CN100587598C

CN100587598C - Photosensitive inorganic paste composition, unbaked sheet-shaped body, and method of producing plasma display front plate

Info

Publication number: CN100587598C
Application number: CN 200580003023
Authority: CN
Inventors: 带谷洋之; 押尾公德; 熊泽明; 节田齐
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2004-01-28
Filing date: 2005-01-27
Publication date: 2010-02-03
Anticipated expiration: 2025-01-27
Also published as: TWI342981B; TW200535564A; JP4271048B2; JP2005215134A; CN1910518A; WO2005073809A1; KR100818222B1; KR20060105885A

Abstract

A photosensitive inorganic paste composition capable of improving pattern accuracy to such an extent to be sufficiently adapted to fine patterning required of plasma displays, a sheet-shaped unbaked body for production of a plasma display front plate using the same, and a method of producing a plasma display front plate. A Norish type I photopolymerization initiator and a hydrogen-withdrawing photopolymerization initiator are used in combination as a photopolymerization initiator in a photosensitive inorganic paste composition comprising at least a photopolymerization initiator, a photopolymerizable monomer and inorganic powders.

Description

The manufacture method of photosensitive inorganic paste composition, sheet-shaped unbaked body and front panel of plasma display

Technical field

The present invention relates to a kind of photosensitive inorganic paste composition, it has the excellent pattern shape by photoetching, and uses said composition to make the not plates of baking of front panel of plasma display, also relates to the method for making front panel of plasma display.

Background technology

The plasma scope that utilizes the electric discharge phenomena of electronics to make a large amount of small unit generation autoluminescences form image has excellent performances such as large tracts of land, thin, light and plane demonstration, these advantages are that traditional monitor is inaccessible, and promoting the use of of this plasma scope begins.

Traditional plasma scope mainly is made of the unit that the vertical direction at display has a straight structures of flank.A kind of unit of lattice structure yet grow up recent years, this unit be not only in vertical direction but also all have flank in the horizontal direction, thereby effectively with the front portion of light from luminous point guiding plasma scope.The lattice structure of unit is by preventing light from contiguous cell leakage, thereby imports light into the front portion very effectively.

Fig. 1 is the exploded perspective view of critical piece that has the plasma scope of grid cell.This plasma display has front panel 1, form compound electrode 11 parallel to each other on the plate, each compound electrode comprises transparency electrode 110 and bus electrode 112, and display also has rear panel 2, and the address electrode parallel to each other 21 that forms on the plate is also staggered with compound electrode 11.Front panel 1 and rear panel 2 combine display device of formation toward each other.Front panel 1 has the transparent glass substrate 10 as display surface, and compound electrode 11 is positioned on the inboard of transparent glass substrate 10, promptly is positioned at the side in the face of rear panel 2.Form one deck dielectric layer 12 and cover compound electrode 11, the wall 16 that forms pattern is arranged on dielectric layer 12, the diaphragm of being made by materials such as MgO 19 is on separate layer 16 and dielectric layer 12.In addition, rear panel 2 comprises substrate 20, and substrate 20 is provided with address electrode 21 in the face of a side of front panel 1.One deck dielectric layer 22 overlay address electrodes 21, illuminating part forms on dielectric layer 22, sees for details as described below.

Illuminating part comprises a plurality of unit, and each unit all is in the staggered locus of compound electrode 11 and address electrode 21.Flank 24 vertical at dielectric layer 22 upper edge displays and that horizontal direction forms is the border of each unit.Fluorescence coating 26 covers the surface of the sidewall and the dielectric layer 22 in the flank of flank 24, promptly is the inwall and the diapire of each unit.In plasma display, the compound electrode of an AC power on front panel applies predetermined voltage and makes cell discharge to form electric field.This discharge generation ultraviolet light further causes fluorescence coating 26 luminous.

Fig. 2 is the plasma display stereographic map of the front panel 1 seen of plate side from behind that has a grid cell.Fig. 3 is the sectional view that has the plasma display of grid cell.As shown in Figure 2, the form with equal space line is provided with a large amount of wall 16 on the dielectric layer 12 of the plasma display of lattice structure.As shown in Figure 3, the energy interlayer 16 contact flanks 24 in the front panel 1, thus form slit X on the top of each unit that flank 24 seals, rare gas can be imported each unit by slit X.

The serigraphy autofrettage is the method for known manufacturing front panel.The serigraphy autofrettage is included in and forms glass paste film on the glass substrate 10, it is formed dielectric layer 12 400～700 ℃ of bakings, on dielectric layer 12, the glass paste composition is extruded certain pattern with silk screen print method then, form separate layer 16 400～700 ℃ of second time bakings then.

Yet the serigraphy autofrettage needs the baking of two steps, has improved production cost.Another problem of this method is that the degree of accuracy of pattern position is very poor.

For example, patent document 1 (Japanese Patent Application Publication No.2002-150949) and patent document 2 (Japanese Patent Application Publication No.2002-328467) have been described above-mentioned known technology.

In order to solve the problem that silk screen print method exists, people have proposed to use photoetching process to make the new method of front panel of plasma display.Fig. 4 A has described to 4C and has used photolithographic production procedure.The first, on glass substrate 10, form the dielectric layer 12A of the not baking that contains non-photosensitive glass paste film and contain the photonasty of photosensitive glass paste film, layer of spacer material 16A unexposed, that do not toast.With irradiate light layer of spacer material 16A (Fig. 4 A) such as ultraviolet light by photomask.Then this layer is developed, photoengraving pattern 16A ' (Fig. 4 B) occurs.Product 400～700 ℃ of bakings, is formed dielectric layer 12 and wall 16 (Fig. 4 C) simultaneously.

Use the advantage of photolithographic manufacture method to be only need carry out a baking procedure, just can toast out dielectric layer 12 and wall 16 simultaneously.Therefore, production cost has just reduced than silk screen print method.

In above-mentioned manufacture method, with a kind of photosensitive glass paste composition of glass dust, a kind of Photoepolymerizationinitiater initiater, a kind of photopolymerizable monomer and a kind of adhesive resin material as formation layer of spacer material 16A.When in the photosensitive glass paste composition, using Photoepolymerizationinitiater initiater, use a kind of position to disconnect to produce atomic group at α carbon, be called the Photoepolymerizationinitiater initiater of Norish I type.

The feature of Norish I type Photoepolymerizationinitiater initiater is to have high setting rate and excellent interior sclerosis character.When using this Norish I type Photoepolymerizationinitiater initiater with excellent interior sclerosis character, can fully proceed to its bottom to the sclerosis of photosensitive glass paste film, obtain a kind of section and slightly be trapezoidal high stability pattern.

Yet in recent years, industry constantly increases the requirement that meticulousr pattern forms, and therefore the problem that occurs is the requirement that traditional photosensitive glass paste composition can not satisfy the fine pattern formation of plasma display fully.

For example, in Fig. 4 A, when the exposure of photosensitive glass paste film formed pattern, the relative photosensitive glass paste of the light of exposure film surface entered with the right angle.Yet the light of exposure is caused halation by the contained glass dust reflection of photosensitive glass paste film, and therefore the light of exposure can arrive wider zone.Correspondingly, the section of the pattern 16A ' that obtains is shown in Figure 5 trapezoidal.Therefore problem wherein is that when the spacing of pattern narrowed down, this trapezoidal effect can more seriously be destroyed the fineness of pattern because plasma display requires meticulousr pattern to form.

In the photolithographic manufacture method of above-mentioned use, the not dielectric layer 12A of baking that contains non-photosensitive glass paste film is come under the photosensitive glass paste film 16A and exposure especially.Correspondingly, the light that the influence of halation is wherein not only reflected owing to the contained glass dust of photosensitive glass paste film, and also the light that the contained glass dust of dielectric layer 12A that does not toast owing to lower floor reflects becomes more serious.Therefore, go up bottom width W relatively _Top, the following bottom width W of pattern _BtmTrend towards becoming very big.

Through the baking processing in later stage, figuratum layer of spacer material 16A ' and the dielectric layer 12A shrink slightly of not toasting.When the contact area (promptly being the bottom area of the layer of spacer material 16A ' of pattern) of dielectric layer 12A of pattern and not baking when area is big, as shown in Figure 6A, because the contraction of each figuratum interval insulant 16A ', dielectric layer 12A as lower floor is stretched, the dielectric layer 12 of area of the pattern is elevated, and causes dielectric layer 12 in uneven thickness.Another problem is that the contraction of figuratum interval insulant 16A ' causes the dielectric layer 12 between the pattern to be subjected to the opposite tension force of direction, and shown in Fig. 6 B, the dielectric layer 12 between the pattern lines will break.

Although hardening is of fine quality different in the Norish I type Photoepolymerizationinitiater initiater, sclerosis may be suppressed by oxygen, and this may stop the sclerous reaction of the surf zone of direct contact oxygen.Therefore, as shown in Figure 5, the surface that the photosensitive glass paste of sensitization takes place usually can cover the hyaline membrane 180 of one deck polyethylene terephthalate and so on starvation.Yet even surface coverage polyethylene terephthalate film, because film is very thin, the oxygen of trace can penetrate film.Therefore, the surface portion of pattern still may be in unhardened state after exposure, and therefore being developed solution washes the flatness on interference pattern surface off.Therefore the problem that produces is, when pattern toasted with this state, the glass dust composition was melted away by baking processing, makes to have an even surface to a certain degree, and is uneven but the surface still keeps, and makes the in uneven thickness of pattern.

The present invention is just in order to solve the problem in the prior art, the present invention relates to photosensitive inorganic paste composition, the pattern fineness is brought up to the degree that the fine pattern that is enough to be applicable to the plasma display requirement forms, also relate to the not plates of baking that use said composition to make front panel of plasma display, and the method for making front panel of plasma display.

