JP4271048B2 - Photosensitive inorganic paste composition, sheet-shaped green body for producing plasma display front plate using the same, and method for producing plasma display front plate - Google Patents

Description

  The present invention relates to a photosensitive inorganic paste composition capable of obtaining a good pattern shape by a photolithography method, a sheet-like green body for producing a plasma display front plate using the same, and a method for producing a plasma display front plate.

  Plasma displays that form images by self-emitting many fine cells using the discharge phenomenon have large screen, thin, lightweight, and flat features that could not be realized with conventional displays. And its spread is planned.

  A conventional plasma display has been mainly a straight cell having ribs in the vertical direction. However, in recent years, a waffle cell having ribs in the horizontal direction as well as in the vertical direction has been developed in order to efficiently guide light from the light emitting part to the front surface of the plasma display. By making the cell a waffle structure, light leakage from adjacent cells can be prevented and light can be guided to the front surface with extremely high efficiency.

  FIG. 1 is an exploded perspective view of a main part of a plasma display having a waffle structure type cell. The plasma display includes a front plate 1 in which a composite electrode 11 composed of a transparent electrode 110 and a bus electrode 112 is formed in parallel with each other, and a back plate 2 in which address electrodes 21 are formed in parallel with each other so as to be orthogonal to the composite electrode 11. Is a display element that is arranged opposite to each other and integrated. The front plate 1 has a transparent glass substrate 10 serving as a display surface, and the composite electrode 11 is disposed on the inner side of the glass substrate 10, that is, on the back plate 2 side. A dielectric layer 12 is formed so as to cover the composite electrode 11, and a patterned spacer layer 16 is provided on the dielectric layer 12. On the surfaces of the dielectric layer 12 and the spacer layer 16, a dielectric layer 12 is formed. A protective film 19 made of MgO or the like is formed. On the other hand, the address electrode 21 is arranged on the front plate 1 side of the substrate 20 of the back plate 2, and a dielectric layer 22 is formed so as to cover the address electrode 21. A light emitting portion is formed.

  The light emitting part located in the space where the composite electrode 11 and the address electrode 21 intersect with each other is composed of a number of cells. A large number of cells are constituted by ribs 24 formed in the vertical and horizontal directions on the dielectric layer 22, and cover the wall surface of the rib 24 and the surface of the dielectric layer 22 in the rib, that is, the inner surface and the bottom surface of each cell. Thus, the phosphor layer 26 is provided. In the plasma display, a predetermined voltage is applied from an AC power source between the composite electrodes on the front plate to form an electric field, whereby discharge is performed in the cell, and the phosphor layer 26 is caused to emit light by ultraviolet rays generated by the discharge.

  FIG. 2 is a perspective view of the front plate 1 of the plasma display having the waffle structure type cell as viewed from the back plate side. FIG. 3 is a cross-sectional view of a plasma display having a waffle structure type cell. As shown in FIG. 2, in the waffle structure type plasma display, a large number of spacer layers 16 arranged in a line at equal intervals are provided on the dielectric layer 12. As shown in FIG. 3, in the front plate 1, since the spacer layer 16 contacts the ribs 24, gaps X are formed in the upper portions of the cells surrounded by the ribs 24, and rare cells are formed through the gaps X to the respective cells. Gas can be introduced.

  As a method for manufacturing such a front plate, a manufacturing method using a screen printing method is known. In the manufacturing method using the screen printing method, a glass paste film is formed on the glass substrate 10 and baked at 400 ° C. to 700 ° C. to form the dielectric layer 12, and then the glass paste composition is formed on the dielectric layer 12. Are laminated in a pattern by screen printing and fired again at 400 ° C. to 700 ° C. to form the spacer layer 16.

  However, since the manufacturing method using the screen printing method requires two baking steps, there is a problem that the manufacturing cost is high and the positional accuracy of the pattern is poor.

JP 2002-150949 A JP 2002-328467 A

  On the other hand, as a method for solving the problems in the screen printing method, a new method for manufacturing a plasma display front plate using a photolithography method has been proposed. A manufacturing process using a photolithography method will be described with reference to FIGS. First, an unfired dielectric layer 12A made of a non-photosensitive glass paste film and a photosensitive unexposed unfired spacer material layer 16A made of a photosensitive glass paste film are formed on the glass substrate 10, and this spacer material layer 16A. Then, ultraviolet rays or the like are irradiated through the photomask 3 (FIG. 4A). Next, development processing is performed to reveal the resist pattern 16A ′ (FIG. 4-2). By baking this at 400 ° C. to 700 ° C., the dielectric layer 12 and the spacer layer 16 are formed simultaneously (FIG. 4-3).

  In the manufacturing method using the photolithography method, since the dielectric layer 12 and the spacer layer 16 can be simultaneously fired by one firing, the manufacturing cost can be suppressed as compared with the manufacturing method using the screen printing method. There are advantages.

In the manufacturing method as described above, a photosensitive glass paste composition containing glass frit, a photopolymerization initiator, a photopolymerizable monomer, and a binder resin as a material for forming the spacer material layer 16A. Is used. As the photopolymerization initiator used in the photosensitive glass paste composition, a so-called Norrish type I photopolymerization initiator that has been cleaved at the α-carbon position to generate a radical has been used.

This Norrish type I photopolymerization initiator is characterized by high curing speed and excellent internal curability. By using a Norrish type I photopolymerization initiator with excellent internal curability, curing proceeds sufficiently to the bottom of the photosensitive glass paste film, and the cross-sectional shape of the pattern becomes slightly tailed, resulting in a highly stable pattern. Is obtained.

  However, in recent years, the demand for pattern miniaturization has further increased, and the conventional photosensitive glass paste composition has been problematic in that it cannot sufficiently cope with the fine patterning required for plasma displays.

For example, when the photosensitive glass paste film is exposed to form a pattern in FIG. 4A, the exposure light is incident on the surface of the photosensitive glass paste film through the photomask 3 in the vertical direction. However, in the photosensitive glass paste film, the exposure light is reflected on the glass frit contained in the film, causing halation, and the reach area of the exposure light is expanded. For this reason, the cross-sectional shape of the pattern 16A ′ obtained is a skirt shape as shown in FIG. In addition, as the pattern required by the plasma display is miniaturized and the pattern pitch is narrowed, the influence of this tailing becomes larger, resulting in a problem that the pattern accuracy is lowered.

  In particular, in the manufacturing method using the photolithography method described above, the exposure is performed in a state where the unfired dielectric layer 12A made of a non-photosensitive glass paste film is placed under the photosensitive glass paste film 16A. Therefore, not only the scattered reflected light of the glass frit contained in the photosensitive glass paste film, but also the scattered reflected light by the glass frit contained in the lower unfired dielectric layer 12A, the influence of halation is extremely high. Big. For this reason, the tendency that the bottom width Wbtm is widened with respect to the top width Wtop of the pattern is more remarkable.

  Due to the subsequent firing process, the patterned spacer material layer 16A ′ and the unfired dielectric layer 12A shrink slightly. At this time, if the area of the bonding portion between the pattern and the unfired dielectric layer 12A, that is, the area of the bottom surface of the patterned spacer material layer 16A ′ is large, the dielectric of the lower layer is caused by contraction of the individual patterned spacer material layer 16A ′. As shown in FIG. 6A, the layer 12 is drawn, and the dielectric layer 12 in the pattern portion is raised, so that the film thickness of the dielectric layer 12 becomes nonuniform. Further, as the patterned spacer material layer 16A ′ contracts, opposite tension acts on the dielectric layer 12 between the patterns, and cracks occur in the dielectric layer 12 located between the pattern lines as shown in FIG. There was also a problem that occurred.

Norrish type I photopolymerization initiator is excellent in internal curability, but suffers from oxygen damage.
In the surface portion that is in direct contact with oxygen, the curing reaction is difficult to proceed. For this reason, usually, in order to block oxygen, the surface of the photosensitive glass paste film is exposed with a transparent film 180 such as polyethylene terephthalate as shown in FIG. However, even if the surface is covered with a polyethylene terephthalate film, some oxygen permeates due to the thin film thickness. For this reason, the surface portion of the pattern remains in an uncured state even after exposure, and this is washed away with the developer, and the flatness of the pattern surface may be disturbed. When the pattern is baked in such a state, the glass frit component is melted and flattened by the baking process, but there is still a problem that unevenness remains on the surface and the film thickness of the pattern becomes non-uniform.

  The present invention has been made in view of the above-described conventional problems, and uses a photosensitive inorganic paste composition that has improved pattern accuracy to such an extent that it can be sufficiently adapted to fine patterning required by a plasma display. The present invention relates to a sheet-shaped green body for producing a plasma display front plate and a method for producing a plasma display front plate.

As a result of intensive studies to solve the above problems, the present inventors have found that a photopolymerization initiator in a photosensitive inorganic paste composition containing at least a photopolymerization initiator, a photopolymerizable monomer, and an inorganic powder. As a result, it was found that by using a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator in combination at the same time, a good pattern shape that can sufficiently cope with the fine patterning required by the plasma display can be obtained. The present invention has been completed based on the findings.

According to a preferred embodiment of the photosensitive inorganic paste composition of the present invention, as a Norrish type I photopolymerization initiator, a benzoin ether compound, a benzyl ketal compound, an α-hydroxyacetophenone compound, an α-aminoacetophenone compound, It is preferable to use at least one compound selected from the group consisting of bisacylphosphine oxide compounds, acylphosphine oxide compounds, phenyldicarbonyl compounds, and phenylacyloxime compounds. Moreover, it is preferable to use at least one compound selected from the group consisting of aromatic ketone compounds, thioxanthone compounds, anthraquinone compounds, and amine compounds as the hydrogen abstraction type photopolymerization initiator. Moreover, 10 to 99 parts by weight of Norrish type I photopolymerization initiator and 1 to 90 parts by weight of hydrogen abstraction type photopolymerization initiator with respect to 100 parts by weight of the total photopolymerization initiator in the photosensitive inorganic paste composition. It is preferable that

  Moreover, the sheet-like unfired body for producing the plasma display front plate of the present inventor is an unfired body in which a spacer material layer made of the above-described photosensitive inorganic paste composition of the present invention is formed on a release support film. Here, in the present specification, “sheet-shaped green body for producing a plasma display front plate” means that each layer formed on the release support film is a release support film when the plasma display front plate is produced. Means a sheet-like material used for peeling off and sticking on a glass substrate.

