flexible supporting elements, e.g. cables
    • E04G3/305—Mobile scaffolds; Scaffolds with mobile platforms suspended by flexible supporting elements, e.g. cables specially adapted for tanks, silos or similar vessels
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G23/00—Working measures on existing buildings
    • E04G23/02—Repairing, e.g. filling cracks; Restoring; Altering; Enlarging
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G3/00—Scaffolds essentially supported by building constructions, e.g. adjustable in height
    • E04G3/28—Mobile scaffolds; Scaffolds with mobile platforms
    • E04G2003/286—Mobile scaffolds; Scaffolds with mobile platforms mobile vertically

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Mechanical Engineering (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials For Photolithography (AREA)
  • Gas-Filled Discharge Tubes (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

To provide a photocurable composition which can be formed into paste without causing secondary coagulation of a heat-resistant black pigment, is excellent in preserving stability, without impairing excellent adhesion to a substrate in a drying step, resolution in an exposing step and a developing step, and firability in a firing step, and can form a fired film retaining sufficient blackness even after firing. The photocurable composition as the first embodiment of this invention comprises (A) a slurry in which the heat-resistant black pigment with a maximum particle size of 5 [mu]m or less is uniformly dispersed in a solvent, (B) an organic binder, (C) a photopolymerizable monomer and (D) a photopolymerization initiator. The second embodiment of the invention further comprises (E) an organic acid and/or (F) a polymerization inhibitor in addition to the above ingredients (A) to (D).

Description

Photocurable composition and the plasma display panel that uses its formation black pattern
Technical field
The present invention relates on the front substrate of plasma display panel (hereinafter to be referred as PDP) to form the alkali-developable useful in fine electrode circuit and the black pattern and the composition of light-cured type, and the PDP that is equipped with the front substrate of lower floor's (black layer) of using said composition to form the bus electrode with white black double-layer structure, black matrix" (Block Star Network マ ト リ Star Network ス).
Prior art
PDP utilizes by plasma discharge is luminous to carry out the flat-panel screens that image and information show, is divided into DC type and AC type according to structure, the driving method of plate.The principle that the colour that is produced by PDP shows is, produce plasma discharge in the space, opposed two interelectrode chambers (discharge space) that on front glass substrate that separates by rib (partition) and back side glass substrate, forms, the fluorophor that the ultraviolet ray excited glass substrate overleaf the inside of the discharge generation by enclosing the gases such as He, Xe in each space, chamber forms produces 3 primary colors visible lights.Each battery space is separated by cancellate rib in DC type PDP, and the rib that is arranged in parallel on by real estate in AC type PDP is separated on the other hand, but the separation of battery space is all finished by rib in any type.Below, on one side with reference to accompanying drawing explanation simply on one side.
Fig. 1 partly represents the structure example of face discharge mode PDP of 3 electrode structures of panchromatic demonstration.In front glass substrate 1 below, by the transparency electrode 3a that is used to discharge or 3b be used to reduce the bus electrode 4a of line resistance of this transparency electrode or a pair of show electrode 2a, 2b that 4b constitutes with predetermined a plurality of arrangement of pitch.On these show electrodes 2a, 2b, be formed for accumulating the transparency dielectric layer 5 (low-melting glass) of electric charge, evaporation protective layer (MgO) in the above by printing, sintering.Protective layer 6 has the protection show electrode, keeps effect such as discharge condition.On the other hand, on the glass substrate 11, separate the strip rib (partition) 12 of discharge space and pitch a plurality of arranging of address electrode (data electrode) 13 to be scheduled to of the interior configuration of each discharge space overleaf.In addition,, dispose red (14a), blue (14b), green (14c) 3 look fluorescent membranes regularly, in panchromatic demonstration, constitute 1 pixel by above-mentioned red, blue, green 3 primary colors fluorescent membrane 14a, 14b, 14c in the inside of each discharge space.
In addition, give birth to a pair of show electrode 2a that forms discharge space, the position, both sides of 2b,, form the black matrix" 10 of strip equally in order further to improve the contrast of image.
Also have, in the PDP of said structure,, between the electrode on the same substrate, discharge, therefore be called as " face discharge mode " owing between a pair of show electrode 2a, 2b, apply the pulse voltage of interchange.
In addition, in the PDP of said structure, because fluorescent membrane 14a, 14b, the 14c of the ultraviolet ray excited back substrate 11 of discharge generation, form the structure of the transparency electrode 3a that sees through front substrate 1, visible light that 3b sees generation.
In the PDP of this spline structure, the formation of above-mentioned bus electrode 4a, 4b can be used photolithography to implement pattern and be formed after by evaporation or three layers of film forming of sputter Cr-Cu-Cr at present.
Yet, because process number is many, cost uprises, be implemented in the method for sintering after the conductivity paste such as silk screen printing silver paste recently, perhaps in order to form the live width below the 150 μ m, coating photoelectric sensitivity conductive paste, by pattern mask exposure back, develop, the then method of sintering.
So in the front substrate of the PDP that forms electrode 4a, 4b, in recent years in order to improve the contrast of picture, when forming bus electrode, go up the black layer of process black paste in the lower floor that becomes the demonstration side (layer that contacts with transparency electrode 3a, 3b), the white layer of printing conductive silver paste forms white electrode of deceiving double-layer structure in the above.In this case, as the black paste, can use the resin combination that has cooperated thermal endurance black pigments such as copper-iron system, copper-black composite oxides such as chromium system, cobaltosic oxide.