Summary of the invention

In order to address the above problem, after having done big quantity research, the inventor finds to use a kind of Norish I type Photoepolymerizationinitiater initiater and a kind of dehydrogenation Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater simultaneously in a kind of photosensitive inorganic paste composition (comprising a kind of Photoepolymerizationinitiater initiater, a kind of phtotpolymerizable monomer and inorganic powder at least), can obtain the excellent pattern shape, be applicable to the needed formation fine pattern of plasma display fully.On the basis of this discovery, produced the present invention.

The preferred embodiment of photosensitive inorganic paste composition according to the present invention, used Norish I type Photoepolymerizationinitiater initiater is preferably and is selected from: at least a compound in benzoin ether compound, benzyl ketals compound, Alpha-hydroxy acetophenone compound, α-amido acetophenone compound, two acylphosphine oxide compound, acylphosphine oxide compound, phenyl dicarbonyl compound and the phenyl acyl group oxime compound.Used dehydrogenation Photoepolymerizationinitiater initiater is preferably and is selected from: at least a compound in aromatic ketone compound, thioxanthones compound, anthraquinone compounds and the amines.In total Photoepolymerizationinitiater initiater of per 100 parts of weight that preferred photosensitive inorganic paste composition comprises, the content of Norish I type Photoepolymerizationinitiater initiater is 10 to 99 parts of weight, and the content of dehydrogenation Photoepolymerizationinitiater initiater is 1 to 90 part of weight.

In the plates that do not toast of manufacturing front panel of plasma display of the present invention, the layer of spacer material that contains photosensitive inorganic paste composition of the present invention forms on removable supporting film.In instructions of the present invention, " make the not plates of baking of front panel of plasma display " and be meant flaky material with the layer that on removable supporting film, forms, when making front panel of plasma display, these material layers are separated from removable supporting film, transfer on the glass substrate.

In the method for manufacturing front panel of plasma display of the present invention, photosensitive inorganic paste composition of the present invention is used to form layer of spacer material.Can carry out exposure-processed and subsequent treatment with the means of routine.A preferred embodiment according to the method for manufacturing front panel of plasma display of the present invention, the softening point of the inorganic powder that layer of spacer material is contained preferably is higher than not the softening point of inorganic powder contained in the dielectric layer of baking, preferably in the dielectric layer than not baking the softening point of contained inorganic powder high 5 ℃ or more than.

The patterned surfaces that the photosensitive inorganic paste film that uses photosensitive inorganic paste composition of the present invention to form provides can be in splendid hardening state after exposure.Therefore the effect of bringing is different with prior art, and developing solution can not washed the unhardened photosensitive inorganic paste material of patterned surfaces off, prevents the pattern thickness inequality that reduces to cause because of figuratum film thickness.

Use Norish I type Photoepolymerizationinitiater initiater and dehydrogenation Photoepolymerizationinitiater initiater by mixing, the section of exposure back pattern can be controlled as near rectangle (seeing Fig. 7 A) or following bottom width W _BtmBe slightly less than bottom width W _TopTrapezoidal (seeing Fig. 7 B).With the problem in the method for photoetching manufactured front panel of plasma display is W _BtmStrengthened, during exposure, the formation of its intermediate interlayer is easy to be subjected to the influence of the light of lower floor's reflection, but this problem can be solved by the present invention.Therefore can reduce and the contact area that does not toast dielectric layer,, also situation in uneven thickness can not take place so when pattern shrank, dielectric layer can not split or be out of shape.

The not plates of baking according to manufacturing front panel of plasma display of the present invention, on removable supporting film, form at least a layer of spacer material that contains photosensitive inorganic paste composition of the present invention in advance, during fabrication, lamination does not toast body on substrate, forms the uniform wall of smooth surface thickness on glass substrate.

Photosensitive inorganic paste composition of the present invention can be used as formation multilayer circuit and various display, such as the material of plasma display, plasma address LCD, Field Emission Display etc., be preferred for making the layer of spacer material of the front panel of plasma display that requires high-fineness.

According to the method for manufacturing front panel of plasma display of the present invention, on glass substrate, form two-layer, promptly contain the non-photosensitive inorganic paste composition not baking dielectric layer and contain the layer of spacer material of photosensitive inorganic paste composition of the present invention.Can carry out exposure-processed and subsequent treatment with the means of routine then, the pattern fineness is improved thus, prevents that dielectric layer from the time deforming and break in baking.

In the method for manufacturing front panel of plasma display of the present invention, the softening point of the inorganic powder that layer of spacer material is contained can be higher than the softening point of inorganic powder contained in the dielectric layer of not baking, and pattern sidewalls can not be sunk when baking like this.

Description of drawings

Fig. 1 is the exploded view with plasma display of lattice structure unit.

Fig. 2 is the stereographic map of front panel of plasma display.

Fig. 3 is the sectional view with plasma display of lattice structure unit.

Fig. 4 A is to use photoetching process to make the synoptic diagram of a step (step of exposure) of front panel of plasma display.

Fig. 4 B is to use photoetching process to make the synoptic diagram of a step (development step) of front panel of plasma display.

Fig. 4 C is to use photoetching process to make the synoptic diagram of a step (baking procedure) of front panel of plasma display.

Fig. 5 is the sectional view of the back pattern of development, and its method by the manufacturing front panel of plasma display of prior art obtains.

Fig. 6 A is the sectional view of the back pattern of baking, and its method by the manufacturing front panel of plasma display of prior art obtains.

Fig. 6 B is the sectional view of another pattern of baking back, and its method by the manufacturing front panel of plasma display of prior art obtains.

Fig. 7 A is the sectional view of the back pattern of development, and it is obtained by the method that the present invention makes front panel of plasma display.

Fig. 7 B is the sectional view of another pattern after developing, and it is obtained by the method that the present invention makes front panel of plasma display.

Fig. 8 A is a schematic flow sheet of making front panel of plasma display with the not plates of baking of making front panel of plasma display.

Fig. 8 B is a schematic flow sheet of making front panel of plasma display with the not plates of baking of making front panel of plasma display.In Fig. 8 A and 8B, label 18 is meant removable film (supporting film 180 or diaphragm 182).

Embodiment

Photosensitive inorganic paste composition of the present invention is a kind of inorganic powder that contains at least, and the composition of Photoepolymerizationinitiater initiater and photopolymerizable monomer wherein mixes and uses Norish I type Photoepolymerizationinitiater initiater and dehydrogenation Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater.

In the plasma display header board of routine is made, use Norish I type Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater separately, therefore the sclerosis character of patterned surfaces is not enough, and lip-deep unhardened photosensitive inorganic paste material can be developed the solution flush away, and the problem that causes is that the thickness that forms the film of pattern reduces.But, by mix using Norish I type Photoepolymerizationinitiater initiater and dehydrogenation Photoepolymerizationinitiater initiater, can improve the sclerosis character of patterned surfaces, the thickness that prevents to form the film of pattern thus reduces, and makes the thickness of the film that forms pattern even.

Use Norish I type Photoepolymerizationinitiater initiater and dehydrogenation light to gather and initiating agent by mixing, the section of pattern can be made near rectangle or following bottom width W _BtmBe slightly less than bottom width W _TopTrapezoidal.Split or be out of shape so can prevent dielectric layer, and obtain uniform thickness.In the photoetching process field,, descend bottom width W usually because the stability of pattern reduces _BtmLess than last bottom width W _Top, be not preferred.But in the photosensitive inorganic paste film, baking processing has melted inorganic powder, makes down bottom width W _BtmThan widening before the baking.Therefore, for following bottom width W _BtmBe slightly less than bottom width W _TopTrapezoidal situation, W in baking _BtmBroadened, therefore made W _BtmNear last bottom width W _TopTo such an extent as to, after baking, the problem of pattern stability can not appear.

Describe embodiments of the invention below in the following order in detail.

(A) photosensitive inorganic paste composition

(B) be used to make the not plates of baking of front panel of plasma display

(C) method of manufacturing front panel of plasma display

(A) photosensitive inorganic paste composition

The transparency of photosensitive inorganic paste composition of the present invention meets with UV light, excimer laser, X-ray and electron beam (back general designation light) carries out the requirement of exposure-processed, can make said composition form patterns of high precision with photoetching process, and be preferred for making plasma display.

(a) Photoepolymerizationinitiater initiater

In the present invention, mix use Norish I type Photoepolymerizationinitiater initiater and dehydrogenation Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater.

As reaction equation (1), the Photoepolymerizationinitiater initiater of Norish I type is a kind of Photoepolymerizationinitiater initiater that can disconnect the generation atomic group in the position of α carbon.On the one hand, as reaction equation (2), the dehydrogenation Photoepolymerizationinitiater initiater can make hydrogen donor (RH) dehydrogenation form atomic group.

Wherein X is a replacement or unsubstituted aryl, and it is an organic group that contains a kind of element among C, H, O, N and the S at least.

Some Photoepolymerizationinitiater initiaters disconnect the atomic group (Y) that produces Norish I type in the position of α carbon, and the hydrogen of sloughing hydrogen donor (RH) then forms the atomic group (R) of dehydrogenation type.In the present invention, can disconnect the scope that the atomic group Photoepolymerizationinitiater initiater that produces atomic group is defined by belonging to Norish I type Photoepolymerizationinitiater initiater in the position of α carbon.Therefore in the present invention, produce atomic group Norish I type and dehydrogenation type Photoepolymerizationinitiater initiater and all be classified into Norish I type Photoepolymerizationinitiater initiater.

(I) Norish I type Photoepolymerizationinitiater initiater

The used Norish I type Photoepolymerizationinitiater initiater of the present invention is preferably the compound of following general formula (I-1) to (I-3) representative:

R wherein ₁₀To R ₁₃Represent an organic group that contains a kind of element among C, H, O, N and the S at least respectively, when there being several R ₁₀The time, they can be mutually the same or different.R ₁₁To R ₁₃May connect in twos, form ring structure, n1 is 0 to 5 integer.