  Moreover, the manufacturing method of a plasma display front plate of this inventor forms a spacer material layer using the above-mentioned photosensitive inorganic paste composition of this invention, and performs the process after an exposure process conventionally. According to a preferred embodiment of the method for producing a plasma display front plate of the present invention, it is preferable that the softening point of the inorganic powder contained in the spacer material layer is higher than the softening point of the inorganic powder contained in the unfired dielectric layer. It is preferable to increase the softening point of the inorganic powder contained in the unfired dielectric layer by 5 ° C. or more.

  The photosensitive inorganic paste film formed using the photosensitive inorganic paste composition of the present invention has a good cured state of the surface of the pattern formed after exposure. Accordingly, the uncured photosensitive inorganic paste material on the surface of the pattern can be washed away with a developer as in the conventional case, so that the film thickness of the pattern can be prevented and a pattern having a uniform film thickness can be formed. Play.

Further, by using a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator in combination, the cross-sectional shape of the pattern after exposure is substantially rectangular as shown in FIG. 7-1 or shown in FIG. 7-2. As described above, the bottom width Wbtm can be controlled to be slightly narrower than the top width Wtop of the pattern. In particular, there is a problem that the bottom width Wbtm is widened under a condition that is easily affected by light reflection of the lower layer during exposure, such as a method of manufacturing a plasma display front plate using a photolithography method. This problem can be solved. As a result, the adhesion area with the unfired dielectric layer can be reduced, so that it is possible to prevent the dielectric layer from being deformed when the pattern shrinks, resulting in non-uniform film thickness and cracks.

  In addition, according to the sheet-shaped green body for producing a plasma display front plate of the present invention, at least a spacer material layer made of the photosensitive inorganic paste composition of the present invention is previously formed on the release support film, By stacking the body on the substrate at the time of manufacture, a spacer layer with good film thickness uniformity and surface smoothness can be formed on the glass substrate.

  The photosensitive insulating paste composition of the present invention is used as a material for producing various displays such as multilayer circuits, plasma displays, plasma addressed liquid crystal displays, field emission displays, etc., but plasma displays that require particularly high precision. It can be suitably used for producing a spacer material layer of the front plate.

  Further, according to the method for producing a plasma display front plate of the present invention, an unfired dielectric layer made of a non-photosensitive inorganic paste composition on a glass substrate, and a spacer material made of the photosensitive inorganic paste composition of the present invention By forming two layers, and thereafter performing the processing after the exposure processing in the conventional manner, the pattern accuracy can be improved, and deformation and cracking of the dielectric layer occurring during firing can be prevented.

  Further, in the method for manufacturing a plasma display front plate according to the present invention, the softening point of the inorganic powder contained in the spacer material layer is set higher than the softening point of the inorganic powder contained in the unfired dielectric layer, which occurs during firing. The sagging of the pattern side wall can be suppressed.

The photosensitive inorganic paste composition according to the present invention is a composition containing at least an inorganic powder, a photopolymerization initiator, and a photopolymerizable monomer, and as a photopolymerization initiator, a Norrish type I photopolymerization initiator and It is characterized by being used in combination with a hydrogen abstraction type photopolymerization initiator.

Conventionally, when manufacturing a plasma display front plate, as the photopolymerization initiator, Norrish type I photopolymerization initiator is used alone, the curability of the surface of the pattern is not sufficient,
There is a problem that the uncured photosensitive inorganic paste material on the surface portion is washed away with a developing solution and the pattern is reduced. On the other hand, by using a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator in combination, the curability of the surface of the pattern is improved, the film thickness of the pattern is prevented, and the film thickness of the pattern is made uniform it can.

In addition, by using a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator in combination, the cross-sectional shape of the pattern is almost rectangular or a trapezoid whose bottom width Wbtm is slightly narrower than the top width Wtop of the pattern. Can do. For this reason, it can prevent that a dielectric material layer deform | transforms at the time of a baking process, a film thickness becomes non-uniform | heterogenous, or a crack arises. Usually, in the field of photolithography, it is considered that a bottom width Wbtm narrower than a top width Wtop is not preferable because the stability of the pattern is lowered. When melted, the bottom width Wbtm is wider than before firing. Therefore, when the bottom width Wbtm is slightly narrower than the top width Wtop, the bottom width Wbtm widens during firing, so that the bottom width Wbtm approaches the top width Wtop, and there is a problem in the stability of the pattern after firing. Will not cause.

Hereinafter, embodiments of the present invention will be described in detail in the following order.
[A] photosensitive inorganic paste composition [B] sheet-shaped green body for manufacturing plasma display front plate [C] method for manufacturing plasma display front plate

[A] photosensitive inorganic paste composition The photosensitive inorganic paste composition of the present invention is a composition containing at least an inorganic powder, a photopolymerization initiator, and a photopolymerizable monomer, and as a photopolymerization initiator, It contains a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator.

  The photosensitive inorganic paste composition of the present invention has transparency necessary for exposure processing by ultraviolet rays, excimer laser, X-rays, electron beams (hereinafter referred to as light rays), and forms a highly accurate pattern by photolithography means. It is a composition which can be used suitably for manufacture of a plasma display.

(A) Photopolymerization initiator In the present invention, a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator are used in combination as the photopolymerization initiator.

The Norrish type I photopolymerization initiator is a type of photopolymerization initiator that is cleaved at the α-carbon position to generate radicals as shown in the following formula (1). On the other hand, the hydrogen abstraction type photopolymerization initiator is a type of photopolymerization initiator that generates a radical by extracting hydrogen from a hydrogen donor (RH) as shown in the following formula (2).

（上記一般式（１）及び（２）において、Ｘは、置換または無置換の芳香族基であり、Ｃ、Ｈ、Ｏ、ＮおよびＳのうち少なくとも１種から構成される有機基である。）

(In the above general formulas (1) and (2), X is a substituted or unsubstituted aromatic group, and is an organic group composed of at least one of C, H, O, N and S. )

In some radical photopolymerization initiators, after cleaving at the α-carbon position to generate a Norrish type I radical, the generated radical (• Y) extracts hydrogen from the hydrogen donor (RH) and further hydrogen There is a type that generates a pull-out type radical (.R). However, in the present invention, it is defined as belonging to the Norrish type I photopolymerization initiator as long as it is cleaved at the α-carbon position to generate a radical. Accordingly, the type of photopolymerization initiator that generates both radicals of Norrish type I and hydrogen abstraction type is classified as a Norrish type I photopolymerization initiator in the present invention.

(I) Norrish type I photopolymerization initiator As the Norrish type I photopolymerization initiator used in the present invention, the following general formulas (I-1) to (I-3)
It is preferable to use the compound represented by these.

（一般式（I-1）において、Ｒ₁₀〜Ｒ₁₃は、それぞれＣ、Ｈ、Ｏ、Ｎ、Ｓのうち少なくとも１種から構成される有機基であり、Ｒ₁₀は複数ある場合同じであっても異なっていてもよく、Ｒ₁₁〜Ｒ₁₃のうち２つが連結して環構造を形成していてもよく、ｎ1は０〜５の整数である）

(In General Formula (I-1), R _{10 to} R ₁₃ are each an organic group composed of at least one of C, H, O, N, and S, and the same is true when there are a plurality of R _10. Or two of R _{11 to} R ₁₃ may be linked to form a ring structure, and n 1 is an integer of 0 to 5)

（一般式（I-2）において、Ｒ₂₀〜Ｒ₂₂は、それぞれＣ、Ｈ、Ｏ、Ｎ、Ｓのうち少なくとも１種から構成される有機基であり、Ｒ₂₀は複数ある場合同じであっても異なっていてもよく、ｎ2は０〜５の整数である）

(In the general formula _{(I-2), R 20} ~R 22 is, C respectively, H, O, N, is an organic group composed of at least one of S, the same case R ₂₀ have a plurality of Or n2 is an integer of 0 to 5)

（一般式（I-3）において、Ｘは、ＯまたはＮであり、Ｒ₃₀およびＲ₃₁は、それぞれＣ、Ｈ、Ｏ、Ｎ、Ｓのうち少なくとも１種から構成される有機基であり、Ｒ₃₀は複数ある場合同じであっても異なっていてもよく、Ｒ₃₂は無置換またはＣ、Ｈ、Ｏ、Ｎ、Ｓのうち少なくとも１種から構成される有機基であり、ｎ3は０〜５の整数である）

(In General Formula (I-3), X is O or N, R ₃₀ and R ₃₁ are each an organic group composed of at least one of C, H, O, N, and S; When there are a plurality of R _{30 s} , they may be the same or different, and R ₃₂ is unsubstituted or an organic group composed of at least one of C, H, O, N and S, and n 3 is 0 to 0. (It is an integer of 5)

Examples of such Norrish type I photopolymerization initiators include benzoin ether compounds, benzyl ketal compounds, α-hydroxyacetophenone compounds, α-aminoacetophenone compounds, bisacylphosphine oxide compounds, acylphosphine oxide compounds, At least one compound selected from the group consisting of a phenyldicarbonyl compound and a phenylacyloxime compound is preferable. Among them, a benzyl ketal compound, a bisacylphosphine oxide compound, and an acylphosphine oxide compound are preferable, and a benzyl ketal compound. Compounds are more preferred.

Hereinafter, specific examples of the Norrish type I photopolymerization initiator represented by the general formulas (I-1) to (I-3) will be exemplified, but the Norrish type I photopolymerization initiator that can be used in the present invention is these. Of course, even if it is an analog of these compounds, it can be used in the present invention as a Norrish type I photopolymerization initiator.