In addition, can attempt will be at present form that CRT shows and black matrix"s such as LCD panel in the photosensitive polymer combination of the photomask formation usefulness that use be diverted to the formation of above-mentioned black matrix".
Yet, in the manufacturing of PDP, having the high temperature sintering operation, photomask forms the carbon black decomposition that contains in the photosensitive polymer combination of usefulness in this operation, and it is difficult that the formation of the black matrix" that can satisfy becomes.
Therefore, even form in the photosensitive polymer combination of usefulness at the photomask that contains optical polymerism composition, combined polymerization initator and light-proofness material, as above-mentioned light-proofness material, also can use the resin combination that has cooperated thermal endurance black pigments such as copper-iron system, copper-black composite oxides such as chromium system, cobaltosic oxide.
Yet, the resin combination that has cooperated thermal endurance black pigments such as copper-iron system, copper-black composite oxides such as chromium system, cobaltosic oxide, storage stability as paste is poor, when particularly cooperating photopolymerization monomer and combined polymerization initator to constitute Photocurable composition together, photopolymerization monomer begins polymerization, and gelation can take place.Therefore, this resin combination need be taken care of at low temperatures, in addition because gelation and mobile reduction, also exist so-called coating operability poor, can not adapt to mass-produced problem.
In addition, be accompanied by the requirement that high fine pattern forms, the thermal endurance black pigment need be with its particle diameter pathization.Yet the thermal endurance black pigment if its particle diameter diminishes, will cause that what is called causes the secondary aggegation when disperseing easily in paste, and be coated with the problem that exists projection to cause nemaline defective in the rete.
Summary of the invention
Therefore the present invention is in order to solve the problem that comprises such prior art, main purpose is to provide and that it(?) can not can causes thermal endurance black pigment secondary aggegation ground carry out pasteization, and storage stability is good, in each operation of drying, exposure, development, sintering, can not damage the adaptation good, clarity, agglutinating property, even behind sintering, can form the Photocurable composition of sintered film with enough blackness with respect to substrate yet.
Another object of the present invention is to provide by such Photocurable composition and forms high meticulous black pattern, particularly forms black layer of (lower floor) telegraph circuit satisfying sufficient interlayer conductivity (interlayer conduction of the white layer of transparency electrode and bus electrode) and blackness in the bus electrode of white black double-layer structure simultaneously and the PDP of black matrix" in front on the substrate.
In order to achieve the above object, basic first scheme of Photocurable composition of the present invention is characterised in that containing (A) is that thermal endurance black pigment below the 5 μ m or cobaltosic oxide black particle are dispersed in slurry in the solvent, (B) organic bond, (C) photopolymerization monomer and (D) Photoepolymerizationinitiater initiater with maximum particle diameter, and alternative plan is characterised in that and also contains (E) organic acid and/or (F) polymerization inhibitor except above-mentioned each composition in addition.
Such Photocurable composition of the present invention both can be a paste shape form, also can be the dry film form of making film like in advance.
According to the present invention, provide by the sinter of this Photocurable composition and form the telegraph circuit (black layer) of front substrate, the PDP of black matrix" in addition.
Description of drawings
Fig. 1 is the part exploded perspective view of the AC type PDP of face discharge mode.
Embodiment
The result that present inventors attentively study to achieve these goals is characterised in that use is that thermal endurance black pigment below the 5 μ m is dispersed in the slurry in the solvent with maximum particle diameter.
Thus, Photocurable composition of the present invention can be made the paste that does not have the secondary agglutinator easily.Its result can provide the PDP that forms high meticulous telegraph circuit and black matrix".
On the other hand, contain the Photocurable composition of filler such as thermal endurance black pigment, do not have the shortcoming that stabilizer at room temperature may tackify if exist.Therefore, for the polymerization that suppresses photopolymerization monomer be considered to because the gelation of the Photocurable composition that the carboxyl reaction in thermal endurance black pigment and the organic bond causes can be used phosphate as stabilizer at present.Yet, in Photocurable composition of the present invention, if use phosphate as stabilizer, the problem of existence be cause in the slurry the sedimentation of thermal endurance black pigment, cause the powder aggegation easily, and then bring harmful effect for the storage stability of slurry.
To this, present inventors make further research again, found that by cooperating the organic acid as stabilizer, preferred organic acid and thermal polymerization inhibitor, can be provided in storage stability under the room temperature also extremely good, also can fully adapt to the Photocurable composition of the property produced in batches.
In addition according to Photocurable composition of the present invention, if use the cobaltosic oxide black particles as above-mentioned thermal endurance black pigment, it is fine and close that the black thin film that forms becomes, even film also can present enough black, its result can obtain not damaging the adaptation good with respect to substrate, clarity, agglutinating property in each operation of drying, exposure, development, sintering, can obtain satisfying simultaneously the pattern of sufficient interlayer conductivity (interlayer conduction of the white layer of transparency electrode and bus electrode) and blackness behind sintering.