R wherein ₂₀To R ₂₂Represent an organic group that contains a kind of element among C, H, O, N and the S at least respectively, when there being several R ₂₀The time, they can be mutually the same or different.N2 is 0 to 5 integer.

Wherein X is O or N, R ₃₀To R ₃₁Represent an organic group that contains a kind of element among C, H, O, N and the S at least respectively, when there being several R ₃₀The time, they can be mutually the same or different.R ₃₂Represent an organic group that contains a kind of element among C, H, O, N and the S at least, n3 is 0 to 5 integer.

Norish I type Photoepolymerizationinitiater initiater is preferably and is selected from: at least a compound in benzoin ether compound, benzyl ketals compound, Alpha-hydroxy acetophenone compound, α-amido acetophenone compound, two acylphosphine oxide compound, acylphosphine oxide compound, phenyl dicarbonyl compound and the phenyl acyl group oxime compound; wherein preferred phenyl ketal compound, two acylphosphine oxide compound and acylphosphine oxide compound, more preferably benzyl ketals compound.

Next introduce general formula (I-1) some examples, but the used Norish I type Photoepolymerizationinitiater initiater of the present invention is not limited to these examples to the Norish I type Photoepolymerizationinitiater initiater of (I-3) representative.Certainly, the analog of these compounds also can be used as Norish I type Photoepolymerizationinitiater initiater of the present invention.

(1) benzoin ether compound

Benzoin methyl ether

Benzoin ethyl ether

Benzoin isopropyl ether

(2) benzyl ketals compound

(3) Alpha-hydroxy acetophenone compound

1-(4-cumenyl)-2-hydroxy-2-methyl-1-acetone

1-(4-dodecylphenyl)-2-hydroxy-2-methyl-1-acetone

(4) alpha-aminoacetophenone compound

(5) two acylphosphine oxide compounds

(6) acylphosphine oxide compound

(7) phenyl dicarbonyl compound

(8) phenyl acyl group oxime compound

(II) dehydrogenation Photoepolymerizationinitiater initiater

The compound that the used dehydrogenation Photoepolymerizationinitiater initiater of the present invention is preferably following general formula (II-1) or (II-2) represents:

R wherein ₄₀And R ₄₁Represent an organic group that contains a kind of element among C, H, O, N and the S at least respectively, when there being several R ₄₀And R ₄₁The time, they can be mutually the same or different.R ₄₀And R ₄₁May connect in twos, form ring structure, n40 and n41 are 0 to 5 integers.

R wherein ₅₀And R ₅₁Represent a hydrocarbon group respectively, R ₅₂Represent an organic group that contains a kind of element among C, H, O, N and the S at least.

The dehydrogenation Photoepolymerizationinitiater initiater is preferably and is selected from: at least a compound in aromatic ketone compound, thioxanthones compound, anthraquinone compounds and the amines (having the dialkylamine group, the aryl compound of alkyl alkanolamine etc.).More preferably thioxanthones compound and have the aromatic of dialkylamine group, more preferably thioxanthones compound.

Next some examples of the dehydrogenation Photoepolymerizationinitiater initiater of introducing general formula (II-1) or (II-2) representing, but the used dehydrogenation Photoepolymerizationinitiater initiater of the present invention is not limited to these examples.Certainly, the analog of these compounds also can be used as dehydrogenation Photoepolymerizationinitiater initiater of the present invention.

(1) aromatic ketone compound

3,3-dimethyl-4-methoxybenzene ketone

Benzophenone

(2) thioxanthones compound

Thioxanthones

2-methyl thioxanthones

The 2-isopropyl thioxanthone

2,4-dimethyl thioxanthones

The 2-clopenthixal ketone

1-chloro-4-propoxyl group thioxanthones

(3) anthraquinone compounds

(4) amines

(i) have the aromatic of dialkylamine group

4, two (the dimethyl amido)-Benzophenones (Michler ketone) of 4-

4-dimethyl amido amyl benzoate

4-dimethyl amine yl benzoic acid N-butoxy ethyl ester

Benzoic acid 2-(dimethyl amido) ethyl ester

4-dimethyl amine yl benzoic acid

4-dimethyl amido methyl benzoate

4-dimethyl amido ethyl benzoate

4-dimethyl amido butyl benzoate

4-dimethyl amine yl benzoic acid 2-Octyl Nitrite

4-dimethyl amine yl benzoic acid 2-isopentyl ester

4-dimethyl amido amyl benzoate

(ii) alkyl alkanolamine

Monoethanolamine

Diethanolamine

Triethanolamine

The N-methylethanolamine

N methyldiethanol amine

The 2-diethyl ethanolamine

Triisopropanolamine

(b) photopolymerizable monomer

Photopolymerizable monomer can be known photopolymerizable monomer, be not limited to following Example: benzyl acrylate, the methacrylic acid phenylester, cyclohexyl acrylate, cyclohexyl methacrylate, the acrylic acid phenoxy ethyl, the methacrylic acid phenoxy ethyl, the phenoxy group polyethylene glycol acrylate, the phenoxy group polyethylene glycol methacrylate-styrene polymer, styrene, Nonylphenoxy polyglycol acrylic monoester, Nonylphenoxy polyglycol metering system acid monoester, Nonylphenoxy polypropylene glycol acrylic monoester, Nonylphenoxy polypropylene glycol metering system acid monoester, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, phthalic acid 2-acryloyl ethoxylated ester, 2-acryloyl ethoxy-2-hydroxyethyl phthalic ester, 2-methacryl ethoxy-2-hydroxypropyl phthalic ester, methyl acrylate, ethyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, the acrylic acid n-propyl, n propyl methacrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, acrylic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, acrylic acid monoethylene glycol ester, the methacrylic acid ethylene glycol ester, acrylic acid glyceride, glyceral methacrylate, acrylic acid dipentaerythritol monoesters, methacrylic acid dipentaerythritol monoesters, DMAM, dimethylaminoethyl acrylate methyl base amido ethyl ester, the acrylic acid tetrahydro furfuryl ester, the methacrylic acid tetrahydro furfuryl ester, the acrylic monoester of phthalic acid modification, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, the diacrylate triethyleneglycol ester, the dimethacrylate triethyleneglycol ester, three acrylic acid trihydroxy methyl propyl ester, trimethyl acrylic acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl ethyl esters, trimethyl acrylic acid trihydroxy methyl ethyl ester, the diacrylate pentaerythritol ester, the dimethacrylate pentaerythritol ester, pentaerythritol triacrylate, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, dipentaerythritoltetraacrylate, tetramethyl acrylic acid dipentaerythritol ester, five acrylic acid dipentaerythritol ester, pentamethyl acrylic acid dipentaerythritol ester, six acrylic acid dipentaerythritol ester, hexamethyl acrylic acid dipentaerythritol ester, the acrylic acid glyceride, glyceral methacrylate, the many epoxy-esters of diacrylate card (cardoepoxy diacrylate), and those fumarates, methylene-succinic acid ester and maleate, in these compounds, use fumarate respectively, methylene-succinic acid ester and maleate replace (methyl) acrylate.

(c) inorganic powder

The contained inorganic powder of photosensitive inorganic paste composition of the present invention is not particularly limited to certain limit, only need satisfy the necessary transparency of exposure light source, and its example comprises glass, pottery (trichroite or the like), metal etc.Particularly, glass dust is for example based on PbO-SiO ₂, PbO-B ₂O ₃-SiO ₂, ZnO-SiO ₂, ZnO-B ₂O ₃-SiO ₂, BiO-SiO ₂, BiO-B ₂O ₃-SiO ₂Deng borosilicic acid lead salt glass, borosilicic acid zinc salt glass, borosilicic acid bismuth salt glass, the oxide of Na, K, Mg, Ca, Ba, Ti, Zr, Al etc., for example cobalt oxide, iron oxide, chromium oxide, nickel oxide, cupric oxide, manganese oxide, neodymia, vanadium oxide, ceria titanium dioxide titan yellow (cerium oxide tipaque yellow), cadmium oxide, ruthenium-oxide, silicon dioxide, magnesium oxide, spinel or the like, fluorescent powder is ZnO:Zn, Zn for example ₃(PO ₄) ₂: Mn, Y ₂SiO ₅: Ce, CaWO ₄: Pb, BaMgAl ₁₄O ₂₃: Eu, ZnS:(Ag, Cd), Y ₂O ₃: Eu, Y ₂SiO ₅: Eu, Y ₃AI ₅O ₁₂: Eu, YBO ₃: Eu, (Y, Gd) BO ₃: Eu, GdBO ₃: Eu, ScBO ₃: Eu, LuBO ₃: Eu, Zn ₂SiO ₄: Mn, BaAl ₁₂O ₁₉: Mn, SrAl ₁₃O ₁₉: Mn, CaAl ₁₂O ₁₉: Mn, YBO ₃: Tb, BaMgAl ₁₄O ₂₃: Mn, LuBO ₃: Tb, GdBO:Tb, ScBO ₃Tb, Sr ₆Si ₃O ₃C ₁₄: Eu, ZnS:(Cu, Al), ZnS:Ag, Y ₂O ₂S:Eu, ZnS:Zn, (Y, Cd) BO ₃: Eu, BaMgAI ₁₂O ₂₃: Eu or the like, and metal powder for example iron, nickel, palladium, tungsten, copper, aluminium, silver, gold, platinum or the like.Since excellent transparency, special preferred glass, pottery etc.Especially, use glass powder (glass dust) can produce optimum effect.When inorganic powder comprised silicon dioxide, aluminium oxide or titanium dioxide, it was opaque just to become, and weakened the transmission of light, so inorganic powder does not preferably contain said components.