ベンゾインメチルエーテル
ベンゾインエチルエーテル
ベンゾインイソプロピルエーテル (1) Benzoin ether compounds

Benzoin methyl ether Benzoin ethyl ether Benzoin isopropyl ether

(2) Benzyl ketal compounds

１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン
１−（４−ドデシルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン (3) α-hydroxyacetophenone compounds

1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one

(4) α-aminoacetophenone compounds

(5) Bisacylphosphine oxide compounds

(6) Acylphosphine oxide compounds

(7) Phenyldicarbonyl compounds

(8) Phenylacyloxime compounds

(II) Hydrogen abstraction type photopolymerization initiator In the present invention, as the hydrogen abstraction type photopolymerization initiator, it is preferable to use a compound represented by the following general formula (II-1) or (II-2).

（一般式（II-1）において、Ｒ₄₀、Ｒ₄₁は、それぞれＣ、Ｈ、Ｏ、ＮおよびＳのうち少なくとも１種から構成される有機基であり、Ｒ₄₀およびＲ₄₁は複数ある場合同じであっても異なっていてもよく、Ｒ₄₀およびＲ₄₁のうち２つが連結して環構造を形成していてもよく、ｎ40、ｎ41はそれぞれ０〜５の整数である）

(In the general formula (II-1), R ₄₀ and R ₄₁ are each an organic group composed of at least one of C, H, O, N and S, and there are a plurality of R ₄₀ and R _41. And may be the same or different, and two of R ₄₀ and R ₄₁ may be linked to form a ring structure, and n ₄₀ and n ₄₁ are each an integer of 0 to 5)

（一般式（II-2）において、Ｒ₅₀およびＲ₅₁は、それぞれ炭化水素基であり、Ｒ₅₂は、Ｃ、Ｈ、Ｏ、ＮおよびＳのうち少なくとも１種から構成される有機基である。）

(In the general formula (II-2), R ₅₀ and R ₅₁ are each a hydrocarbon group, and R ₅₂ is an organic group composed of at least one of C, H, O, N and S. .)

  The hydrogen abstraction type photopolymerization initiator is at least one selected from the group consisting of aromatic ketone compounds, thioxanthone compounds, anthraquinone compounds, and amine compounds (aromatic compounds having a dialkylamino group, alkylalkanolamines, etc.). Among these compounds, thioxanthone compounds and aromatic compounds having a dialkylamino group are preferred, and thioxanthone compounds are more preferred.

  Hereinafter, specific examples of the hydrogen abstraction type photopolymerization initiator represented by the general formula (II-1) or (II-2) will be exemplified, but the hydrogen abstraction type photopolymerization initiator that can be used in the present invention includes these. Of course, even if it is an analog of these compounds, it can be used in the present invention as a hydrogen abstraction type photopolymerization initiator.

３，３−ジメチル−４−メトキシベンゾフェノン
ベンゾフェノン (1) Aromatic ketone compounds

3,3-dimethyl-4-methoxybenzophenone benzophenone

チオキサントン
２−メチルチオキサントン
２−イソプロピルチオキサントン
２，４−ジメチルチオキサントン
２−クロロチオキサントン
１−クロロ−４−プロポキシチオキサントン (2) Thioxanthone compounds

Thioxanthone 2-methylthioxanthone 2-isopropylthioxanthone 2,4-dimethylthioxanthone 2-chlorothioxanthone 1-chloro-4-propoxythioxanthone

(3) Anthraquinone compounds

４，４−ビス（ジメチルアミノ）−ベンゾフェノン（ミヒラーケトン）
ペンチル−４−ジメチルアミノベンゾエート
Ｎ-ブトキシエチル-４-ジメチルアミノベンゾエート
２-（ジメチルアミノ）エチルベンゾエート
４−ジメチルアミノ安息香酸
４−ジメチルアミノ安息香酸メチル
４−ジメチルアミノ安息香酸エチル
４−ジメチルアミノ安息香酸ブチル
４−ジメチルアミノ安息香酸−２−エチルヘキシル
４−ジメチルアミノ安息香酸−２−イソアミル
ペンチル−４−ジメチルアミノベンゾエート
(ii)アルキルアルカノールアミン
モノエタノールアミン
ジエタノールアミン
トリエタノールアミン
Ｎ-メチルエタノールアミン
Ｎ-メチルジエタノールアミン
２-ジエチルエタノールアミン
トリイソプロパノールアミン (4) Amine compounds
(i) an aromatic compound having a dialkylamino group

4,4-bis (dimethylamino) -benzophenone (Michler's ketone)
Pentyl-4-dimethylaminobenzoate N-butoxyethyl-4-dimethylaminobenzoate 2- (dimethylamino) ethylbenzoate 4-dimethylaminobenzoate 4-dimethylaminobenzoate methyl 4-dimethylaminobenzoate ethyl 4-dimethylaminobenzoate Butyl acid 4-dimethylaminobenzoic acid-2-ethylhexyl 4-dimethylaminobenzoic acid-2-isoamylpentyl-4-dimethylaminobenzoate
(ii) Alkylalkanolamine monoethanolamine diethanolamine triethanolamine N-methylethanolamine N-methyldiethanolamine 2-diethylethanolamine triisopropanolamine

(B) Photopolymerizable monomer The photopolymerizable monomer may be a known photopolymerizable monomer and is not particularly limited. For example, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenoxyethyl acrylate , Phenoxyethyl methacrylate, phenoxy polyethylene glycol acrylate, phenoxy polyethylene glycol methacrylate, styrene, nonyl phenoxy polyethylene glycol mono acrylate, nonyl phenoxy polyethylene glycol mono methacrylate, nonyl phenoxy polypropylene glycol mono acrylate, nonyl phenoxy polypropylene glycol mono methacrylate, 2-hydroxy-3 -Phenoxypropyl acrylate, 2-acryloyl Roxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl acrylate, n-propyl Methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, glycerol acrylate , Glycerol methacrylate, dipentaerythritol monoacrylate Dipentaerythritol monomethacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, phthalic acid modified monoacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, Triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate Tacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glycerol acrylate Glycerol methacrylate, cardo epoxy diacrylate, fumaric acid ester in which (meth) acrylate of these exemplary compounds is replaced with fumarate, itaconic acid ester in place of itaconate, maleic acid ester in place of maleate, and the like.

(C) Inorganic powder The inorganic powder contained in the photosensitive inorganic paste composition of the present invention is not particularly limited as long as it satisfies the transparency required for the exposure light source. For example, glass, ceramics (cordylite, etc.) ) And metals. Specifically, PbO—SiO ₂ , PbO—B ₂ O ₃ —SiO ₂ , ZnO—SiO ₂ , ZnO—B ₂ O ₃ —SiO ₂ , BiO—SiO ₂ , BiO—B ₂ O ₃ -SiO ₂ system borosilicate lead glass, borosilicate zinc glass, and glass powders such as borosilicate bismuth glass, cobalt oxide, iron oxide, chromium oxide, nickel oxide, copper oxide, manganese oxide, neodymium oxide, vanadium oxide, Cerium oxide yellow, cadmium oxide, ruthenium oxide, silica, magnesia, spinel and other oxides such as Na, K, Mg, Ca, Ba, Ti, Zr, Al, ZnO: Zn, Zn ₃ (PO ₄ ) _{2: Mn, Y 2 SiO 5} : Ce, CaWO 4: Pb, BaMgAl 14 O 23: Eu, ZnS: (Ag, Cd), Y 2 O 3: Eu, Y 2 SiO 5: Eu, Y 3 A1 5 _{12: Eu, YBO 3: Eu} , (Y, Gd) BO 3: Eu, GdBO 3: Eu, ScBO 3: Eu, LuBO 3: Eu, Zn 2 SiO 4: Mn, BaAl 12 O 19: Mn, SrAl 13 _{O 19: Mn, CaAl 12 O} 19: Mn, YBO 3: Tb, BaMgAl 14 O 23: Mn, LuBO 3: Tb, GdBO: Tb, ScBO 3: Tb, Sr6 Si 3 O 3 Cl 4: Eu, ZnS: (Cu, Al), phosphor powder such as ZnS: Ag, Y ₂ O ₂ S: Eu, ZnS: Zn, (Y, Cd) BO ₃ : Eu, BaMgAl ₁₂ O ₂₃ : Eu, iron, nickel, palladium, Examples thereof include metal powders such as tungsten, copper, aluminum, silver, gold, and platinum. In particular, glass, ceramics and the like are preferable because of excellent transparency. Among them, the most remarkable effect appears when glass powder (glass frit) is used. When the inorganic powder contains silicon oxide, aluminum oxide, or titanium oxide, turbidity is generated and the light transmittance is lowered. Therefore, it is desirable not to include these components.

  Although the particle diameter of the inorganic powder depends on the shape of the pattern to be produced, the average particle diameter is preferably 0.1 to 10 μm, more preferably 0.5 to 8 μm. If the average particle size exceeds 10 μm, surface irregularities will occur during the formation of a highly accurate pattern, and this is not preferred. If the average particle size is less than 0.1 μm, fine cavities are formed during firing, causing insulation failure, and dispersibility. Is unfavorable because it becomes defective. Examples of the shape of the inorganic powder include a spherical shape, a block shape, a flake shape, and a dendrite shape, and these can be used alone or in combination of two or more.

  In addition to black, the inorganic powder can contain inorganic pigments that develop colors such as red, blue, and green. By using the photosensitive insulating paste composition containing the pigment, a pattern of each color can be formed, which is suitable for producing a color filter of a plasma display panel. The inorganic powder may be a mixture of fine particles having different physical properties. In particular, the shrinkage rate during firing can be suppressed by using glass powder or ceramic powder having different thermal softening points. This inorganic powder is preferably blended by changing the combination of the shape and physical property values according to the properties of the partition walls and the like.

  As described above, since the average particle size of the inorganic powder is 1 to 10 μm and a particle size of 10 μm or less, the properties of the inorganic powder are not impaired in order to prevent the secondary aggregation and improve the dispersibility. The surface may be previously treated with a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a surfactant, or the like. As the treatment method, after dissolving the treatment agent in an organic solvent or water, the inorganic powder is added and stirred, the solvent is distilled off, and the heat treatment is preferably performed at about 50 to 200 ° C. for 2 hours or more. Moreover, you may add the said processing agent at the time of paste-izing of a photosensitive composition.