Thereby, if use the black layer material of such Photocurable composition as the bus electrode of the white black double-layer structure that forms on the PDP front substrate, be clipped in sandwich between transparency electrode such as ITO or nesa coating and the white layer because bus electrode has black layer, therefore can fully satisfy the interlayer conduction of transparency electrode and white layer and the black when the picture side is observed simultaneously.
And, Photocurable composition of the present invention, because storage stability thickness good and that use is thin can obtain enough contrasts as mentioned above, therefore batch process and the cost degradation for PDP is exceedingly useful.
Be illustrated particularly at Photocurable composition of the present invention below.
At first, be that the slurry (A) that thermal endurance black pigment below the 5 μ m is dispersed in the solvent can be according at present known method by making the thermal endurance black pigment be evenly dispersed in that modulation forms in the solvent with maximum particle diameter.For example, using mixer such as ball mill to make solvent, dispersant and thermal endurance black pigment mix fully disperses modulation to form.
Here, as stable on heating black pigment,, therefore can use inorganic pigment with tone stability under the high temperature owing in the substrate manufacture operation of PDP, follow 500～600 ℃ high temperature sintering.Oxide such as Cr, Co, Cu, Ni, Fe, Mn and composite oxides etc. are arranged particularly, but be not limited to these, these can use more than 2 kinds alone or in combination.Particularly in the present invention, copper-chromium is that black composite oxide, copper-iron are black composite oxide, cobaltosic oxide etc., and therefore densification and excellent color tone because the black thin film that forms behind sintering becomes are fit to use.
It is below the 2 μ m that this thermal endurance black pigment preferably uses average grain diameter, more preferably the following particulate of the above 1 μ m of 0.01 μ m.Its reason be because, if average grain diameter is below the 2 μ m, ground forms fine and close sintered film even a small amount of interpolation also can not can damage adaptation etc., and the resin combination that can provide lower floor's (black layer) electrode of satisfying sufficient interlayer conductivity (interlayer conduction of the white layer of transparency electrode and bus electrode) and black simultaneously to use.On the other hand, if the average grain diameter of thermal endurance black pigment greater than 2 μ m, the compactness variation of sintered film, the degree of blackness of the lower electrode film of formation reduces easily.In addition, if less than 0.01 μ m,, therefore be not suitable for because covering power reduces, manifests transparent feel.
In addition, the thermal endurance black pigment preferably uses specific area at 1.0～20m 2Cobaltosic oxide particulate in the/g scope.Its reason be because, if the not enough 1.0m of its specific area 2/ g, the precision of the circuit pattern that forms by exposing reduces, and obtains the linearity at line edge or the sintered film of enough blackness and becomes difficult.On the other hand, if surpass 20m 2/ g, the surface area of particle becomes excessive, and lower floor's development relative deficiency takes place when developing easily.
The combined amount of the thermal endurance black pigment in this slurry, suiting to be adjusted into respect to 100 mass parts organic bonds (B) is the scope of 1～120 mass parts, preferred 30～100 mass parts.Its reason is because if the use level of thermal endurance black pigment is also lacked than above-mentioned scope, then can not get enough blackness behind sintering, on the other hand, if combined amount surpasses above-mentioned scope, the permeability variation of light, clarity reduce, cost uprises in addition, is unfavorable.
The solvent that uses in the above-mentioned slurry can be selected arbitrarily, but in order to prevent the solvent upset, solvent and the kind used in hope and the paste are same.
In addition, the concentration of the solid constituent in the slurry can be selected arbitrarily, if but consider operability etc., be preferably 50～80 quality %.That is, to be preferably with respect to 100 mass parts slurries be the ratio of 20～50 mass parts to the use level of solvent.
In addition, the dispersant that uses in the above-mentioned slurry, as long as can disperse the thermal endurance black pigment equably, limit especially, for example can enumerate the chemical Off ロ-macromolecule dispersing agents such as レ Application made of マ リ ア リ system series and common prosperity society that Japanese grease is made.
The combined amount of this dispersant, being suitably with respect to 100 mass parts thermal endurance black pigments is 1～20 mass parts.Under the situation that the use level of this dispersant is lacked than above-mentioned scope, can not obtain sufficient dispersion effect, on the other hand, add and also can not get better dispersion effect even surpass above-mentioned scope volume.
Secondly, as above-mentioned organic bond (B), can use the resin that contains carboxyl, itself have a photoresist of the carboxyl that contains the ethene unsaturated double-bond and have any in the resin of the carboxyl that does not contain the ethene unsaturated double-bond specifically.As the resin that can be fit to use (in oligomer and the polymer any all can), can be listed below.