The particle diameter of inorganic powder depends on the shape of the pattern that will form, but the average particulate diameter of inorganic powder is 0.1～10 μ m, more preferably uses 0.5～8 μ m.Owing to form uneven surfaces when forming the pinpoint accuracy pattern, is not preferred greater than the average particulate diameter of 10 μ m therefore.And less than the average particulate diameter of 0.1 μ m owing in baking, form small hole, cause the defective that insulate and dispersed not enough, therefore neither be preferred.The shape of inorganic powder may be sphere, bulk, thin slice and dendroid, can use a kind of shape wherein, or the combination of two or more shapes.

Inorganic powder may contain the inorganic pigment that sends red, indigo plant and green glow except black inorganic pigment.Can use the photonasty insulation paste composition that contains pigment to form motley pattern, be applicable to the chromatic filter of preparation plasma display device.In addition, inorganic powder can be the potpourri of the different molecule of physical property.Especially, can use different glass powder of thermal softening point and ceramic powders when baking, to suppress to shrink.Inorganic powder can chemical combination to together changing shape, various physical values or the like, this depends on the character of partition wall etc.

As mentioned above, the average particulate diameter of inorganic powder is 1～10 μ m, just 10 μ m or littler.Therefore secondary gathers and in order to improve dispersibility, can carry out pre-service to powder surface with silane coupling agent, metatitanic acid alkali couplant, aluminium base couplant, surfactant etc. in order to prevent, and handles the degree of the character of not destroying inorganic powder.In a kind of method that should handle, reagent treatment can be dissolved in organic solvent or the water, add inorganic powder and stirring then, then solvent is distilled, then in about 50～200 ℃ of thermal treatments 2 hours or longer time.Can when being changed into paste, photosensitive composite add this treating agent.

(d) adhesive resin

Usually in photosensitive inorganic paste composition, add adhesive resin to improve coating character and film forming.In the present invention, adhesive resin can be a kind of known adhesive resin, and has no particular limits.Can use acrylic resin, cellulose derivative, polyvinyl alcohol (PVA), polyvinyl butyral, polyglycol, urethane resin and melamine resin.Preferably contain acrylic resin, the acrylic resin of a hydroxyl is particularly arranged, the pattern of Xing Chenging has excellent degree of accuracy and better anti-development like this.

In photosensitive inorganic paste composition of the present invention, the preferred mixing used acrylic resin and the water soluble dyes derivant that a hydroxyl is arranged, because can improve effective sunlight like this, such as the transmission of UV light, excimer laser, X-ray, electron beam etc., thereby form pattern with excellent degree of accuracy.

Have the acrylic resin of a hydroxyl to comprise a kind of multipolymer, it is polymerized as main comonomer by the hydroxyl monomer, if necessary, also can with other comonomer copolymerization.The adduct of the preferred cyclic ethers of hydroxyl monomer, alkylene oxide wherein adds and is incorporated in the acrylic or methacrylic acid, oxirane particularly, epoxypropane, or epoxy butane adduct, or the adduct of these potpourris, its example has: the acrylic acid hydroxy methyl, methacrylic acid hydroxyl methyl esters, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxy-propyl ester, methacrylic acid 2-hydroxy propyl ester, acrylic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, acrylic acid 2-hydroxyl butyl ester, methacrylic acid 2-hydroxyl butyl ester, acrylic acid 3-hydroxyl butyl ester, methacrylic acid 3-hydroxyl butyl ester, acrylic acid 4-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester or the like, and epoxidised ester compounds, for example: acrylic or methacrylic acid and C1 are to the monoesters of C10 ethylene glycol, acrylic acid glyceride, glyceral methacrylate, the dipentaerythritol acrylic monoester, methacrylic acid dipentaerythritol monoesters, ester modified Hydroxyethyl Acrylate in ε-caproic acid, ester modified methacrylic acid hydroxyl ethyl ester in ε-caproic acid, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester or the like.

Can comprise with other comonomer of hydroxyl monomer copolymerization, for example, α, beta-unsaturated carboxylic acid, for example acrylic acid, methacrylic acid, itaconic acid, citraconic acid, methylene-succinic acid, maleic acid, fumaric acid or the like, and acid anhydrides or its half ester; α, β-unsaturated carbonyl acid ester, for example: methyl acrylate, ethyl acrylate, the acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, the acryllic acid isobutyl ester, the acrylic acid second month in a season-butyl ester, cyclohexyl acrylate, 2-EHA, acrylic acid octadecane ester, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, the methacrylic acid second month in a season-propyl ester, n-BMA, isobutyl methacrylate, the methacrylic acid second month in a season-butyl ester, cyclohexyl methacrylate, methacrylic acid 2-Octyl Nitrite, methacrylic acid octadecane ester, acrylic acid 2,2,2-trifluoro methyl esters, methacrylic acid 2,2,2-trifluoro methyl esters or the like; Styrene and styrene derivative, α-Jia Jibenyixi for example, ρ-vinyltoluene or the like.In addition, also can use vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, vinyl acetate, Class C acid glycidyl ester, glycidyl methacrylate or the like.Above-mentioned substance can be separately or two kinds or two or more mixing use.

Used water-soluble cellulose derivative can be various known types, and have no particular limits, its example can be carboxymethyl cellulose, Carboxymethyl Cellulose, hydroxyethyl cellulose, HEMC, hydroxypropyl cellulose, ethylhydroxyethylcellulose, carboxymethylethylcellulose, hydroxypropyl methylcellulose or the like.Above-mentioned substance can be separately or two kinds or two or more mixing use.

(e) recombination rate of each component

In photosensitive inorganic paste composition of the present invention, the ratio of Norish I type Photoepolymerizationinitiater initiater and dehydrogenation Photoepolymerizationinitiater initiater is as follows.The ratio of Norish I type Photoepolymerizationinitiater initiater is between 1 to 90 weight portion, and the ratio of dehydrogenation Photoepolymerizationinitiater initiater can be between 10 to 99 weight portions.The ratio of preferred Norish I type Photoepolymerizationinitiater initiater is between 10 to 50 weight portions, and the ratio of dehydrogenation Photoepolymerizationinitiater initiater can be between 50 to 90 weight portions.The ratio of preferred Norish I type Photoepolymerizationinitiater initiater is between 20 to 40 weight portions, and the ratio of dehydrogenation Photoepolymerizationinitiater initiater can be between 60 to 80 weight portions, and aforementioned proportion all is based on two kinds of component total amounts as 100 weight portions.

Especially, when photosensitive inorganic paste composition of the present invention was used as the layer of spacer material of front panel of plasma display, the preferred ratio of dehydrogenation Photoepolymerizationinitiater initiater in the Photoepolymerizationinitiater initiater of photosensitive inorganic paste composition was decided to be higher relatively.Especially, the ratio of Norish I type Photoepolymerizationinitiater initiater is between 10 to 90 weight portions, and the ratio of dehydrogenation Photoepolymerizationinitiater initiater can be between 10 to 90 weight portions.The ratio of preferred Norish I type Photoepolymerizationinitiater initiater is between 20 to 50 weight portions, and the ratio of dehydrogenation Photoepolymerizationinitiater initiater can be between 50 to 80 weight portions.The ratio of preferred NorishI type Photoepolymerizationinitiater initiater is between 30 to 40 weight portions, the ratio of dehydrogenation Photoepolymerizationinitiater initiater can be between 60 to 70 weight portions, and aforementioned proportion all is based on Photoepolymerizationinitiater initiater total amount with photosensitive inorganic paste composition as 100 weight portions.

When making front panel of plasma display, the dielectric layer 12A that does not toast that will contain one deck non-photosensitive inorganic paste layer is as the lower floor under the photosensitive inorganic paste film 16A, and exposure.Therefore, the influence of halation (halation) is not only because the light that the contained inorganic powder of photosensitive inorganic paste film reflects, also, therefore has the following bottom width W of exposure back pattern owing to the light as the contained inorganic powder reflection of the dielectric layer 12A that does not toast of lower floor becomes more serious _BtmBecome big trend.Yet the section of pattern can be near bottom width W under rectangle or the pattern after the recombination rate of Norish I type Photoepolymerizationinitiater initiater to the dehydrogenation Photoepolymerizationinitiater initiater is in the above-mentioned scope, exposes _BtmBe slightly less than bottom width W _TopTrapezoidal, therefore can prevent that contraction the cause dielectric layer of pattern when baking is out of shape and breaks.

In photosensitive inorganic paste composition of the present invention, water-soluble cellulose derivative is as follows with the ratio of the acrylic resin that a hydroxyl is arranged.Based on two kinds of component total amounts as 100 weight portions, the ratio of water-soluble cellulose derivative is between 50 to 90 weight portions, the ratio with acrylic resin of a hydroxyl can be between 50 to 10 weight portions.The ratio of preferred water-soluble cellulose derivative is between 60 to 80 weight portions, and the ratio with acrylic resin of a hydroxyl can be between 40 to 20 weight portions.The ratio of preferred water-soluble cellulose derivative is between 60 to 70 weight portions, and the ratio that the acrylic resin of a hydroxyl is arranged can be between 40 to 30 weight portions.

Based on the total amount of water-soluble cellulose derivative and photo polymerization monomer as 100 weight portions, the scope of used Photoepolymerizationinitiater initiater more preferably is 0.2 to 5 weight portion preferably at 0.1 to 10 weight portion.When the ratio of Photoepolymerizationinitiater initiater is lower than 0.1 weight portion, then can reduce sclerosis character.When the ratio of Photoepolymerizationinitiater initiater is higher than 10 weight portions, because the absorption of initiating agent, bottom may harden insufficient.