(D) Binder resin A binder resin is usually added to the photosensitive inorganic paste composition in order to improve coatability and film-forming property. Such a binder resin may be a known binder resin in the present invention, and is not particularly limited. An acrylic resin, a cellulose derivative, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, a urethane resin, and a melamine resin can be used. . The inclusion of an acrylic resin, particularly an acrylic resin having a hydroxyl group, is preferable because development resistance is improved and a highly accurate image can be formed.

  In the photosensitive inorganic paste composition of the present invention, the transmittance of actinic rays such as ultraviolet rays, excimer lasers, X-rays and electron beams is improved by using a combination of an acrylic resin having a hydroxyl group and a water-soluble cellulose derivative. However, it is preferable because a highly accurate pattern can be formed.

  Examples of the acrylic resin having a hydroxyl group include a copolymer obtained by polymerizing a monomer having a hydroxyl group as a main copolymerizable monomer and, if necessary, other monomers copolymerizable therewith. As the monomer having a hydroxyl group, an alkylene oxide adduct obtained by adding an alkylene oxide to acrylic acid or methacrylic acid, specifically an adduct of ethylene oxide, propylene oxide, butylene oxide, or a mixed adduct thereof is suitable. For example, hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Butyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate , 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the like, and monoesterified products of acrylic acid or methacrylic acid and glycols having 1 to 10 carbon atoms, glycerol acrylate, glycerol methacrylate, dipenta Mention may be made of epoxy ester compounds such as erythritol monoacrylate, dipentaerythritol monomethacrylate, ε-caprolactone-modified hydroxyl ethyl acrylate, ε-caprolactone-modified hydroxyl ethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate.

  Examples of other monomers copolymerizable with the monomer having a hydroxyl group include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, citraconic acid, itaconic acid, maleic acid, and fumaric acid, and These anhydrides or half-esterified products, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, sec-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , Β-unsaturated carboxylic acid esters such as sec-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, 2,2,2-trifluoromethyl acrylate, 2,2,2-trifluoromethyl methacrylate Styrenes such as styrene, α-methylstyrene, and p-vinyltoluene are preferable. Further, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, and the like can also be used. These may be used alone or in combination of two or more.

  As the water-soluble cellulose derivative, known ones can be used and are not particularly limited, and examples thereof include carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl ethyl cellulose, hydroxypropyl methyl cellulose and the like. Can be mentioned. You may use these individually or in mixture of 2 or more types.

(E) Compounding ratio of each component In the photosensitive inorganic paste composition of the present invention, the ratio of the Norrish I type photopolymerization initiator to the hydrogen abstraction type photopolymerization initiator is Norrish I with respect to 100 parts by weight of the total of the two components. 1 to 90 parts by weight of the photopolymerization initiator, 10 to 99 parts by weight of the hydrogen abstraction type photopolymerization initiator, preferably 10 to 50 parts by weight of the Norrish type I photopolymerization initiator, and the hydrogen abstraction type photopolymerization initiator 50
It is preferable to be in the range of ~ 90 parts by weight, more preferably 20 to 40 parts by weight of Norrish type I photopolymerization initiator and 60 to 80 parts by weight of hydrogen abstraction type photopolymerization initiator.

In particular, when the photosensitive inorganic paste composition of the present invention is used as a spacer material layer for a plasma display front plate, the proportion of the hydrogen abstraction type photopolymerization initiator in the photopolymerization initiator in the photosensitive inorganic paste composition is increased. It is preferable to set to. Specifically, 10 to 90 parts by weight of Norrish type I photopolymerization initiator and 10 to 90 parts of hydrogen abstraction type photopolymerization initiator are added to 100 parts by weight of the total amount of photopolymerization initiator in the photosensitive inorganic paste composition. Parts by weight, preferably 20 to 50 parts by weight of Norrish type I photopolymerization initiator, and 50 to 50 parts of hydrogen abstraction type photopolymerization initiator.
80 parts by weight, more preferably 30 to 40 parts by weight of Norrish type I photopolymerization initiator and 60 to 70 parts by weight of hydrogen abstraction type photopolymerization initiator are preferred.

In the production of the plasma display front plate, exposure is performed in a state in which an unfired dielectric layer 12A made of a non-photosensitive inorganic paste film is placed under the photosensitive inorganic paste film 16A during pattern formation. Therefore, not only the scattered reflected light of the inorganic powder contained in the photosensitive inorganic paste film, but also the scattered reflected light from the inorganic powder contained in the lower unfired dielectric layer 12A, the influence of halation is increased, There is a tendency that the bottom width Wbtm of the cross-sectional shape of the pattern after the exposure increases. However, by setting the blending ratio of the Norrish type I photopolymerization initiator and the hydrogen abstraction type photopolymerization initiator within the above range, the cross-sectional shape of the pattern after exposure is almost rectangular or the bottom width with respect to the top width Wtop of the pattern. The trapezoidal shape of Wbtm can be made slightly narrow, and deformation and cracking of the dielectric layer caused by shrinkage of the pattern during firing can be prevented.

  In the photosensitive inorganic paste composition of the present invention, the ratio of the water-soluble cellulose derivative and the acrylic resin having a hydroxyl group is 50 to 90 parts by weight of the water-soluble cellulose derivative with respect to 100 parts by weight of the total of the two components. 50 to 10 parts by weight of an acrylic resin having a group, preferably 60 to 80 parts by weight of a water-soluble cellulose derivative, 40 to 20 parts by weight of an acrylic resin having a hydroxyl group, and more preferably 60 to 70 parts by weight of a water-soluble cellulose derivative. The acrylic resin having a hydroxyl group is preferably in the range of 40 to 30 parts by weight.

  The photopolymerization initiator is preferably in the range of 0.1 to 10 parts by weight, more preferably in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the total of the water-soluble cellulose derivative and the photopolymerizable monomer. Used. When the photopolymerization initiator is less than 0.1 part by weight, curability is lowered. Moreover, when a photoinitiator exceeds 10 weight part, the bottom part hardening defect by absorption of an initiator is seen.

  The ratio of organic components such as water-soluble cellulose derivatives and binder resins such as acrylic resins, photopolymerization initiators, and the like, and the total amount of inorganic components including glass frit and other inorganic powders is 100% by weight of the total of the photosensitive inorganic paste composition. 10 to 40 parts by weight of organic component, 90 to 60 parts by weight of inorganic component, preferably 15 to 35 parts by weight of organic component, 85 to 65 parts by weight of inorganic component, and more preferably 20 to 65 parts by weight of organic component. A range of 30 parts by weight and 80 to 70 parts by weight of the inorganic component is preferable.

  In forming the spacer material layer, a solvent may be added as necessary in order to maintain the viscosity of the photosensitive inorganic paste composition of the present invention within a suitable range.

  As the solvent contained in the photosensitive inorganic paste composition, the organic component has good solubility, can impart appropriate viscosity to the photosensitive inorganic paste composition, and can be easily removed by evaporation. If it is, it will not be specifically limited. Particularly preferred solvents include ketones, alcohols and esters having a boiling point of 100 to 200 ° C.

  Specific examples of such solvents include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol, and diacetone alcohol; Ether-based alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; acetic acid -Saturated aliphatic monocarboxylic acid alkyl such as n-butyl and amyl acetate Stealth; Lactic acid esters such as ethyl lactate and lactate-n-butyl; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 2-methoxy Butyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate , 4-ethoxybutyl acetate, 4-propoxybutyl acetate, ether esters such as 2-methoxypentyl acetate, and the like. It can be used in combination or species.

  The content of the solvent is preferably 300 parts by weight or less, more preferably 10 to 70 parts by weight, and most preferably 25 to 35 parts by weight with respect to 100 parts by weight of the total of the inorganic component and the organic component.

  In addition to the above, addition of UV absorbers, sensitizers, polymerization inhibitors, plasticizers, thickeners, organic solvents, dispersants, antifoaming agents, organic or inorganic precipitation inhibitors, etc., as necessary Agent ingredients can be added.

The polymerization inhibitor is added to improve the thermal stability during storage. Specific examples thereof include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol. N-phenylnaphthylamine, 2,6-di-t-butyl-p-methylphenol, chloranil, pyrogallol and the like.

Furthermore, as a plasticizer for improving the followability to the substrate, phthalates, specifically dibutyl phthalate (DBP), dioctyl phthalate (DOP), polyethylene glycol, glycerin, tartaric acid diesters, specifically tartaric acid Specific examples of citrate esters such as diethyl and dibutyl tartrate include triethyl citrate and tributyl citrate.

Specific examples of antifoaming agents include alkylene glycol-based, silicone-based and higher alcohol-based antifoaming agents such as polyethylene glycol (molecular weight 400 to 800), which reduce bubbles in the paste or film. The pores after firing can be reduced.

[B] Sheet-like unfired body for plasma display front plate production The sheet-like unfired body for plasma display front plate production of the present invention is formed on the release supporting film from the coating film of the photosensitive inorganic paste composition of the present invention. An unfired body on which at least a spacer material layer is formed.

  As a main supply form of the sheet-shaped green body according to the present invention, a one-layer structure including only a spacer material layer and a two-layer structure including a spacer material layer and an unfired dielectric layer or a combustible intermediate layer And a three-layer structure comprising a spacer material layer, an unfired dielectric layer, and a combustible intermediate layer. These 1-layer to 3-layer structures are protected by a release film that can be easily peeled on both sides, and are easy to store, transport, and handle.

  Since the sheet-like green body according to the present invention is manufactured in advance and can be stored for a predetermined period of time although it has an expiration date, it is used immediately when manufacturing a plasma display front plate. In other words, the manufacturing efficiency of the front panel of the plasma display can be improved.

Specific examples of main supply forms of the sheet-shaped green body of the present invention will be described below.
One is a sheet-like green body in which a coating film of the photosensitive inorganic paste composition of the present invention is formed on a release support film. A spacer material layer is formed by applying and drying the photosensitive inorganic paste composition of the present invention diluted to a concentration suitable for application with a solvent on a peelable support film. A protective film is coated on the spacer material layer as a protective layer.