(1) by making unsaturated carboxylic acid (a) and contain the resin that contains carboxyl that compound (b) copolymerization of unsaturated double-bond obtains
(2) by at unsaturated carboxylic acid (a) with contain the photoresist that contains carboxyl that addition ethene unsaturated group obtains as side group in the copolymer of compound (b) of unsaturated double-bond
(3) feasible copolymer and the secondary hydroxyl of unsaturated carboxylic acid (a) reaction generation and the photoresist that contains carboxyl that multi-anhydride (d) reaction obtains that contains the compound (c) of epoxy radicals and unsaturated double-bond and contain the compound (b) of unsaturated double-bond
(4) make the copolymer contain the acid anhydrides (e) of unsaturated double-bond and to contain the compound (b) of unsaturated double-bond react the photoresist that contains carboxyl that obtains with the compound (f) that contains hydroxyl and unsaturated double-bond
(5) secondary hydroxyl and the multi-anhydride (d) that makes multi-functional epoxy compound (g) and unsaturated monocarboxylic (h) reaction generate reacts the photoresist that contains carboxyl that obtains
(6) make and to react the resin that contains carboxyl that obtains with multi-anhydride (d) by the secondary hydroxyl that contains 1 carboxyl in epoxy radicals and 1 molecule in the copolymer of the compound (b) contain unsaturated double-bond and (methyl) glycidyl acrylate, do not contain organic acid (i) the reaction generation of ethene unsaturated double-bond
(7) make the polymer (j) that contains hydroxyl react the resin that contains carboxyl that obtains with multi-anhydride (d)
(8) make the polymer (j) that contains hydroxyl react the resin that contains carboxyl that obtains, react the photoresist that contains carboxyl that obtains with the compound that contains epoxy radicals and unsaturated double-bond (c) with multi-anhydride (d)
The above-mentioned resin that contains the photoresist of carboxyl and contain carboxyl can be used alone or as a mixture, but preferably cooperates with the ratio of 10～80 quality % that add up to total composition in either case.When the use level of these polymer was more very few than above-mentioned scope, it is inhomogeneous that the distribution of the above-mentioned resin in the film of formation becomes easily, is difficult to obtain the enough photo-curables and the photocuring degree of depth, becomes difficult by selecting exposure, development to form pattern.On the other hand, if more too much than above-mentioned scope, fold and live width that pattern takes place during owing to sintering are easily shunk, and are unfavorable therefore.
In addition, as the above-mentioned resin that contains the photoresist of carboxyl and contain carboxyl, suitable use separately weight average molecular weight be 1000～100000, preferred 5000～70000 and acid number be 50～250mgKOH/g, and be 350～2000, preferred 400～1500 resin for its pair of the photoresist key equivalent that contains carboxyl.Being lower than at the molecular weight of above-mentioned resin under 1000 the situation, will the adaptation of film bringing harmful effect when developing, on the other hand, being higher than under 100000 the situation, because poor visualization takes place easily, is unfavorable therefore.In addition, be lower than at acid number under the situation of 50mgKOH/g, dissolubility with respect to alkaline aqueous solution is insufficient, poor visualization takes place easily, be higher than under the situation of 250mgKOH/g on the other hand, because the dissolving of the deterioration and the photocuring part (exposed portion) of film adaptation takes place when developing, be unfavorable therefore.In addition, for the situation of the photoresist that contains carboxyl, if two key equivalents of photoresist are less than 350, if easy residual residue when sintering then is on the other hand greater than 2000, because the operation degree of freedom when developing is narrow, and needing high exposure when photocuring, is unfavorable therefore.
Secondly, the photopolymerization monomer in the Photocurable composition of the present invention (C) uses for the photo-curable and the raising development that promote composition.As this photopolymerization monomer (C), specifiable is acrylic acid 2-hydroxyl ethyl ester for example, acrylic acid 2-hydroxypropyl acrylate, diacrylate diethylene glycol (DEG) ester, the diacrylate triethyleneglycol ester, polyethyleneglycol diacrylate, urethane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetracrylate, the triacrylate of trimethylolpropane oxirane modification, the triacrylate of trimethylolpropane epoxy pronane modification, five acrylic acid dipentaerythritol ester, six acrylic acid dipentaerythritol ester and corresponding to each methyl acrylic ester of aforesaid propylene acid esters; The list of polyacid such as phthalic acid, adipic acid, maleic acid, furoate clothing, butanedioic acid, trimellitic acid, terephthalic acids and hydroxyalkyl (methyl) acrylate-, two-, three-or its above polyester etc., but be not limited to specific these, these esters can separately or mix more than 2 kinds and use in addition.In these photopolymerization monomers, contain the polyfunctional monomer of 2 above acryloyl groups or methacryl in preferred 1 molecule.
The use level of this photopolymerization monomer (C), being suitably for respect to the above-mentioned organic bond of 100 mass parts (contain the photoresist of carboxyl and/or contain the resin of carboxyl) is 20～100 mass parts (B).The use level of photopolymerization monomer (C) than above-mentioned scope after a little while, the sufficient photo-curable of composition is difficult to obtain, become when excessive if surpass above-mentioned scope on the other hand, become early, therefore take place to solidify inhomogeneous easily owing to compare the photocuring at surperficial position with the position, deep of film.
Secondly, as the Photoepolymerizationinitiater initiater in the Photocurable composition of the present invention (D), specifiable is for example benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, acetophenones such as 1-dichloroacetophenone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-aminoacetophenone classes such as 1-ketone; Anthraquinone classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthene ketones such as 4-diisopropyl thioxanthones; Ketal classes such as acetophenone dimethyl ketal, benzyl dimethyl ketal; Benzophenones such as benzophenone; Perhaps xanthones; (2,6-dimethoxy benzoyl)-2,4,4-amyl group phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, ethyl-2,4, phosphinoxides such as 6-trimethylbenzoyl phenyl phosphine oxide; Various peroxides etc., these known habitual Photoepolymerizationinitiater initiaters can separately or mix use more than 2 kinds.The cooperation ratio of these Photoepolymerizationinitiater initiaters (D) is suitably for respect to the above-mentioned organic bond of 100 mass parts (contain the photoresist of carboxyl and/or contain the resin of carboxyl) and is (B) 1～30 mass parts, preferred 5～20 mass parts.