Organic component (for example the adhesive resin of water-soluble cellulose derivative and acrylic resin and so on, Photoepolymerizationinitiater initiater or the like) is as follows with the ratio of inorganic component (for example glass dust and other inorganic powder).Based on the photosensitive inorganic paste composition total amount as 100 weight portions, the ratio of organic component is between 10 to 40 weight portions, the ratio of inorganic component can be between 90 to 60 weight portions.The ratio of preferred organic component is between 15 to 35 weight portions, and the ratio of inorganic component can be between 85 to 65 weight portions.The ratio of preferred organic component is between 20 to 30 weight portions, and the ratio of inorganic component can be between 80 to 70 weight portions.

When forming layer of spacer material, if necessary can add a kind of solvent and remain in the OK range with viscosity with photosensitive inorganic paste composition of the present invention.

The contained solvent of photosensitive inorganic paste composition has no particular limits, as long as it can dissolve organic component fully, can make photosensitive inorganic paste composition have suitable viscosity, and can pass through drying evaporative removal easily.The preferred especially boiling point of solvent is at 100～200 ℃ ketone, pure and mild ester.

The example of these solvents comprises ketone, for example diethyl (first) ketone, methyl butyl (first) ketone, dipropyl (first) ketone, cyclohexanone or the like; And alcohol, for example n-amyl alcohol, 4-methyl-2-amylalcohol, cyclohexanol, diacetone alcohol or the like; Ether alcohol, for example glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or the like; Saturated alkyl aliphatic monocarboxylic acid ester, for example n-butyl acetate, amyl acetate or the like; Lactate, for example ethyl lactate, n-butyl lactate or the like; With ether base ester, for example molten fine acetic acid esters of methyl, the molten fine acetic acid esters of ethyl, propylene glycol methyl ether acetate, propylene glycol list ethylether acetic acid esters, 3-ethoxyl ethyl propionate, 2-methoxyacetic acid butyl ester, 3-methoxyacetic acid butyl ester, 4-methoxyacetic acid butyl ester, 2-methyl-3-methoxyacetic acid butyl ester, 3-methyl-3-methoxyacetic acid butyl ester, 3-ethyl-3-methoxyacetic acid butyl ester, 2-ethoxyacetic acid butyl ester, 4-ethoxyacetic acid butyl ester, 4-propoxyl group butyl acetate, 2-methoxyacetic acid pentyl ester or the like.Above-mentioned substance can be separately or two kinds or two or more mixing use.

Based on the total amount of inorganic component and organic component as 100 weight portions, the amount of solvent is preferably smaller or equal to 300 weight portions, more preferably 10 to 70 weight portions, most preferably 25 to 35 weight portions.

Except said components, if necessary, for example can add additive component: the suspending agent of UV absorbing agent, emulsion, polymerization inhibitor, plastifier, thickening agent, organic solvent, spreading agent, defoamer and organic or inorganic.

Can add polymerization inhibitor and improve the thermal stability in when storage, special example comprises: p-dihydroxy-benzene, p-dihydroxy-benzene monoesters, N nitrosodiphenyl amine, phenothiazine, right-tert-butyl catechol, N-nonox, 2,6-two-tert-butyl group-p-methyl phenol, chloranil, pyrogallol or the like.

The plastifier that improves the plasticity on the substrate comprises phthalic ester, particularly dibutyl phthalate (DBP), dioctyl phthalate (DOP), polyglycol, glycerine, diester tartaric acid used, particularly diethyl tartrate, dibutyl tartrate etc. and citrate, particularly triethyl citrate, tributyl citrate etc.).

The special example of defoamer comprises the defoamer based on alkylene ethylene glycol, for example polyglycol

(molecular weight 400 to 800), silicone and higher alcohol, defoamer can reduce the foam in cream or the film, can reduce the hole after the baking.

(B) the not plates of baking of manufacturing front panel of plasma display

In the plates of the not baking of manufacturing front panel of plasma display of the present invention, on the removable supporting film of one deck, form one deck layer of spacer material at least, this layer comprises filming that photosensitive inorganic paste composition of the present invention makes.

The not plates of baking of the present invention can include only the single layer structure of layer of spacer material, comprise layer of spacer material and the dielectric layer of not baking or the double-decker of burnable intermediate layer may, or comprise that the form of the three-decker of layer of spacer material, the dielectric layer that does not toast and burnable intermediate layer may provides.Can protect the two sides of these individual layers with the supporting film removed that can peel off easily, therefore not toast body and can store easily, transport and handle to three-decker.

The plates of not baking of the present invention can store one section preset time in the term of validity after manufacturing, and can use when making front panel of plasma display at once, have therefore improved the efficient of making front panel of plasma display.

To describe not some specific examples of the plates of baking of the present invention below in detail.

An example is that the not plates of baking with one deck photosensitive inorganic paste composition coating of the present invention are formed on the strippable supporting film.By forming layer of spacer material with solvent dilution to suitable photosensitive inorganic paste composition coating of the present invention and the drying that is applied to the concentration on the strippable supporting film.Cover layer of spacer material as protective seam with layer protecting film then.

Another example is the not plates of baking with dielectric layer of layer of spacer material and not baking.The layer of spacer material that contains photosensitive inorganic paste composition of the present invention is formed on the strippable supporting film.The not dielectric layer of baking that contains the non-photosensitive inorganic paste composition is formed on the layer of spacer material, and is capped the diaphragm of last layer as protective seam.

Also having an example is the not plates of baking that are formed with one deck burnable intermediate layer may on layer of spacer material.Comprising one deck is formed on the strippable supporting film by the layer of spacer material of filming that photosensitive inorganic paste composition of the present invention constitutes.One deck burnable intermediate layer may water-soluble or water-swellable is formed on the layer of spacer material, and is capped the diaphragm of last layer as protective seam.

Also having an example is the not plates of baking that are formed with the dielectric layer that one deck burnable intermediate layer may and one deck do not toast on layer of spacer material.In Fig. 8 A, comprise the layer of spacer material 16A that films that one deck is made of photosensitive inorganic paste composition of the present invention and be formed on the strippable supporting film 180.One deck burnable intermediate layer may 14 water-soluble or water-swellable forms on layer of spacer material 16A, forms the not dielectric layer 12A of baking that one deck contains non-photosensitive inorganic paste film on it again.Cover the dielectric layer 12A of not baking as protective seam with layer protecting film.

In these examples, most preferably use on strippable supporting film, be formed with one deck by filming of constituting of photosensitive inorganic paste composition of the present invention and be capped the not plates of baking of last layer as the diaphragm of protective seam.

To describe each layer that constitutes the plates that the present invention do not toast below respectively, introduce the method for making the plates that the present invention do not toast then in detail.

(a) layer of spacer material

Layer of spacer material 16A is by forming pattern with photoetching process, remove organic material then, simultaneously baking inorganic powder and obtain one deck wall 16A in baking procedure.In the present invention, make layer of spacer material 16A with photosensitive inorganic paste composition of the present invention.

In the present invention, Norish I type Photoepolymerizationinitiater initiater and dehydrogenation Photoepolymerizationinitiater initiater are used in mixing, and the section that can make exposure back pattern is near rectangle or following bottom width W _BtmBe slightly less than bottom width W _TopTrapezoidal.In ensuing baking processing, the layer of spacer material 16A that forms pattern may shrink.Yet, shorten the following bottom width W of pattern slightly _Btm, just can prevent that pattern from deforming or break owing to shrinking.

When the contained glass dust of layer of spacer material that forms pattern melts in baking processing (seeing for details following), the sidewall of pattern may sink.Bottom width W under pattern form is _BtmBe slightly less than bottom width W _TopTrapezoidal the time, preferably causing wittingly to sink with baking processing increases down bottom width W _Btm, to improve the stability of pattern.

On the one hand,, preferably after baking processing, still can keep this rectangle, prevent preferably that therefore the sidewall of pattern from taking place sagging when baking processing when the section of the pattern that forms during near rectangle.For the softening point height of the glass dust that the softening point of preferably that layer of spacer material is contained glass dust is set more containedly than the dielectric layer of not baking takes place to sink when the baking processing in the sidewall that prevents pattern.Especially, the softening point of the glass dust that the softening point by the contained glass dust of layer of spacer material is set more containedly than the dielectric layer of not baking exceeds at least 5 ℃, preferably at least 7 ℃, more preferably at least 10 ℃, then the sidewall of pattern takes place to sink when baking processing and can be controlled in insignificant degree.

The thickness of the layer of spacer material that is obtained by filming of constituting of photosensitive inorganic paste composition of the present invention by drying is 10～50 μ m, preferred 15～40 μ m.

(b) dielectric layer that does not toast

Hong Kao dielectric layer 12A does not comprise the inorganic paste film that is coated with film preparation that is formed by the non-photosensitive inorganic paste composition by drying.In baking procedure, organic material is removed, and inorganic powder is toasted simultaneously, and Hong Kao dielectric layer 12A has not just become dielectric layer 12.It is inorganic powder and adhesive resin that the inorganic paste composition of the dielectric layer 12A that formation is not toasted comprises key component.

Same inorganic powder described in (A) photosensitive inorganic paste composition can be used as the inorganic powder that contains in the non-photosensitive inorganic paste composition of the dielectric layer that formation do not toast and uses.

The adhesive resin that contains in the non-photosensitive inorganic paste composition can be known adhesive resin, not special restriction can be used acrylic resin, cellulose derivative, polyvinyl alcohol (PVA), polyvinyl butyral, polyglycol, vibrin and urethane resin.Preferably contain acrylic resin, the acrylic resin of a hydroxyl is particularly arranged, have excellent Thermoadhesive for glass substrate like this.Same acrylic resin described in (A) photosensitive inorganic paste composition can be used as the acrylic resin with a hydroxyl and uses.