  One is a sheet-like unfired body having a spacer material layer and an unfired dielectric layer. A spacer material layer made of the photosensitive inorganic paste composition of the present invention is formed on a peelable support film. An unfired dielectric layer made of a non-photosensitive inorganic paste composition is formed on the spacer material layer, and a protective film is coated thereon as a protective layer.

  One is a sheet-like green body in which a combustible intermediate layer is formed on a spacer material layer. A spacer material layer made of a coating film of the photosensitive inorganic paste composition of the present invention is formed on a peelable support film. A water-soluble or water-swellable combustible intermediate layer is formed on the spacer material layer, and a protective film is coated thereon as a protective layer.

One is a sheet-like green body in which a combustible intermediate layer and a green dielectric layer are formed on a spacer material layer. In FIG. 8A, a spacer material layer 16 </ b> A made of a coating film of the photosensitive inorganic paste composition of the present invention is formed on a peelable support film 180. A water-soluble or water-swellable combustible intermediate layer 14 is formed on the spacer material layer 16A, and an unfired dielectric layer 12A made of a non-photosensitive inorganic paste film is formed thereon. A protective film 182 is coated on the unfired dielectric layer 12A as a protective layer.
Among these specific examples, a sheet-like unfired body in which a coating film of the photosensitive inorganic paste composition of the present invention is formed on a release support film and a protective film is coated is most preferably used.

  Hereinafter, after explaining each layer which comprises the sheet-like unbaking body of this invention, the manufacturing method of the sheet-like unbaking body of this invention is explained in full detail.

(A) Spacer material layer The spacer material layer 16A is a layer that becomes the spacer layer 16 by forming a pattern by a photolithography method and then removing organic substances in the baking step and sintering inorganic powder. In the present invention, the spacer material layer 16A is prepared using the above-described photosensitive inorganic paste composition of the present invention.

In the present invention, a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator are used in combination at the same time, so that the cross-sectional shape of the pattern after exposure is substantially rectangular or the bottom width Wbtm with respect to the top width Wtop of the pattern. Can be a slightly narrow trapezoidal shape. Although the patterned spacer material layer 16A shrinks in the subsequent baking treatment, deformation and cracking when the pattern shrinks can be prevented by slightly narrowing the bottom width Wbtm of the pattern.

  When the glass frit contained in the patterned spacer material layer is melted by a baking process described later, sagging may occur on the pattern side wall. If the pattern has a trapezoidal shape with the bottom width Wbtm slightly narrower than the top width Wtop, the bottom width Wbtm is slightly reduced by consciously generating the sagging on the pattern side wall in the baking process in order to improve the stability of the pattern. It is preferable to spread.

  On the other hand, when the pattern cross section is obtained in a substantially rectangular state, it is preferable to maintain this rectangular shape even after the baking process, and therefore it is preferable to prevent the pattern sidewall from sagging during the baking process described above. In order to prevent sagging of the pattern side walls during the firing process, it is preferable that the softening point of the glass frit contained in the spacer material layer is higher than the softening point of the glass frit contained in the unfired dielectric layer. In particular, the softening point of the glass frit contained in the spacer material layer is 5 ° C. or more, preferably 7 ° C. or more, more preferably 10 ° C. or more higher than the softening point of the glass frit contained in the unfired dielectric layer. By setting, the sagging of the pattern side wall during the firing process can be suppressed to a level that can be almost ignored.

  The film thickness of the spacer material layer obtained by drying the coating film of the photosensitive inorganic paste composition of the present invention is 10 to 50 μm, preferably 15 to 40 μm.

(B) Unfired dielectric layer The unfired dielectric layer 12A is composed of an inorganic paste film obtained by drying a coating film formed using a non-photosensitive inorganic paste composition. The unfired dielectric layer 12 </ b> A is a layer in which the organic substance is removed in the firing step and the inorganic powder is sintered to become the dielectric layer 12. The inorganic paste composition for forming the unfired dielectric layer 12A contains an inorganic powder and a binder resin as essential components.

  As the inorganic powder contained in the non-photosensitive inorganic paste composition for forming the unfired dielectric layer, the same powder as described in the section [A] Photosensitive inorganic paste composition can be used.

  The binder resin contained in the non-photosensitive inorganic paste composition may be a known binder resin, and is not particularly limited, but is not limited to acrylic resin, cellulose derivative, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polyester resin, urethane. A resin or the like can be used. It is preferable that an acrylic resin, particularly an acrylic resin having a hydroxyl group, is contained because excellent heat adhesion to a glass substrate is exhibited. About the acrylic resin which has a hydroxyl group, the same thing as what was demonstrated in the term of [A] photosensitive inorganic paste composition can be used.

  The ratio of the inorganic component obtained by adding the glass frit and the inorganic particles to the organic component such as the binder resin is 10 to 40 parts by weight of the organic component and 90% of the inorganic powder with respect to 100 parts by weight of the total of the inorganic component and the organic component. -60 parts by weight, preferably 15 to 35 parts by weight of organic component, 85 to 70 parts by weight of inorganic powder, more preferably 20 to 30 parts by weight of organic component, and 80 to 70 parts by weight of inorganic powder. When the organic component is less than 10 parts by weight, film formation cannot be performed, and when the organic component exceeds 40 parts by weight, shrinkage increases after firing, which is not preferable.

  In forming the unfired dielectric layer, a solvent may be added as necessary in order to maintain the viscosity of the non-photosensitive inorganic paste composition in a suitable range. About the solvent contained in a non-photosensitive inorganic paste composition, the same thing as what was demonstrated in the term of [A] photosensitive inorganic paste composition can be used. In order to maintain the viscosity of the non-photosensitive inorganic paste composition in a suitable range, the content of the solvent is preferably 300 parts by weight or less, more preferably the viscosity with respect to 100 parts by weight of the total of the inorganic component and the organic component. The conversion is most preferably 3000 cps or more and 5000 cps or more.

  In addition to inorganic powders, binder resins and solvents, non-photosensitive inorganic paste compositions include various additives such as plasticizers, dispersants, tackifiers, surface tension modifiers, stabilizers and antifoaming agents. It may be contained as an optional component.

  The unfired dielectric layer can be formed by forming a coating film of the non-photosensitive inorganic paste composition and then drying the coating film to remove the solvent.

  The thickness of the unfired dielectric layer after drying is 10 to 100 μm, preferably 25 to 70 μm.

(C) The combustible intermediate layer The combustible intermediate layer 14 is water-soluble or water-swellable, and is removed by floating the spacer material layer remaining at the development removal site by washing with water and dissolving or swelling. It is a layer to do. The combustible intermediate layer 14 is a layer that can optionally be provided on the spacer material layer 16A.

  This combustible intermediate layer is located between the unfired dielectric layer and the spacer material layer, as will be described in detail in the manufacturing method described later when the plasma display front plate is manufactured. When the spacer material layer is patterned by irradiating the pattern light to the spacer material layer in such a laminated state and developing the spacer material layer, a spacer material is formed on the exposed surface of the combustible intermediate layer between the pattern convex portions. May remain. The residue of the spacer material remaining between the pattern protrusions was melted by the baking process, and the dielectric layer exposed surface, which should be a uniform smooth surface, was deteriorated to a rough surface. On the other hand, when a combustible intermediate layer is provided between the unfired dielectric layer and the spacer material layer, a soot of spacer material is formed on the surface of the combustible intermediate layer, When the combustible intermediate layer is water-soluble, the spacer material residue is washed away together with the exposed combustible intermediate layer by the developer (water or aqueous solution). Further, when the combustible intermediate layer is water-swellable, it is swollen by the developer, the spacer material residue existing on the surface thereof is lifted, and is easily carried away by the developer.

  The spacer material residue as described above can be removed by the developer, and the combustible intermediate layer that has finished its role is completely burned out by the firing treatment of the unfired dielectric layer and the unfired spacer material layer. . As a result, a dielectric layer and a spacer layer having the same configuration and dimensions as the conventional one are formed on the glass substrate of the front plate. The difference between the obtained front plate and the conventional front plate is that the exposed surface of the dielectric layer between the spacer layer and the adjacent spacer layer has been manufactured according to the present invention as compared with the conventional method in which unevenness was present. In the face plate, the exposed surface is smooth. This is a particularly remarkable effect obtained by providing a water-soluble or water-swellable combustible intermediate layer between the unfired dielectric layer and the spacer material layer.

  The combustible intermediate layer 14 is water-soluble or water-swellable, and is not particularly limited as long as it is decomposed and burnt down by baking at 400 to 700 ° C. At least a water-soluble resin and a water-swellable resin are not limited. It is preferable to consist of one type. The combustible intermediate layer is preferably formed using a combustible intermediate layer composition containing at least one of a water-soluble resin and a water-swellable resin and a solvent.

  As the water-soluble resin, polyvinyl alcohol, polyvinyl alcohol derivatives, water-soluble cellulose and the like can be preferably used. In addition, as the water-swellable resin, a partially crosslinked water-soluble resin can be used. You may use these individually or in mixture of 2 or more types.

  Specific examples of the polyvinyl alcohol derivative include silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, mercapto group-containing polyvinyl alcohol, and butyral resin.

  Specific examples of the water-soluble cellulose include carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl ethyl cellulose, hydroxypropyl methyl cellulose and the like.

  Among these, polyvinyl alcohol and hydroxymethyl cellulose are preferable from the viewpoint of water solubility, thermal decomposability, and solvent resistance (resistance to the solvent of the dielectric layer).

As a solvent used to form the combustible intermediate layer, the water-soluble resin or water-swellable resin has good solubility, can give a viscosity suitable for coating, and easily evaporates when dried. If it can remove, it will not specifically limit, Organic solvents, such as water and isopropyl alcohol, can be used.

  The combustible intermediate layer is prepared by diluting the water-soluble resin or water-swellable resin with a solvent to a concentration suitable for coating, forming a coating film using the composition, and drying to remove the solvent. Can be formed.