In addition, above-mentioned Photoepolymerizationinitiater initiater (D) can mix N, N-dimethylamino ethyl benzoate, N, using more than a kind or 2 kinds in the light sensitizer of tertiary amines such as N-dimethylamino benzoic acid isopentyl ester, amyl group-4-dimethylaminobenzoic acid ester, triethylamine, triethanolamine.
In addition, under the situation that requires the darker photocuring degree of depth, may be combined in the visibility region two luxuriant titanium class Photoepolymerizationinitiater initiaters such as Irgacure-784 that the Ciba Speciality Chemicals society of causing radical polymerization makes as required and use as the leuco dye of auxiliary curing agent.
In the present invention, in Photocurable composition, mix under the situation of excessive inorganic filler and glass powder, exist the storage stability of the composition that obtains poor, because gelation and mobile reduction cause being coated with the tendency of operability variation.Thereby, in composition of the present invention, in order to improve the storage stability of composition, preferred add for as the metal or the oxide powder complexing of the composition of inorganic filler and glass powder or form salt etc. effectively certain compound be that organic acid (E) is as stabilizer.As this organic acid (E), specifiablely be acid such as malonic acid, adipic acid, formic acid, acetic acid, acetoacetic acid, citric acid, stearic acid, maleic acid, fumaric acid, phthalic acid.These acid can separately or mix more than 2 kinds to be used.Such organic acid is preferably being that the ratio of 0.1～10 mass parts is added with respect to the above-mentioned glass powder of 100 mass parts and inorganic fine particles.
On the other hand, the past is used the stabilizer of phosphate as cobalt always, is not very effective for cobaltosic oxide still.
In addition on the one hand, in Photocurable composition of the present invention, cooperate under the situation of photopolymerization monomer, exist the storage stability of the composition that obtains poor, because gelation and mobile reduction cause being coated with the tendency of operability variation.Therefore, in composition of the present invention,, preferably add the thermal polymerization inhibitor (F) of photopolymerization monomer in order to improve the storage stability of composition.As this thermal polymerization inhibitor (F), specifiable is phenthazine, quinhydrones, N-nonox, chloranil, pyrogallol, benzoquinones, tert-butyl catechol etc., and these can separately or mix use more than 2 kinds.Such thermal polymerization inhibitor (F) is preferably with respect to the above-mentioned organic bond of 100 mass parts to be the ratio interpolation of 0.01～1 mass parts.
Also have, Photocurable composition of the present invention, can cooperate softening point as required with the ratio of the amount of not damaging Photocurable composition characteristic of the present invention is 400～600 ℃ glass powder, electroconductive powder.
In order to improve the adaptation of conductor circuit behind the sintering, glass powder can be with respect to 100 mass parts cobaltosic oxide (Co 3O 4) thermal endurance black pigment such as black particles is that the ratio that 200 mass parts are following, preferred 150 mass parts are following is added.As this glass powder, preferred glass inversion point (Tg) is that 300～500 ℃, glass softening point (Ts) are 400～600 ℃ glass powder.In addition, from the clarity aspect, preferably using average grain diameter is the glass powder that 20 μ m are following, preferred 5 μ m are following.
By add above-mentioned glass powder in Photocurable composition, the film behind the exposure imaging can be easy to sintering below 600 ℃.But, in composition of the present invention, used the good organic bond of flammability, make that removing adhesive before the glass powder fusion is over, if but the softening point of glass powder is lower than 400 ℃, under than this also low temperature fusion takes place, wrapping organic bond easily, because remaining organic bond decomposes, bubbling easily in the composition, is unfavorable therefore.
As glass powder, be fit to use the amorphism frit as main component such as lead oxide, bismuth oxide or zinc oxide.
In the present invention, as the diluent that is used for the paste composition livering or be used for the diluent that the corresponding viscosity of various painting process is adjusted, can cooperate the organic solvent of Sq.Concrete specifiable is ketones such as methyl ethyl ketone, cyclohexanone; Toluene, dimethylbenzene, durol etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methyl cellosolve, carbitol, methyl carbitol, butyl carbitol, Glycol Monomethyl ether, DPG monomethyl ether, DPG monoethyl ether, triethylene glycol monoethyl ether; Acetates such as ethyl acetate, butyl acetate, cellosolve acetate, butylacetic acid cellosolve, carbitol acetate, butyl carbitol acetate, Glycol Monomethyl ether acetic acid esters; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol, terpineol; Aliphatic hydrocarbon such as octane, decane; Petroleum-type solvents such as benzinum, naphtha, hydrotreated naphtha, solvent naphtha, these solvents can separately or mix use more than 2 kinds.
Photocurable composition of the present invention in addition as required can also hybrid silicone class, propylene class froth breaking levelling agent, be used to improve other additives such as silane coupler of film adaptation.Moreover, in the time of can also adding known habitual antioxidant and sintering as required as with particulates such as the metal oxide of substrate binding constituents, Si oxide, boron oxide compound.