Total inorganic component, i.e. glass dust and inorganic particle, and organic component, for example the ratio of adhesive resin etc. is as follows.As 100 weight portions, the ratio of organic component is at 10 to 40 weight portions with inorganic component and organic component total amount, and the ratio of inorganic component is 90 to 60 weight portions.The ratio of preferred organic component is between 15 to 35 weight portions, and the ratio of inorganic component is between 85 to 65 weight portions.The ratio of preferred organic component is between 20 to 30 weight portions, and the ratio of inorganic component is between 80 to 70 weight portions.Amount outside above-mentioned scope is not preferred, and this is because during less than 10 weight portions, can not form film as the ratio of machine component, and during greater than 40 weight portions, after the baking serious contraction may take place as the ratio of machine component.

When forming the dielectric layer of not baking, if necessary can add a kind of solvent and remain in the OK range with viscosity with the non-photosensitive inorganic paste composition.Can be used as the contained solvent of non-photosensitive inorganic paste composition as same solvent in (A) photosensitive inorganic paste composition.For the viscosity that makes the non-photosensitive inorganic paste composition remains in the OK range, with inorganic component and organic component total amount as 100 weight portions, quantity of solvent is preferably smaller or equal to 300 weight portions, more preferably the amount of solvent is for obtaining the viscosity more than or equal to 3000cps, more preferably greater than the viscosity that equals 5000cps.

The non-photosensitive inorganic paste composition for example also may contain various selectable additive components: plastifier, spreading agent, tackifier, surface tension modifier, stabilizing agent and denaturant except containing inorganic powder, adhesive resin and solvent.

Can form filming of non-photosensitive inorganic paste composition by elder generation, dry then with the removal solvent, thus form the dielectric layer that does not toast.

Hong Kao dielectric layer is not 10 to 100 μ m at dried thickness, preferred 25 to 70 μ m.

(c) burnable intermediate layer may

Burnable intermediate layer may 14 is water-soluble or water-swellable, and it can dissolve or expand when washing, has carried out removing the residual layer of spacer material of handling in some zone through developing thereby raise and remove.One deck burnable intermediate layer may 14 optionally is set on layer of spacer material 16A.

When producing front panel of plasma display, this burnable intermediate layer may is arranged between the dielectric layer and layer of spacer material of not baking, described in the method for making of back.When being in the layer of spacer material of this stratification state with the rayed that forms pattern, and develop when forming the interval insulant layer pattern, interval insulant may remain on the surface after the exposure of the burnable intermediate layer may between the pattern projection.These interval insulants residual between the pattern projection melt by baking processing, and the surface after the dielectric layer exposure should be even flat surface, and is but therefore destroyed, forms uneven surface.In order to address this problem, between dielectric layer that does not toast and layer of spacer material, burnable intermediate layer may is set, residual like this interval insulant can form on the burnable intermediate layer may surface, if burnable intermediate layer may is water-soluble, the then residual interval insulant meeting and the burnable intermediate layer may of exposure area are developed solution (water or aqueous solution) together and wash off.When the burnable intermediate layer may water-swellable, the middle layer runs into developing solution and expands, and has raised the residual interval insulant on the interlayer surfaces, can easily wash off residual with developing solution.

The residual burnable intermediate layer may that can remove interval insulant by developing solution is after finishing the work, by the dielectric layer of not baking and the layer of spacer material of not toasting being toasted and thoroughly being burnt.As a result, on glass substrate, form and prior art structure and measure-alike dielectric layer and layer of spacer material, as front panel.The difference of front panel of the present invention and prior art front panel is in the prior art, and the dielectric layer of the exposure between wall and the adjacent wall is uneven, and the surface after the exposure of the front panel that the present invention makes is smooth.Here it is provides the vital role of the burnable intermediate layer may of water-soluble or water-swellable between dielectric layer that does not toast and layer of spacer material.

Because burnable intermediate layer may 14 is water-soluble or water-swellable, thoroughly decompose and burn at 400～700 ℃, so there is no particular restriction in the middle layer, but preferably include at least a in water soluble resin and the hydroexpansivity resin.Burnable intermediate layer may preferably forms with a kind of burnable intermediate layer may composition, and composition comprises a kind of solvent, and at least a in water soluble resin and the hydroexpansivity resin.

Polyvinyl alcohol (PVA), polyvinyl alcohol derivative, water-soluble cellulose etc. are preferably as water soluble resin.The partial cross-linked product of water soluble resin is preferably as the hydroexpansivity resin.Above-mentioned substance can be separately or two kinds or two or more mixing use.

The special example of polyvinyl alcohol derivative comprises, for example silanol modified polyethylene alcohol, cation-modified polyvinyl alcohol (PVA), the polyvinyl alcohol (PVA) that contains sulfydryl, butyral resin or the like.

The special example of water-soluble cellulose comprises, for example carboxymethyl cellulose, Carboxymethyl Cellulose, hydroxyethyl cellulose, HEMC, hydroxypropyl cellulose, ethylhydroxyethylcellulose, carboxymethylethylcellulose, hydroxypropyl methylcellulose or the like.

Wherein, weigh the pure and mild Carboxymethyl Cellulose of preferably polyethylene from water-soluble, pyrolytic and solvent resistance (solvent the anti-dielectric layer) angle.

There is no particular restriction to form the used solvent of burnable intermediate layer may, as long as it can dissolve the resin of water soluble resin or water-swellable fully, can access the viscosity that is suitable for being coated with, and can pass through drying evaporative removal easily, can select the organic solvent of water and propyl alcohol and so on for use.

With solvent the resin of water soluble resin or water-swellable is diluted to the concentration that is suitable for being coated with, forms filming of composition then, and, just can form burnable intermediate layer may by the dry solvent of removing.

The ratio of the resin of water soluble resin or water-swellable in forming the burnable intermediate layer may composition of burnable intermediate layer may be preferably smaller or equal to 50% quality, is more preferably less than to equal 30% quality, most preferably equals 0.1～20% quality.

The thickness of burnable intermediate layer may is preferably smaller or equal to 20 μ m, is more preferably less than to equal 10 μ m, is more preferably smaller or equal to 5 μ m.Burnable intermediate layer may can not be too thick, because in ensuing development step, the unexposed not material spacer layer layer of baking of photonasty also may be washed off.The optimum thickness of burnable intermediate layer may is 0.1～3 μ m.

(d) make the not method of the plates of baking

The supporting film of selecting for use when making the plates that the present invention do not toast 180, the removable film of this layer can make each layer that forms easily be peeled off thereon, and can will not toast layer and transfer on the glass substrate, and the use of this layer is not had special restriction.The example of this layer comprises the elastic membrane of thickness 15～125 μ m, contains synthetic resin films such as polyethylene terephthalate, tygon, polypropylene, polycarbonate, Polyvinylchloride.Supporting film preferably can be stripped from, so that shift.

For the dielectric layer 12A that forms layer of spacer material 16A, burnable intermediate layer may 14 and do not toast on supporting film, the composition of formation equivalent layer can prepare and be applied on the supporting film 180 with applicator, stripe shape spreader, wire bar spreader, finedraw coating machine, curtain flow coater etc.Especially, preferred cylinder coating machine is because it can effectively form layer thickness thick film very uniformly.Behind the dried coating film, can be coated with this desciccator diaphragm, make each laminated together like this, prepare the not plates of baking of the present invention with the following used another kind of composition of one deck.

Preferably layer protecting film 182 is attached to the reverse side of supporting film 180, stably to protect photonasty paste composition layer etc. before use.Polyethylene terephthalate film, polypropylene screen or the polyethylene film of about 15～125 μ m of this diaphragm preferred thickness, coating silicone or on it through overbaking.

(C) method of manufacturing front panel of plasma display

The method of making front panel of plasma display of the present invention is included in glass and is formed with dielectric layer and the layer of spacer material that the substrate surface of electrode will not toast and extrudes with this sequential layer, then with the rayed layer of spacer material that forms pattern, it is developed to form pattern on layer of spacer material, simultaneously the dielectric layer and the figuratum layer of spacer material of formation of the not baking on the glass substrate are carried out baking processing then, on glass substrate, form dielectric layer and layer of spacer material simultaneously.

The burnable intermediate layer may of water miscible or water-swellable selectively is provided between dielectric layer that does not toast and layer of spacer material in the present invention.Between the dielectric layer and layer of spacer material formed thereon of not baking, the developer solution that preferably will run into aqueous solution or wall can dissolve or expand, and can be pressed into the middle layer by the material layer that baking processing is thoroughly burnt.Ensuing exposure-processed and subsequent treatment are carried out with the technology of routine.Wherein residual material spacer layer can be removed before baking processing in the depression between pattern, and baking processing thoroughly burns up the middle layer, and the layer structure after the baking is the same with prior art.

(a) on glass substrate, form each layer

Extrude the dielectric layer of not baking and the method for layer of spacer material does not have particular restriction at glass substrate, can extrude each layer with known method, for example, rubbing method, silk screen print method or the like.Yet, consider that from the angle that forms the smooth layer of thickness uniform outer surface the method that the plates that do not toast with above-mentioned the present invention form equivalent layer is most preferred.

Describe the example that the plates that use the present invention not toast are made the method for front panel of plasma display below in detail.At first, preparation has the not plates of baking with supporting film, layer of spacer material and the protective seam of this order lamination.

Be formed with the dielectric layer that independent formation one deck does not toast on the glass baseplate surface of electrode.The method that forms the dielectric layer that does not toast does not have particular restriction, but preferably the non-photosensitive inorganic paste composition is applied on the supporting film, dry back forms the not dielectric layer of baking, and if necessary form burnable intermediate layer may with coating and drying, then it is laminated on the glass substrate, the dielectric layer surface in contact that does not toast is formed with the glass baseplate surface of electrode like this.Hot roller is moved to supporting film, just the dielectric layer that does not toast can be transferred on the glass substrate.

Then, peel off on the plates that diaphragm is never toasted, then the layer of spacer material that comes out is attached on the dielectric layer of not baking.Move hot roller then on supporting film, layer of spacer material just is hot-pressed to the not dielectric surface of baking like this.