  The ratio of the water-soluble resin or the water-swellable resin in the combustible intermediate layer composition for forming the combustible intermediate layer is preferably 50% by weight or less, more preferably 30% by weight or less, and 0.1 to 20 Most preferred is% by weight or less.

  The thickness of the combustible intermediate layer is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. If the combustible intermediate layer is too thick, the pattern of the photosensitive unexposed unfired spacer material layer is caused to flow in a later development step, which is not preferable. The optimum film thickness of the combustible intermediate layer is 0.1 to 3 μm.

(D) Manufacturing method of sheet-shaped green body As support film 180 used for manufacturing the sheet-shaped green body of the present invention, each layer formed on the support film can be easily peeled off from the support film. Any release film can be used as long as the green layer can be transferred onto a glass substrate. For example, the film may be made of a synthetic resin film such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl chloride having a film thickness of 15 to 125 μm. A flexible film is mentioned. It is preferable that the support film is subjected to a release treatment as necessary so that transfer is easy.

  In forming the spacer material layer 16A, the combustible intermediate layer 14, and the unfired dielectric layer 12A on the support film, the composition for forming each layer is adjusted, and an applicator, bar coater, Apply to the support film using a wire bar coater, slit coater, curtain flow coater or the like. In particular, a roll coater is preferable because it is excellent in film thickness uniformity and a film having a large thickness can be formed efficiently. After the coating film is dried, each layer is laminated by applying a composition for forming the next layer on the dried coating film, and the sheet-like green body of the present invention is produced. To do.

  A protective film 182 is preferably attached to the surface opposite to the support film 180 in order to stably protect the photosensitive paste composition layer and the like when not in use. As the protective film, a polyethylene terephthalate film, a polypropylene film, a polyethylene film or the like having a thickness of about 15 to 125 μm coated or baked with silicone is suitable.

[C] Method for Producing Plasma Display Front Plate A method for producing a plasma display front plate of the present invention comprises laminating an unfired dielectric layer and a spacer material layer in order from the lower layer on the electrode forming surface of the glass substrate, The spacer material layer is irradiated with pattern light and developed to pattern the spacer material layer, and the unfired dielectric layer on the glass substrate and the patterned spacer material layer are simultaneously fired to obtain a glass substrate. The dielectric layer and the spacer layer are simultaneously formed thereon.

  In the present invention, a water-soluble or water-swellable combustible intermediate layer may optionally be provided between the unfired dielectric layer and the spacer material layer. A material layer that can be dissolved and removed or swelled by developing water or an aqueous solution for obtaining a spacer layer and burnt out by a firing treatment is used as an intermediate layer between the unfired dielectric layer and the spacer material layer formed thereon. The spacer material residue remaining in the recesses between the patterns can be removed before the baking process by performing the processes after the exposure process in the same manner as before, and the intermediate process is performed by the baking process. Since the layer is burned out and no longer exists, the laminated structure after firing is the same as the conventional one, which is preferable.

(A) Formation of each layer on glass substrate The method for laminating the unfired dielectric layer and the spacer material layer on the glass substrate is not particularly limited. For example, known methods such as a coating method and a screen printing method are known. It is possible to laminate each layer using the method described above. However, from the viewpoint that a layer having good film thickness uniformity and surface smoothness can be formed, a method of forming each layer using the above-described sheet-like green body of the present invention is most preferable.

  The process of manufacturing a plasma display front plate using the sheet-shaped green body of the present invention will be described. First, a sheet-like green body is prepared in which a support film, a spacer material layer, and a protective film are laminated in this order.

  In addition, an unfired dielectric layer is formed separately on the electrode formation surface of the glass substrate. The method for forming the unfired dielectric layer is not particularly limited, but the unfired dielectric layer is formed by applying and drying the non-photosensitive inorganic paste composition on the support film, and if necessary, by coating and drying. A glass is formed by forming a combustible intermediate layer, laminating the unfired dielectric layer on the glass substrate so as to contact the electrode mounting surface of the glass substrate, and moving a heating roller on the support film. It is preferred to transfer the unfired dielectric layer onto the substrate.

  Next, the protective film of the sheet-like green body is peeled off, the exposed spacer material layer is overlaid on the green dielectric layer, and the heating roller is moved from above the support film, so that the spacer material layer is unfired dielectric layer. It is thermocompression bonded to the surface of the body layer.

The thermocompression bonding is preferably performed by heating the surface temperature of the glass substrate 10 to 80 to 140 ° C., with a roll pressure of 1 to 5 kg / cm ² and a moving speed of 0.1 to 10.0 m / min. The glass substrate may be preheated, and the preheat temperature is selected, for example, in the range of 40 to 120 ° C.

  Next, the case where a plasma display front plate is manufactured using the following sheet-shaped green body will be described. First, a sheet-like unfired body in which a support film, a spacer material layer, an unfired dielectric layer, and a protective film are laminated in this order is prepared. The protective film of the sheet-like green body is peeled off from the electrode mounting surface of the glass substrate, the green dielectric layer is overlaid, and the heating roller is moved from the support film, whereby the green dielectric layer and the spacer material The layer is heat bonded onto the glass substrate.

  The case where a plasma display front plate is manufactured using the following sheet-shaped green body will be described. First, a sheet-like unfired body in which a support film, a spacer material layer, a combustible intermediate layer, and a protective film are laminated in this order is prepared. Further, an unfired dielectric layer is separately formed on the electrode formation surface of the glass substrate. The protective film of the sheet-like green body is peeled to expose the combustible intermediate layer, and this exposed combustible intermediate layer is overlaid on the green dielectric layer formed on the electrode mounting surface of the glass substrate. In addition, the heating roller is moved from above the support film, and the combustible intermediate layer and the spacer material layer are heated and bonded to the surface of the glass substrate.

  The case where a plasma display front plate is manufactured using the following sheet-shaped green body will be described with reference to FIGS. First, a sheet-like unfired body in which the support film 180, the spacer material layer 16A, the combustible intermediate layer 14, the unfired dielectric layer 12A, and the protective film 182 are laminated in this order is manufactured (FIG. 8-1). The sheet-like green body protective film 182 is peeled off to expose the green body dielectric layer 12A, and this green body dielectric layer 12A is overlaid on the electrode 11 installation surface of the glass substrate 10 so that the support film 180 is covered. The heating roller 40 is moved, and the unfired dielectric layer 12A and the combustible intermediate layer 14 are heated and bonded to the surface of the glass substrate (FIG. 8-2).

(B) Exposure / development process The processes after the exposure process can be performed as usual. The exposure / development process will be described with reference to FIGS. After the unfired dielectric layer 12A and the spacer material layer 16A are formed on the glass substrate by the above-described method, the spacer material layer in the pattern portion is cured by exposing the spacer material layer 16A together with the photomask 3 (Fig. 4-1).

In the present invention, since the Norrish type I photopolymerization initiator and the hydrogen abstraction type photopolymerization initiator are used in combination, the influence of oxygen damage can be suppressed. For this reason, at the time of exposure, even if the surface of the spacer material layer 16A is not covered with a transparent film, the surface can be cured. However, if dust or the like adheres to the surface of the spacer material layer 16A due to static electricity, the quality deteriorates. Therefore, when a transparent film is used as the support film 180 in the sheet-like green body of the present invention, each layer is placed on the glass substrate. After the formation, it is preferable to expose the support film 180 on the spacer material layer 16A, and to expose the support film 180 after the exposure is completed.

  As a radiation irradiation apparatus used in exposure, an ultraviolet irradiation apparatus generally used in a photolithography method, an exposure apparatus used in manufacturing a semiconductor and a liquid crystal display device, or the like can be used.

  Next, the uncured portion 16A of the photosensitive unexposed unfired spacer material layer is removed by development to reveal the resist pattern 16A ′ (see FIG. 4-2).

  In the above development processing, a general-purpose alkali developer or water is used, and alkali components of the alkali developer include alkali metal hydroxides such as lithium, sodium, and potassium, carbonates, bicarbonates, phosphates, pyrrolines. Acid salts, primary amines such as benzylamine and butylamine, secondary amines such as dimethylamine, dibenzylamine and diethanolamine, tertiary amines such as trimethylamine, triethylamine and triethanolamine, morphophorin, piperazine and pyridine Polyamines such as cyclic amine, ethylenediamine, hexamethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylbenzylammonium hydroxide Examples include ammonium hydroxides, trimethylsulfonium hydroxides, trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, dimethylbenzylsulfonium hydroxide, and other sulfonium hydroxides, choline, silicate-containing buffers, etc. In view of damage due to the alkali component, water is preferable.

By using a combination of a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator, the cross-sectional shape of the resulting pattern is almost rectangular as shown in FIG. 7-1 or as shown in FIG. In addition, the bottom width Wbtm can be a trapezoid that is slightly narrower than the top width Wtop of the pattern. For this reason, it is possible to prevent the dielectric layer from being deformed or cracked during the firing process.

(C) Firing By firing the laminate on which the pattern is formed, the glass frit contained in the unfired dielectric layer 12A and the photosensitive unexposed unfired spacer material layer 16A ′ is sintered, and the dielectric layers 12, The spacer layer 16 is formed. As a result, the plasma display front plate of the present invention in which the spacer layer 16 is patterned on the dielectric layer 12 is obtained (see FIG. 4-3).

  The temperature used for the firing may be a temperature at which the organic substance in the photosensitive inorganic paste composition is burned out and the inorganic powder is sintered, and is fired at 400 to 700 ° C. for 10 to 90 minutes. Can be selected.

In order to prevent sagging of the pattern side wall during the firing process, when the softening point of the inorganic powder contained in the spacer material layer is made higher than the softening point of the inorganic powder contained in the unfired dielectric layer, the firing temperature is set to The softening point T ₁ (° C.) or less of the inorganic powder contained in the material layer and the softening point T ₂ (° C.) (T ₂ <T ₁ ) or more of the inorganic powder contained in the unfired dielectric layer are preferred. In particular, it is preferable to fire at a firing temperature slightly lower than the softening point T _{1 of the} inorganic powder contained in the spacer material layer. Preferred firing temperatures are T ₂ ° C or higher and T ₁ ° C or lower, more preferably (T ₁ -5) ° C or higher and T ₁ ° C or lower, more preferably (T ₁ -7) ° C or higher and T ₁ ° C or lower, Particularly, (T ₁ -10) ° C. is preferable.