Photocurable composition of the present invention, forming under the situation of film like in advance, can be on substrate lamination, but under the situation of paste shape composition, using the coating process that it is suitable that silk screen print method, rod are coated with method, knife coating etc. for example to become at substrate on the glass plate of PDP front substrate is coated with, then in order to obtain dry to touch, use heated air circulation type drying oven, far infrared drying stove etc. to descend dry about 5～40 minutes at about 60～120 ℃, make organic solvent evaporation, obtain tack-free filming.Then, the exposure of selecting, development, sintering, the telegraph circuit of formation predetermined pattern.
As exposure process, can use the contact exposure and the noncontact exposure of the negative mask that contains the regulation exposing patterns.As exposure light source, use Halogen lamp LED, high-pressure mercury-vapor lamp, laser, metal halide lamp, black light lamp, electrodeless lamp etc.Exposure is preferably 50～1000mJ/cm 2About.
As developing procedure, can use spray-on process, infusion process etc.As developer solution, be fit to use amine aqueous solutions such as the metal alkaline aqueous solution such as NaOH, potassium hydroxide, sodium carbonate, potash, sodium metasilicate and monoethanolamine, diethanol amine, triethanolamine, rare alkaline aqueous solution of the following concentration of particularly about 1.5 quality %, as long as but can make and contain the carboxyl saponification of carboxy resin in the composition and remove uncured portion (unexposed portion) just passable, be not limited to above-mentioned developer solution.In addition, in order to remove the unwanted developer solution in back that develops, preferably wash or the acid neutralization.
In sintering circuit, the substrate after the development carries out about 400～600 ℃ heat treated under air or nitrogen atmosphere, form desirable black pattern.Also have, programming rate at this moment preferably sets below 20 ℃/minute.
Embodiment
Below with reference to embodiment and comparative example the present invention is specifically described, but obviously the present invention is not limited to the following examples.Also have, " part " of appearance and " % " all are quality criteria unless otherwise specified.(synthesis example 1)
In the flask of being furnished with thermometer, blender, dropping funel and reflux condenser, with 0.76: 0.24 mol ratio pack into methyl methacrylate and methacrylic acid, add the DPG monomethyl ether as solvent, azodiisobutyronitrile as catalyst, nitrogen atmosphere, 80 ℃ of following stirrings 2～6 hours, obtain resin solution.Cool off this resin solution, use methylnaphthohydroquinone as polymerization inhibitor, Xiuization 4-butyl-phosphonium as catalyst, under the condition of 95～105 ℃ and 16 hours, make that glycidyl methacrylate is the addition mol ratio generation addition reaction of 0.12 mole ratio with the carboxyl with respect to 1 mole of above-mentioned resin, take out the cooling back, generates organic bond A.The resin of this organic bond A, weight average molecular weight is about 10000, and acid number is 59mgKOH/g, and two key equivalents are 950.Also have, the mensuration of the weight average molecular weight of the copolymer resins that obtains is by with (strain) Shimadzu Seisakusho Ltd. system Port Application プ LC-6AD and clear and electrician's (strain) makes カ ラ system Shodex (registered trade mark) KF-804, these three high-speed liquid chromatographies that connect into of KF-803, KF-802 are measured.(synthesis example 2)
Except packing into methyl methacrylate and methacrylic acid than to be made as mol ratio be 0.87: 0.13 and do not make the glycidyl methacrylate generation addition reaction, with the above-mentioned synthesis example 1 same organic bond B that generates.The resin of this organic bond B, weight average molecular weight is about 10000, and acid number is 74mgKOH/g.
Use the organic bond A or the B that obtain thus,, after the blender stirring, undertaken pasteization by the grinding of 3 bench roller formula grinders according to ratio of components complexing compositions as follows.Grinding condition is to obtain the 1kg sample size at room temperature 30 minutes.
Also have, in this embodiment, with maximum particle diameter is that thermal endurance black pigment below the 5 μ m evenly is dispersed to the slurry (A) in the solvent, be to be 10 parts dispersant by using with respect to 100 parts of black particle, make that maximum particle diameter is that the 5 μ m concentration of black particle in TPM (tripropylene glycol monomethyl ether) following, that average grain diameter is the cobaltosic oxide of 0.2 μ m is 70%, adopt ball mill evenly to disperse modulation to form (solvent strength of slurry second month in a season: 100 parts of slurries are had 23 parts of solvents).Wherein, as dispersant, the macromolecule dispersing agent that uses Japanese grease to make: AKM-0531 for slurry (A-1), uses the macromolecule dispersing agent of the chemical manufacturing of common prosperity society: being of DOPA-15B slurry (A-2).