The roller pressure scope of preferred hot pressing is 1～5 kg/cm ², translational speed is 0.1～10.0 meter/minute, the surperficial heating-up temperature of glass substrate 10 is 80～140 ℃.Can be to the glass substrate preheating, preheating can be chosen in 40～120 ℃ of scopes.

Introducing another then uses the following not plates of baking to make the example of the method for front panel of plasma display.At first, preparation has supporting film, layer of spacer material, the dielectric layer of not baking and the not plates of baking of diaphragm with this order lamination.Never after peeling off diaphragm on Hong Kao the plates, the dielectric layer that does not toast is attached to the glass baseplate surface that is formed with electrode.Move hot roller on supporting film, the dielectric and the layer of spacer material of baking just are not hot-pressed on the glass substrate like this.

Introducing another then uses the following not plates of baking to make the example of the method for front panel of plasma display.At first, preparation has the not plates of baking with supporting film, layer of spacer material, burnable intermediate layer may and the diaphragm of this order lamination.The glass baseplate surface that is formed with electrode on the surface forms the dielectric layer that one deck does not toast separately.Never peel off diaphragm on Hong Kao the plates to expose burnable intermediate layer may, then the burnable intermediate layer may that comes out is attached to the not dielectric layer of baking that the surface is formed with the glass baseplate surface formation of electrode.Move hot roller then on supporting film, burnable intermediate layer may and layer of spacer material just are hot-pressed to glass baseplate surface like this.

With reference to Fig. 8 A and Fig. 8 B, introduce another and use the following not plates of baking to make the example of the method for front panel of plasma display then.At first, preparation has supporting film 180, barrier material layer 16A, burnable intermediate layer may 14, the dielectric layer 12A of not baking and the not plates (Fig. 8 A) of baking of diaphragm 182 with this order lamination.Never peel off protective seam 182 on Hong Kao the plates to expose the not dielectric layer 12A of baking, the not dielectric layer 12A of baking that will come out then is attached to the glass baseplate surface 10 that the surface is formed with electrode.Move hot roller 40 then on supporting film 180, dielectric layer 12A, burnable intermediate layer may 14 and the layer of spacer material 16A of baking just are not hot-pressed to glass baseplate surface (Fig. 8 B) like this.

(b) exposure/development treatment

Can carry out exposure-processed and subsequent treatment with conventional method.Describe exposure/development treatment with reference to Fig. 4 A in detail to 4C.According to said method, Hong Kao dielectric layer 12A and layer of spacer material 16A do not form on glass substrate, and photomask 3 is positioned on the layer of spacer material 16A, and layer of spacer material exposure is so that harden (Fig. 4 A) at pattern part then.

In the present invention, use Norish I type Photoepolymerizationinitiater initiater and dehydrogenation Photoepolymerizationinitiater initiater simultaneously, therefore can prevent the inhibiting effect of oxygen.Therefore, promptly be that layer of spacer material 16A surface is not coated with hyaline membrane, the sclerosis on surface still can be carried out.Yet, when materials such as dust owing to static adheres to layer of spacer material 16A surface, may influence quality.Therefore, if in the plates that the present invention does not toast with hyaline membrane as supporting film 180, then on glass substrate after the lamination, the supporting film 180 that preferably will be retained on the layer of spacer material 16A exposes, and removes supporting film 180 after the exposure again.

As used irradiation apparatus in the exposure, can use the exposure device that uses in the manufacturing of ultraviolet irradiation device commonly used in photoetching process or semiconductor and LCD.

Then, remove the unexposed unhardened part 16A that does not toast layer of spacer material of photonasty, so just formed photoresist pattern 16A ' (seeing Fig. 4 B) by developing.

In development treatment, can use common alkaline development solution.Alkaline components in alkaline development solution comprises: oxyhydroxide, carbonate, hydrocarbonate, phosphate, with alkaline metal lithium for example, sodium, the pyrophosphate of potassium etc., primary amine is benzylamine for example, butylamine or the like, secondary amine is dimethylamine for example, dibenzylamine, diethanolamine or the like, tertiary amine is trimethylamine for example, triethylamine, triethanolamine or the like, cyclammonium is morpholine for example, piperazine, pyridine or the like, polyamine is the 2-ethylenediamine for example, hexamethylenediamine or the like, ammonium hydroxide is Tetramethylammonium hydroxide for example, tetraethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl benzylic hydrogens amine-oxides or the like, the trimethyl sulfonium hydroxide, sulfonium hydroxide, trimethyl sulfonium hydroxide for example, the diethylmethyl sulfonium hydroxide, dimethyl benzyl sulfonium hydroxide or the like, choline, the damping fluid that contains silicate, wherein consider of the infringement of alkali composition to powder, so preferred water.

Can make the pattern section that mixes use Norish I type Photoepolymerizationinitiater initiater and the initiating agent acquisition of the poly-back of dehydrogenation light near rectangle, as Fig. 7 A, or following bottom width W _BtmBe slightly less than bottom width W _TopTrapezoidal, as Fig. 7 B.Therefore can prevent that dielectric layer from deforming or break when baking processing.

(c) baking

Can the thin layer of top formation pattern be toasted, toast the dielectric layer 12A and the unexposed contained glass dust of layer of spacer material 16A ' that do not toast of photonasty of not baking thus, these layers can be changed into dielectric layer 12 and layer of spacer material 16 respectively thus.Obtain to be included in the front panel of plasma display of the present invention that forms the layer of spacer material 16 of pattern on the dielectric layer 12 thus.

The temperature of using in the baking can be burnt the organic material in the photosensitive inorganic paste composition, and inorganic powder then obtains baking, can be chosen in 400～700 ℃ of bakings 10～90 minutes.

Softening point that the softening point of the contained inorganic powder of layer of spacer material is higher than inorganic powder contained in the dielectric layer of not baking is sunk when the baking to prevent pattern sidewalls.Baking temperature preferably is not higher than the softening point T of the contained inorganic powder of layer of spacer material ₁(℃), be not less than not the softening point T of inorganic powder contained in the dielectric layer of baking ₂(℃) (T ₂＜T ₁).Especially, preferred baking temperature is a little less than the softening point T1 of the contained inorganic powder of layer of spacer material.Baking temperature is preferably greater than and equals T ₂℃, and smaller or equal to T ₁℃, more preferably more than or equal to (T ₁-5) ℃, and smaller or equal to T ₁℃, be more preferably more than or equal to (T ₁-7) ℃, and smaller or equal to T ₁℃, especially preferably about (T ₁-10) ℃.

After making front panel of plasma display with said method; this front panel has the figuratum layer of spacer material of one deck; this layer forms on dielectric layer; dielectric layer forms on glass substrate; be formed with electrode on the glass substrate, preferably the protective seam 19 with one deck MgO etc. covers unlapped dielectric layer and layer of spacer material.

Embodiment

Illustrate in greater detail the present invention below with reference to following examples.Yet, the invention is not restricted to this.

＜experimental example 1 〉

(preparation photosensitive inorganic paste composition)

The hydroxypropyl cellulose of 22 weight portions is as water-soluble cellulose derivative, styrene/methacrylic acid hydroxy methacrylate=55/45 (weight %) multipolymer (Mw=40000) of 14 weight portions is as the acryl resin with a hydroxyl, the 2-methacryl ethoxy of 60 weight portions-2-hydroxypropyl phthalic ester (trade name: HO-MPP, Kyoeisha Chemical Co., Ltd. make) as photo polymerization monomer, 0.9 2 of weight portion, 2-dimethoxy-2-phenyl acetophenone (trade name: IR-651, Norish I type, Chiba-Geigy makes) and 1.8 weight portions 2,4-diethyl thioxanthone (trade name: DETX-S, the dehydrogenation type, Nippon Kayaku Co., Ltd. make) as Photoepolymerizationinitiater initiater, 3.9 the tartrate butyl ester of weight portion is as plastifier, 0.1 the azo dyes of weight portion (trade name: DyeSS, Daito Chemix Corporation makes) as the UV absorbing agent, and the 3-methoxyl-3-methyl butyl ketone of 100 weight portions is as solvent, above-mentioned substance was stirred 3 hours with stirrer, prepare organic principle solution.Then, the softening point as inorganic constituents of organic principle solution of 40 weight portions (solids content 50%) and 80 weight portions is that 581 ℃ glass dust is blended together, and makes photosensitive inorganic paste composition.

＜experimental example 2 〉

(preparation non-photosensitive inorganic paste composition)

The isobutyl methacrylate of 45 weight portions/methacrylic acid hydroxyl ethyl ester=60/40 (weight %) multipolymer (Mw=70000) is as the acryl resin with a hydroxyl, the dibutyl tartrate of 5 weight portions is as plastifier, and the 3-methoxyl-3-methyl butyl ketone of 50 weight portions is as solvent, above-mentioned substance was stirred 3 hours at 80 ℃ with the stirrer of being furnished with water-bath, prepare organic principle solution.Then, this organic principle solution (solids content 50%) of 40 weight portions and the softening point of 80 weight portions are that 574 ℃ glass dust is blended together, and make the non-photosensitive inorganic paste composition.

＜experimental example 3 〉

(preparation forms the composition of burnable intermediate layer may)

The polyvinyl alcohol (PVA) of 4 weight portions (Ltd. makes for trade name: PVA-235, Kuraray Co.), and the isopropyl alcohol of the water of 53 weight portions and 43 weight portions with stirrer stirring 12 hours, is prepared the impermeable layer composition with above-mentioned substance as solvent.

＜embodiment 1 〉

The non-photosensitive inorganic paste composition that experimental example 2 is made is coated in to form on the supporting film of being made by polyethylene terephthalate films, and resulting to film at dried thickness be 60 μ m.This is filmed on 80 ℃ of preheating glass substrates with 100 ℃ laminating temperature then, 2.5 kg/cm ²Lamination pressure and 1.0 meters/minute laminate speed carry out lamination, form the not dielectric layer of baking.