  In this way, a dielectric layer is formed on a glass substrate having an electrode formed on the surface, and a plasma display front plate having a spacer layer patterned on the dielectric layer is manufactured and then exposed to the surface. The dielectric layer and the spacer layer are preferably covered with a protective film 19 such as MgO.

  Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not limited to the following Example.

<Experimental example 1>
(Preparation of photosensitive inorganic paste composition)
22 parts by weight of hydroxypropylcellulose as a water-soluble cellulose derivative, 14 parts by weight of a styrene / hydroxyethyl methacrylate = 55/45 (wt%) copolymer (Mw = 40000) as an acrylic resin having a hydroxy group, a photopolymerizable monomer 2-methacryloyloxyethyl-2-hydroxypropyl phthalate (trade name HO-MPP, manufactured by Kyoeisha Chemical Co., Ltd.) 60 parts by weight, photopolymerization initiator 2,2-dimethoxy-2-phenylacetophenone (trade name IR -651, manufactured by Ciba Geigy Corp., Norrish type I) 0.9 parts by weight and 2,4-diethylthioxanthone (trade name DETX-S, manufactured by Nippon Kayaku Co., Ltd., hydrogen extraction type) 1.8 parts by weight, butyl tartrate as a plasticizer 3.9 parts by weight, azo dye (trade name dye SS, Daito as UV absorber) 3 hours was prepared by mixing the organic component liquid mix Co., Ltd.) and 0.1 part by weight of a solvent as 3-methoxy-3-methyl butanol 100 parts by weight of agitator. Next, a photosensitive inorganic paste composition was prepared by kneading 40 parts by weight of the organic component liquid (solid content 50%) and 80 parts by weight of glass frit having a softening point of 581 ° C. as an inorganic component.

<Experimental example 2>
(Preparation of non-photosensitive inorganic paste composition)
45 parts by weight of isobutyl methacrylate / hydroxyethyl methacrylate = 60/40 (wt%) copolymer (Mw = 70,000) as an acrylic resin having a hydroxy group, 5 parts by weight of dibutyl phthalate as a plasticizer, and 3-methoxy- as a solvent An organic component liquid was prepared by stirring 50 parts by weight of 3-methylbutanol with a stirrer with a water bath at 80 ° C. for 2 hours. Next, the organic component liquid was kneaded with 40 parts by weight (solid content 50%) and 80 parts by weight of a glass frit having a softening point of 574 ° C. to prepare a non-photosensitive inorganic paste composition.

<Experimental example 3>
(Preparation of combustible intermediate layer forming composition)
A penetration preventing layer composition was prepared by mixing 4 parts by weight of polyvinyl alcohol (trade name PVA-235, manufactured by Kuraray Co., Ltd.), 53 parts by weight of water and 43 parts by weight of isopropyl alcohol as a solvent with a stirrer for 12 hours.

<Example 1>
After coating the non-photosensitive inorganic paste composition of Experimental Example 2 onto a support film made of polyethylene terephthalate so that the film thickness after drying was 60 μm, a coating film was formed. The preheated glass was laminated at a laminating temperature of 100 ° C., a laminating pressure of 2.5 kg / cm ² , and a laminating speed of 1.0 m / min to form an unfired dielectric layer.

Next, the photosensitive inorganic paste composition prepared above was applied onto the unfired dielectric layer so that the film thickness after drying was 40 μm, and then 400 mJ / mm by an ultrahigh pressure mercury lamp through a test angle pattern mask. Ultraviolet exposure was performed with a dose of cm ² . Subsequently, spray development was performed for 30 seconds at a spraying pressure of 3.0 kg / cm ² using water at a liquid temperature of 30 ° C. to form a pattern. When the adhesiveness of the obtained pattern was evaluated, the remaining minimum line width was 60 μm, and the formed minimum space was 60 μm. The cross-sectional shape of the obtained pattern was a trapezoid in which the bottom width Wbtm was narrower than the top width Wtop, and Wtop: Wbtm was 1: 0.9.

  In addition, in order to evaluate the shape stability after firing the pattern, a pattern having a mask line width of 200 μm is prepared by the above method, heated at a heating rate of 10 ° C./min, and held at 580 ° C. for 30 minutes. As a result, a good firing pattern was maintained. The cross-sectional shape of the pattern after firing was a rectangular shape with Wtop: Wbtm of approximately 1: 1.

<Example 2>
The non-photosensitive inorganic paste composition of Experimental Example 2 was applied using a lip coater on a support film made of release polyethylene terephthalate (trade name: Pureex A24, manufactured by Teijin DuPont Films Ltd.) The solvent was completely removed by drying at 100 ° C. for 6 minutes, and an unfired dielectric layer having a thickness of 60 μm was formed on the support film.
Next, the combustible intermediate layer forming composition of Experimental Example 3 was applied onto the unfired dielectric layer formed on the support film using a lip coater, and the coating film was dried at 100 ° C. for 6 minutes to obtain a solvent. Was completely removed and a 0.5 μm thick combustible intermediate layer was formed on the unfired dielectric layer.
The photosensitive inorganic paste composition of Experimental Example 1 was applied onto the combustible intermediate layer formed on the support film using a lip coater, and the coating film was dried at 100 ° C. for 6 minutes to remove the solvent. Completely removed, a photosensitive unexposed unfired spacer material layer having a thickness of 40 μm was formed. Next, a protective film made of release polyethylene terephthalate (trade name Purex A53, manufactured by Teijin DuPont Films Ltd.) is laminated on the photosensitive unexposed unfired spacer material layer to form a water-developable photosensitive film having a five-layer structure. Manufactured.

While peeling off the release polyethylene terephthalate (trade name Purex A24, manufactured by Teijin DuPont Films Ltd.), which is a support film for the water-developable photosensitive film prepared above, The formed glass substrate was laminated at 105 ° C. by a hot roll laminator. The air pressure was 3 kg / cm ² and the laminating speed was 1.0 m / min.
The photosensitive film layer was exposed to ultraviolet rays at a dose of 300 mJ / cm ² with a long high pressure mercury lamp through a test angle pattern mask. Subsequently, after the polyethylene terephthalate of the protective film was peeled off, a pattern was formed by spray development for 30 seconds at a spraying pressure of 3 kg / cm ² using water at a liquid temperature of 30 ° C. When the adhesion and pattern shape of the obtained pattern were evaluated, the remaining minimum line width was 60 μm, the formed minimum space was 60 μm, and a good pattern shape was obtained. The cross-sectional shape of the obtained pattern was a trapezoid in which the bottom width Wbtm was narrower than the top width Wtop, and Wtop: Wbtm was 1: 0.9.
In addition, in order to evaluate the shape stability after firing the pattern, a pattern having a mask line width of 200 μm is created by the above method, and the firing process is performed by heating at a heating rate of 10 ° C./min and holding at 580 ° C. for 30 minutes. As a result, a good firing pattern was maintained. The cross-sectional shape of the pattern after firing was a rectangular shape with Wtop: Wbtm of approximately 1: 1.

<Example 3>
After coating the combustible intermediate layer forming composition of Experimental Example 3 on a support film made of polyethylene terephthalate so that the film thickness after drying was 0.5 μm, a coating film was formed, followed by drying at 100 ° C. for 6 minutes. The solvent was removed to form a combustible intermediate layer. Further, on the combustible intermediate layer, the non-photosensitive inorganic paste composition of Experimental Example 2 was applied and dried so that the film thickness after drying was 60 μm to form a coating film. An unfired dielectric layer formed on a glass preheated to 80 ° C. at a laminating temperature of 100 ° C., a laminating pressure of 2.5 kg / cm ² , a laminating speed of 1.0 m / min, and a combustible intermediate layer formed on the top. Formed. Subsequently, the support film was peeled off.

Next, the photosensitive inorganic paste composition prepared above was applied onto the unfired dielectric layer so that the film thickness after drying was 40 μm, and then 400 mJ / mm by an ultrahigh pressure mercury lamp through a test angle pattern mask. Ultraviolet exposure was performed with a dose of cm ² . Subsequently, spray development was performed for 30 seconds at a spraying pressure of 3.0 kg / cm ² using water at a liquid temperature of 30 ° C. to form a pattern. When the adhesiveness of the obtained pattern was evaluated, the remaining minimum line width was 60 μm, and the formed minimum space was 60 μm. The cross-sectional shape of the obtained pattern was a trapezoid in which the bottom width Wbtm was narrower than the top width Wtop, and Wtop: Wbtm was 1: 0.9.

  In addition, in order to evaluate the shape stability after firing the pattern, a pattern having a mask line width of 200 μm is prepared by the above method, heated at a heating rate of 10 ° C./min, and held at 580 ° C. for 30 minutes. As a result, a good firing pattern was maintained. The cross-sectional shape of the pattern after firing was a rectangular shape with Wtop: Wbtm of approximately 1: 1.

<Comparative Example 1>
0.9 part by weight of Norrish type I 2,2-dimethoxy-2-phenylacetophenone (trade name: IR-651, manufactured by Ciba Geigy) was used alone as the photopolymerization initiator used in the photosensitive inorganic paste composition. Except that the photosensitive inorganic paste composition and the insulating sheet composition were prepared in the same manner as in Example 1 and the adhesion was evaluated in the same manner. The remaining minimum line width was 60 μm, but it was formed. The minimum space was 100 μm. The cross-sectional shape of the obtained pattern was a trapezoid having a bottom width Wbtm wider than the top width Wtop, and Wtop: Wbtm was 0.6 : 1 .