In addition, as glass powder, use 60%PbO, 20%B 2O 3, 15%SiO 2, 5%Al 2O 3Pulverize and make thermalexpansioncoefficient 300=70 * 10 -7/ ℃, glass transition point is that 445 ℃, average grain diameter are the glass powder of 1.6 μ m.The conductive paste of white layer electrode (upper strata) usefulness;
100.0 parts of organic bond A
50.0 parts of pentaerythritol triacrylates
5.0 parts of 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) fourths-1-ketone
80.0 parts of tripropylene glycol monomethyl ethers
450.0 parts in silver powder
22.0 parts of glass powders
The paste of 1.0 parts of black layer electrode (lower floor) usefulness of phosphate; (composition example 1)
100.0 parts of organic bond B
50.0 parts of pentaerythritol triacrylates
5.0 parts of 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) fourths-1-ketone
40.0 parts of tripropylene glycol monomethyl ethers
50.0 parts in slurry (A-1) (composition example 2)
100.0 parts of organic bond B
50.0 parts of pentaerythritol triacrylates
7.5 parts of 2-methyl isophthalic acids-[4-(methyl mercapto) phenyl]-2-morpholinyl third-1-ketone
2,1.0 parts of 4-diethyl thioxanthones
40.0 parts of tripropylene glycol monomethyl ethers
50.0 parts in slurry (A-1) (composition example 3)
100.0 parts of organic bond B
50.0 parts of pentaerythritol triacrylates
7.5 parts of 2-methyl isophthalic acids-[4-(methyl mercapto) phenyl]-2-morpholinyl third-1-ketone
2,1.0 parts of 4-diethyl thioxanthones
40.0 parts of tripropylene glycol monomethyl ethers
50.0 parts in slurry (A-1)
1.0 parts of malonic acid (composition example 4)
100.0 parts of organic bond B
50.0 parts of pentaerythritol triacrylates
7.5 parts of 2-methyl isophthalic acids-[4-(methyl mercapto) phenyl]-2-morpholinyl third-1-ketone
2,1.0 parts of 4-diethyl thioxanthones
40.0 parts of tripropylene glycol monomethyl ethers
50.0 parts in slurry (A-1)
1.0 parts of malonic acid
0.1 part of phenthazine (composition example 5)
100.0 parts of organic bond B
50.0 parts of pentaerythritol triacrylates
7.5 parts of 2-methyl isophthalic acids-[4-(methyl mercapto) phenyl]-2-morpholinyl third-1-ketone
2,1.0 parts of 4-diethyl thioxanthones
40.0 parts of tripropylene glycol monomethyl ethers
50.0 parts in slurry (A-2)
1.0 parts of malonic acid
0.1 part of phenthazine (comparative composition example 1)
100.0 parts of organic bond B
50.0 parts of pentaerythritol triacrylates
5.0 parts of 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) fourths-1-ketone
80.0 parts of tripropylene glycol monomethyl ethers
Cobaltosic oxide (Co 3O 4)
Average grain diameter: 35.0 parts of 0.2 μ m
1.0 parts of phosphates
For the various pastes in composition example 1～5 that obtains thus and the comparative composition example 1, estimate maximum particle diameter, the wire shaped behind the sintering, the stability of paste, resistivity, interlayer conduction, the L of cobaltosic oxide *Value.Its evaluation method is as described below.(maximum particle diameter of cobaltosic oxide)
The fineness gauge that the paste of black layer electrode (lower floor) usefulness that obtains at combinations thereof, use can 2.5 μ m units be measured 5～25 μ m is measured the maximum particle diameter of cobaltosic oxide.(stability of paste)
The various pastes of 300g composition example 3,4, comparative composition example 1 are put into closed container respectively, placed 1 month down, estimate the tackify rate (%) of paste at 40 ℃.(wire shaped behind the sintering)
On the glass substrate that has the ITO film, use 300 purpose polyester screen to be coated with to estimate the paste of usefulness comprehensively, then, use the heated air circulation type drying oven 90 ℃ dry 20 minutes down, form the dry to touch good film.Secondly, on this film, use the 300 purpose polyester screen conductivity paste of the white layer of coating electrode (upper strata) usefulness comprehensively, then, use the heated air circulation type drying oven 90 ℃ dry 20 minutes down, form the good white black two-layer film of dry to touch.Then, use metal halide lamp as light source, line/egative film of μ m carries out pattern exposure at interval=50/100 in use, makes that the accumulation light quantity on the composition is 300mJ/cm 2, follow 0.5wt%Na at 25 ℃ 2CO 3The aqueous solution develops, washing, and the speed with 5 ℃/minute heats up under air atmosphere at last, at 30 minutes pattern-making sintered base plates of 550 ℃ of following sintering.Then, same with the situation that above-mentioned resistivity is estimated except sintering, make the pattern sintered base plate.
At the sintered base plate that obtains thus, use the microscopic examination pattern, have or not the irregular corrugationless etc. that departs from, has on the evaluation line.(resistivity, interlayer conduction)
Except using the negative mask exposure of pattern dimension, similarly make the test substrate with the evaluation of above-mentioned (wire shaped behind the sintering) as 0.4cm * 10cm.At the test substrate that obtains thus, use milliohmmeter to measure the resistance value of sintered film, then use サ-Off コ--(surface coated device) to measure the thickness of sintered film, calculate the resistivity of sintered film.