The photosensitive inorganic paste composition of as above preparation is coated on the dielectric layer of not baking, and dried like this film thickness is 40 μ m, use 400 millis of ultraviolet high-pressure sodium lamp ejaculation burnt then/centimetre ²Ultraviolet ray expose through square pattern test mask.Use 30 ℃ of fluid temperatures then, expulsion pressure 3.0 kg/cm ²Water carry out spray developing 30 seconds to form pattern.Then the adhesiveness of the pattern that obtains is assessed, the width that found that the extra fine wire that stays is 60 μ m, minimum formation be spaced apart 60 μ m.The section of gained pattern is a ladder type, wherein descends bottom width W _BtmLess than last bottom width W _Top, and W _Btm: W _TopIt is 1: 0.9.

In order to assess the stability of the pattern form after the baking, formed the pattern of mask live width 200 μ m according to the method described above, and carried out baking processing, wherein sample heats under the temperature conditions that raises with 10 ℃/minute speed, place then 580 ℃ 30 minutes.The result has kept the pattern after the good baking.The section of the pattern after the baking is rectangle, wherein W _Btm: W _TopBe almost 1: 1.

＜embodiment 2 〉

The non-photosensitive inorganic paste composition of experimental example 2 being made with flange spreader (lip coater) is coated in by removable polyethylene terephthalate (trade name: Purex A24, TeijinDuPont Films Japan Limited manufacturing) on the supporting film that constitutes, resulting filming 100 ℃ of dryings 6 minutes with thorough removal solvent, forming thickness thus on supporting film is the not dielectric layer of baking of 60 μ m.

The composition of the formation burnable intermediate layer may of experimental example 3 being made with flange spreader (lip coater) is coated on the dielectric layer of the not baking on the supporting film, film 100 ℃ of dryings 6 minutes with thorough removal solvent, forming thickness thus on the dielectric layer of not baking is the burnable intermediate layer may of 0.5 μ m.

The photosensitive inorganic paste composition of experimental example 1 being made with flange spreader (lip coater) is coated on the burnable intermediate layer may on the supporting film, film 100 ℃ of dryings 6 minutes with thorough removal solvent, therefore forming thickness is the unexposed not layer of spacer material of baking of photonasty of 40 μ m.Then; one deck is contained removable polyethylene terephthalate (trade name: Purex A53; TeijinDuPont Film manufacturing) diaphragm is stacked on the layer of spacer material of the unexposed not baking of photonasty, makes the photosensitive film of the aqueous developable of 5 layers of structure.

When photosensitive film is laminated to when being formed with female electrode and being preheating on 80 ℃ the glass substrate at 150 ℃ by hot roller, removable polyethylene terephthalate (trade name: Purex A24, TeijinDuPont Films makes) supporting film that forms is stripped from, and this supporting film is exactly the photosensitive film of the water development made of said method.Air pressure is 3 kg/cm ², laminate speed is 1.0m/min.

With 300 millis that the ultraviolet high-pressure sodium lamp penetrates burnt/centimetre ²Ultraviolet ray through square pattern test mask the photonasty rete is exposed.After removing the polyethylene terephthalate diaphragm, with 30 ℃ of fluid temperatures, expulsion pressure 3 kg/cm ²Water carry out spray developing 30 seconds to form pattern.Then the adhesiveness and the pattern form of the pattern that obtains are assessed, the width that found that the extra fine wire that stays is 60 μ m, minimum formation be spaced apart 60 μ m, this is good pattern form.The section of gained pattern is a ladder type, wherein descends bottom width W _BtmLess than last bottom width W _Top, and W _Btm: W _TopIt is 1: 0.9.

＜embodiment 3 〉

The composition of the formation burnable intermediate layer may that experimental example 3 is made is coated in to form on the supporting film of being made by polyethylene terephthalate films, and filming at dried thickness is 0.5 μ m.This is filmed 100 ℃ of dryings 6 minutes removing solvent, thereby forms burnable intermediate layer may.The non-photosensitive inorganic paste composition of then experimental example 2 being made applies thereon, and the thickness of filming that dry back forms is 60 μ m.The surface of filming is attached on the glass substrate of 80 ℃ of preheatings, then with 100 ℃ laminating temperature, and 2.5 kg/cm ²Lamination pressure and 1.0 meters/minute laminate speed carry out lamination, form be formed with on it burnable intermediate layer may not the baking dielectric layer.Remove supporting film then.

The photosensitive inorganic paste composition of as above preparation is coated on the dielectric layer of not baking, and dried like this coated film thickness is 40 μ m, use 400 millis of ultraviolet high-pressure sodium lamp ejaculation burnt then/centimetre ²Ultraviolet ray expose by square pattern test mask.Use 30 ℃ of fluid temperatures then, expulsion pressure 3.0 kg/cm ²Water carry out spray developing 30 seconds to form pattern.Then the adhesiveness of the pattern that obtains is assessed, the width that found that the extra fine wire that stays is 60 μ m, minimum formation be spaced apart 60 μ m.The section of gained pattern is a ladder type, following bottom width W _BtmLess than last bottom width W _Top, and W _Btm: W _TopIt is 1: 0.9.

＜Comparative Examples 1 〉

The preparation method of photosensitive inorganic paste composition and insulation layer composition is with embodiment 1, difference is the Norish I type Photoepolymerizationinitiater initiater 2 with 0.9 weight portion, 2-dimethoxy-2-phenyl acetophenone (trade name: IR-651, Chiba-Geigy makes) separately as the Photoepolymerizationinitiater initiater in the photosensitive inorganic paste composition, adhering appraisal procedure is the same.Although found that the 100 μ m that are spaced apart of minimum formation, the width of the extra fine wire that stays is 60 μ m.The section of gained pattern is a ladder type, following bottom width W _BtmGreater than last bottom width W _Top, and W _Top: W _BtmIt is 0.6: 1.。

＜Comparative Examples 2 〉

The same example of the preparation method of photosensitive inorganic paste composition and insulation layer composition, difference is the dehydrogenation type 2 with 1.8 weight portions, 4-dimethyl thioxanthones (trade name: DETX-S, NipponKayaku Co., Ltd. make) separately as the Photoepolymerizationinitiater initiater in the photosensitive inorganic paste composition, 30 seconds spray developing method is the same.Found that pattern has been washed off, can not be hardened.

Practicality

As indicated above, photosensitive inorganic paste composition of the present invention draws the photopolymerization of Norish I type Send out agent and dehydrogenation Photoepolymerizationinitiater initiater and mix use, obtained good pattern, it is many to be preferably used as formation The material of layer circuit and various displays, these displays are such as plasma display, plasma address Liquid crystal display (plasma address liquid crystal display), be particularly preferred for make wanting Ask the layer of spacer material of the front panel of plasma display of pinpoint accuracy.

Claims

One kind not the baking plates, be used to make front panel of plasma display, described front panel comprises: a surface forms the glass substrate of several electrodes, one deck is formed on the dielectric layer on the described substrate, and be formed on the uniform wall of several layer thicknesses on the described dielectric layer, the described not plates of baking comprise:

The removable supporting film of one deck, which is provided with the unexposed not layer of spacer material of baking of photonasty, described layer of spacer material contains Photoepolymerizationinitiater initiater, photopolymerizable monomer and inorganic powder, and described Photoepolymerizationinitiater initiater contains a kind of Norish I type Photoepolymerizationinitiater initiater and a kind of dehydrogenation Photoepolymerizationinitiater initiater simultaneously;

Be arranged on the not dielectric layer of baking on the described layer of spacer material, the described not dielectric layer of baking contains inorganic powder and adhesive resin;

It is characterized in that the softening point of the inorganic powder that described layer of spacer material is contained is higher than the softening point of inorganic powder contained in the dielectric layer of not baking.
2. the not plates of baking according to claim 1, be used to make front panel of plasma display, it is characterized in that the softening point of contained inorganic powder is high at least 5 ℃ in the dielectric layer of the softening point of the inorganic powder that described layer of spacer material is contained than not baking.
3. the not plates of baking according to claim 1 are used to make front panel of plasma display, and the described not plates of baking comprise the burnable intermediate layer may of being located at the water-soluble or water-swellable on the described layer of spacer material.
4. method of making front panel of plasma display, described front panel comprises that a surface is formed with the glass substrate of several electrodes, one deck is formed on the dielectric layer on the described substrate, is formed on the uniform wall of several layer thicknesses on the described dielectric layer, and described method comprises:

(a) have on the glass baseplate surface of electrode on the surface, utilize the described not plates of baking of claim 1, form dielectric layer and the unexposed not layer of spacer material of baking of one deck photonasty that one deck does not toast successively;

(b) with the described layer of spacer material of rayed that forms pattern, develop then, form the interval insulant layer pattern thus; And

(c) toast simultaneously on the described glass substrate described not the baking dielectric layer and figuratum layer of spacer material, on described glass substrate, form described dielectric layer and described wall thus simultaneously.
5. the method for manufacturing front panel of plasma display according to claim 4 is characterized in that, the softening point of the inorganic powder that described layer of spacer material is contained is than at least 5 ℃ of the softening point height of contained inorganic powder in the dielectric layer of described not baking.
6. the method for manufacturing front panel of plasma display according to claim 5, it is characterized in that, in described step (c), described baking temperature is not less than the softening point of inorganic powder contained in the dielectric layer of described not baking, is not higher than the softening point of the contained inorganic powder of described layer of spacer material.
7. the method for manufacturing front panel of plasma display according to claim 4, it is characterized in that, in described step (a), the not plates of baking of lamination manufacturing front panel of plasma display according to claim 1 and 2, the described so not dielectric layer of baking is located on the described glass substrate.