<Comparative example 2>
The above except that 1.8 parts by weight of hydrogen abstraction-type 2,4-diethylthioxanthone (trade name DETX-S, manufactured by Nippon Kayaku Co., Ltd.) was used alone as a photopolymerization initiator used in the photosensitive inorganic paste composition. When a photosensitive inorganic paste composition and an insulating sheet composition were prepared by the same method as in the Examples and spray development was performed for 30 seconds by the same method, the pattern flowed and the pattern could not be formed.

As described above, the photosensitive inorganic paste composition according to the present invention can obtain a good pattern shape by simultaneously combining a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator. As a material for producing various displays such as a plasma display and a plasma addressed liquid crystal display, it can be suitably used for producing a spacer material layer for a plasma display front plate requiring high precision.

It is an expanded view of the plasma display which has a waffle structure type cell. It is a perspective view of the back surface of a plasma display front plate. It is sectional drawing of the plasma display which has a waffle structure type cell. It is a figure which shows the manufacturing process (exposure process) of the plasma display front plate using the photolithographic method. It is a figure which shows the manufacturing process (development process) of the plasma display front plate using the photolithography method. It is a figure which shows the manufacturing process (baking process) of the plasma display front plate using the photolithographic method. It is sectional drawing which shows the pattern after the development obtained by the manufacturing method of the plasma display front board of a prior art. It is sectional drawing which shows the pattern after baking obtained by the manufacturing method of the plasma display front plate of a prior art. It is sectional drawing which shows the other pattern after baking obtained by the manufacturing method of the plasma display front board of a prior art. It is sectional drawing which shows the pattern after the development obtained by the manufacturing method of the plasma display front plate of this invention. It is sectional drawing which shows the other pattern after the development obtained by the manufacturing method of the plasma display front plate of this invention. It is a figure which shows the manufacturing process of the plasma display front board using the sheet-like unbaking body for plasma display front board manufacture. It is a figure which shows the manufacturing process of the plasma display front board using the sheet-like unbaking body for plasma display front board manufacture.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Front plate 10 Glass substrate 11 Electrode 110 Transparent electrode 112 Bus electrode 12 Dielectric layer 12A Unbaked dielectric layer 14 Burnable intermediate layer 16 Spacer layer 16A Spacer material layer 16A 'Resist pattern 18 Release film 180 Support film 182 Protection Film 19 Protective film 2 Back plate 20 Substrate 21 Address electrode 22 Dielectric layer 24 Rib 26 Phosphor layer 3 Photomask 40 Heating roller 42 Take-up roller

Claims (11)

Used to form spacers,
A photosensitive inorganic paste composition for spacer formation containing at least a photopolymerization initiator, a photopolymerizable monomer, and an inorganic powder,
As the photopolymerization initiator, simultaneously containing a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator,
The Norrish type I photopolymerization initiator is a benzyl ketal compound, and the hydrogen abstraction type photopolymerization initiator is a thioxanthone compound,
Ri wherein the inorganic powder is a glass frit der,
The Norrish type I photopolymerization initiator is 30 to 40 per 100 parts by weight of the total of the Norrish type I photopolymerization initiator and the hydrogen abstraction type photopolymerization initiator in the photosensitive inorganic paste composition for spacer formation. parts, the hydrogen abstraction-type photopolymerization initiator spacer formation photosensitive inorganic paste composition comprising 60 to 70 parts by weight der Rukoto. A dielectric plate is formed on a glass substrate having a large number of electrodes formed on the surface, and a plasma display front plate having at least a plurality of spacer layers of uniform thickness formed on the dielectric layer. A sheet-like green body,
A photosensitive film containing at least a photopolymerization initiator simultaneously containing a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator, a photopolymerizable monomer, and an inorganic powder on a release support film. Comprising at least an unfired spacer material layer,
The Norrish type I photopolymerization initiator is a benzyl ketal compound, and the hydrogen abstraction type photopolymerization initiator is a thioxanthone compound,
Ri wherein the inorganic powder is a glass frit der,
30 to 40 of the Norrish type I photopolymerization initiator is used for 100 parts by weight of the total of the Norrish type I photopolymerization initiator and the hydrogen abstraction type photopolymerization initiator in the photosensitive unexposed unfired spacer material layer. parts, the hydrogen extraction photopolymerization initiator and wherein 60 to 70 parts by weight der Rukoto plasma display front plate producing sheet-like green body. The sheet-like unfired body for producing a plasma display front plate according to claim 2 , further comprising an unfired dielectric layer containing at least an inorganic powder and a binder resin on the spacer material layer. The sheet-like uncoated sheet for plasma display front plate production according to claim 3 , wherein the softening point of the inorganic powder contained in the spacer material layer is higher than the softening point of the inorganic powder contained in the unfired dielectric layer. Fired body. 5. The plasma display according to claim 4 , wherein the softening point of the inorganic powder contained in the spacer material layer is 5 ° C. or more higher than the softening point of the inorganic powder contained in the unfired dielectric layer. Sheet-like green body for face plate production. The sheet-like green body for producing a plasma display front plate according to claim 2 , further comprising a water-soluble or water-swellable combustible intermediate layer on the spacer material layer. A plasma display front plate manufacturing method in which a dielectric layer is formed on a glass substrate on which a large number of electrodes are formed, and at least a plurality of spacer layers having a uniform thickness are formed on the dielectric layer. And
(A) On the electrode forming surface of the glass substrate,
An unsintered dielectric layer containing at least an inorganic powder and a binder resin, and
Photosensitive unexposed unfired spacer material comprising at least a photopolymerization initiator containing a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator, a photopolymerizable monomer, and an inorganic powder. Forming the layers in the stacking order;
(B) patterning the spacer material layer by irradiating and developing pattern light on the spacer material layer;
(C) simultaneously firing the unfired dielectric layer on the glass substrate and the patterned spacer material layer to form the dielectric layer and the spacer layer on the glass substrate simultaneously;
The Norrish type I photopolymerization initiator is a benzyl ketal compound, and the hydrogen abstraction type photopolymerization initiator is a thioxanthone compound,
Ri wherein the inorganic powder is a glass frit der contained in the spacer material layer,
30 to 40 of the Norrish type I photopolymerization initiator is used for 100 parts by weight of the total of the Norrish type I photopolymerization initiator and the hydrogen abstraction type photopolymerization initiator in the photosensitive unexposed unfired spacer material layer. parts, the manufacturing method of a plasma display front plate, wherein the hydrogen extraction photopolymerization initiator and wherein 60 to 70 parts by weight der Rukoto. 8. The plasma display according to claim 7 , wherein the softening point of the inorganic powder contained in the spacer material layer is 5 ° C. or more higher than the softening point of the inorganic powder contained in the unfired dielectric layer. Manufacturing method of face plate. In the step (c), the firing temperature is set to a temperature not lower than the softening point of the inorganic powder contained in the unfired dielectric layer and not higher than the softening point of the inorganic powder contained in the spacer material layer. A method for producing a plasma display front plate according to claim 8 . A plasma display front plate manufacturing method in which a dielectric layer is formed on a glass substrate on which a large number of electrodes are formed, and at least a plurality of spacer layers having a uniform thickness are formed on the dielectric layer. And
(A) On the electrode forming surface of the glass substrate,
An unsintered dielectric layer containing at least an inorganic powder and a binder resin, and
Photosensitive unexposed unfired spacer material comprising at least a photopolymerization initiator containing a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator, a photopolymerizable monomer, and an inorganic powder. Forming the layers in the stacking order;
(B) patterning the spacer material layer by irradiating and developing pattern light on the spacer material layer;
(C) simultaneously firing the unfired dielectric layer on the glass substrate and the patterned spacer material layer to form the dielectric layer and the spacer layer on the glass substrate simultaneously;
The Norrish type I photopolymerization initiator is a benzyl ketal compound, and the hydrogen abstraction type photopolymerization initiator is a thioxanthone compound,
Ri wherein the inorganic powder is a glass frit der contained in the spacer material layer,
30 to 40 of the Norrish type I photopolymerization initiator is used for 100 parts by weight of the total of the Norrish type I photopolymerization initiator and the hydrogen abstraction type photopolymerization initiator in the photosensitive unexposed unfired spacer material layer. parts, the hydrogen abstraction type photopolymerization initiator is a method for producing a plasma display front plate according to claim 60 to 70 parts by weight der Rukoto,
In the step (a), after forming an unfired dielectric layer on the glass substrate, the spacer material layer is formed of the sheet-like unfired body for manufacturing a plasma display front plate according to claim 2 or 6. A method of manufacturing a front panel of a plasma display, comprising stacking so as to be positioned on the unfired dielectric layer. A plasma display front plate manufacturing method in which a dielectric layer is formed on a glass substrate on which a large number of electrodes are formed, and at least a plurality of spacer layers having a uniform thickness are formed on the dielectric layer. And
(A) On the electrode forming surface of the glass substrate,
An unsintered dielectric layer containing at least an inorganic powder and a binder resin, and
Photosensitive unexposed unfired spacer material comprising at least a photopolymerization initiator containing a Norrish type I photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator, a photopolymerizable monomer, and an inorganic powder. Forming the layers in the stacking order;
(B) patterning the spacer material layer by irradiating and developing pattern light on the spacer material layer;
(C) simultaneously firing the unfired dielectric layer on the glass substrate and the patterned spacer material layer to form the dielectric layer and the spacer layer on the glass substrate simultaneously;
The Norrish type I photopolymerization initiator is a benzyl ketal compound, and the hydrogen abstraction type photopolymerization initiator is a thioxanthone compound,
Ri wherein the inorganic powder is a glass frit der contained in the spacer material layer,
30 to 40 of the Norrish type I photopolymerization initiator is used for 100 parts by weight of the total of the Norrish type I photopolymerization initiator and the hydrogen abstraction type photopolymerization initiator in the photosensitive unexposed unfired spacer material layer. parts, the hydrogen abstraction type photopolymerization initiator is a method for producing a plasma display front plate according to claim 60 to 70 parts by weight der Rukoto,
In the step (a), the sheet-like green body for producing a plasma display front plate according to any one of claims 3 to 5 , wherein the green dielectric layer is positioned on the glass substrate. And a method of manufacturing a plasma display front plate.

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