In addition, place tester on the white layer electrode (upper strata) of sintered film and ITO film, carry out the affirmation of conducting, the situation of conducting is designated as zero, not the situation of conducting be designated as *.(L *Value)
Except using the negative mask exposure of pattern dimension, similarly make the test substrate with the evaluation of above-mentioned (wire shaped behind the sintering) as 3cm * 10cm.At the test substrate that obtains thus, use color colorimeter (ミ ノ Le カ メ ラ (strain) manufacturing, CR-221) to measure L according to JIS-Z-8729 *a *b *Chromatic value is L with the index of representing brightness *Value is estimated as the index of degree of blackness.This L *It is good more to be worth more little degree of blackness.
These evaluation results are as shown in table 1.
Table 1
The composition example Comparative composition example 1
??1 ??2 ????3 ????4 ????5
Maximum particle diameter (μ m) Below 5 Below 5 Below 5 Below 5 Below 5 ????12.5
The tackify rate (%) of paste ??- ??- ????10 ????5 ????5 ????10
Wire shaped behind the sintering Do not have Do not have Do not have Do not have Do not have Have
Layer is asked conducting ??○ ??○ ????○ ????○ ????○ ????○
Resistivity (* 10 -6Ωcm) ??3.2 ??3.3 ????3.2 ????3.2 ????3.2 ????3.4
?L *Value ??8.1 ??8.4 ????8.3 ????8.2 ????8.1 ????9.7
Can obviously learn the little and even dispersion of the maximum particle diameter of the cobaltosic oxide in the Photocurable composition paste of the present invention from the result shown in this table 1.
Can learn, on the wire shaped behind the sintering, do not have irregularly to depart from fold etc. in addition, can form high meticulous telegraph circuit according to Photocurable composition of the present invention.
Also have, can learn Photocurable composition of the present invention, not only can form high meticulous sintering pattern, even also can form the good black layer electrode (lower floor) that behind sintering, also can satisfy enough interlayer conductions and blackness simultaneously of storage stability.Can learn that particularly storage stability is good under the situation of mixed organic acid and polymerization inhibitor.
Also have, no problem at the adaptation behind the paste evaluation sintering of above-mentioned evaluation usefulness.This adaptation is that cellophane tape is peeled off, whether figuratum peeling off estimated by using.
As mentioned above, Photocurable composition according to the present invention can not can cause thermal endurance black pigment secondary aggegation ground carry out pasteization, and storage stability is good, in each operation of drying, exposure, development, sintering, can not damage the adaptation good, clarity, agglutinating property, even behind sintering, can form sintered film with enough blackness with respect to substrate yet.
And, according to Photocurable composition of the present invention, can be provided in black layer (lower floor) telegraph circuit that can satisfy enough interlayer conductivity (interlayer conduction of the white layer of transparency electrode and bus electrode) and blackness in the bus electrode that forms white black double-layer structure on the front substrate of PDP simultaneously etc., the meticulous black pattern of height.
Such Photocurable composition of the present invention, owing to improve the productivity ratio of paste, storage stability is good and use thin thickness can obtain enough contrasts, therefore a large amount of productions and the cost degradation for PDP is exceedingly useful.

Claims (9)

1. Photocurable composition, it is characterized in that containing (A) is that thermal endurance black pigment below the 5 μ m is dispersed in slurry in the solvent, (B) organic bond, (C) photopolymerization monomer and (D) Photoepolymerizationinitiater initiater with maximum particle diameter.
2. as the Photocurable composition of record in the claim 1, it is characterized in that also containing (E) organic acid.
3. as the Photocurable composition of record in claim 1 or 2, it is characterized in that also containing (F) polymerization inhibitor.
4. Photocurable composition, it contains (A), and to adopt macromolecule dispersing agent be that thermal endurance black pigment below the 5 μ m is dispersed in slurry in the solvent, (B) organic bond, (C) photopolymerization monomer and (D) Photoepolymerizationinitiater initiater with maximum particle diameter, it is characterized in that
Thermal endurance black pigment in the above-mentioned slurry (A) is being the mixed of 1～120 mass parts with respect to 100 mass parts organic bonds (B), macromolecule dispersing agent in the above-mentioned slurry in (A) is being the mixed of 1～20 mass parts with respect to 100 mass parts thermal endurance black pigments, solvent in the above-mentioned slurry (A) is being the mixed of 20～50 mass parts with respect to 100 mass parts slurries
Above-mentioned photopolymerization monomer (C) to be being the mixed of 20～100 mass parts with respect to 100 mass parts organic bonds (B), and above-mentioned Photoepolymerizationinitiater initiater (D) is being the mixed of 1～30 mass parts with respect to 100 mass parts organic bonds (B).
5. as the Photocurable composition of record in the claim 4, it is characterized in that also containing the inorganic filler components that contains above-mentioned thermal endurance black pigment with respect to 100 mass parts is the organic acid (E) of 0.01～1 mass parts.
6. as the Photocurable composition of record in claim 4 or 5, it is characterized in that also containing with respect to 100 mass parts organic bonds (B) is the polymerization inhibitor (F) of 0.01～1 mass parts.
7. as the Photocurable composition of record in claim 1 or 4, it is characterized in that above-mentioned thermal endurance black pigment is cobaltosic oxide black particle.
8. the Photocurable composition of putting down in writing in any one as claim 1～7 is characterized in that using as the black material of plasma display panel.
9. plasma display panel, it is equipped with the sinter of the Photocurable composition of being put down in writing in any one by aforesaid right requirement 1～7 to form the front substrate of black pattern.
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