KR20040010277A - Photosensitive glass paste composition and plasma display panel - Google Patents

Abstract

PURPOSE: To provide a photosensitive glass paste composition that gives a glass sintered compact having a high aspect ratio and excellence in shape uniformity, that is capable of perfectly decomposing and removing a binding resin by the calcining treatment conducted at a relatively low temperature condition(600°C or lower) and that is capable of forming a glass sintered compact by the simple process. CONSTITUTION: The photosensitive glass paste composition which contains (A) a glass powder, (B) a polyfunctional (meth)acrylate and (C) a photopolymerization initiator and of which the viscosity is 100,000-3,000,000 cp is obtained.

Description

Photosensitive Glass Paste Composition and Plasma Display Panel

The present invention relates to a photosensitive glass paste composition, and more particularly, to a photosensitive glass paste composition which can be preferably used for forming partition walls and the like of a plasma display panel.

Recently, a plasma display has attracted attention as a flat fluorescent display. 1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel (hereinafter also referred to as "PDP"). In the same figure, 1 and 2 are the glass substrates which oppose, 3 is a partition, and the cell is partitioned by the glass substrate 1, the glass substrate 2, and the partition 3. 4 is a transparent electrode fixed to the glass substrate 1, 5 is a bus electrode formed on the transparent electrode 4 for the purpose of lowering the resistance of the transparent electrode, 6 is an address electrode fixed to the glass substrate 2, 7 is The fluorescent material retained in the cell, 8 is a dielectric layer formed on the surface of the glass substrate 1 to cover the transparent electrode 4 and the bus electrode 5, and 9 is a portion of the glass substrate 2 to cover the address electrode 6. The dielectric layer 10 formed on the surface is a protective film made of, for example, magnesium oxide. The partition 3 is mainly formed from a glass sintered body, for example, 30-60 micrometers in width, and 100-150 micrometers in height.

As the formation method of the partition 3, the following methods are mainly mainly present.

(1) A paste-like composition (glass paste composition) containing a glass powder, a binder resin, and a solvent is produced, and the glass paste composition is applied to the surface of the glass substrate 1 by screen printing and dried several times. The method of forming a partition molding material film | membrane and then baking this partition molding material layer to remove an organic substance and to sinter glass powder (screen printing method).

(2) A paste-like composition (glass paste composition) containing a glass powder, a binder resin and a solvent is produced, and the glass paste composition is applied to the surface of the glass substrate 1 by screen printing or a blade coater or the like and dried. After forming a barrier rib forming material layer, applying a resist liquid thereon, transferring a dry film resist, exposing and developing, and then blasting the non-exposed part mainly by a blasting apparatus, and then remaining resist layer A method of forming a partition wall forming material layer by peeling, followed by firing the partition wall forming material layer to remove an organic substance and sintering the glass powder (sand blast method).

(3) A paste-like composition (photosensitive glass paste composition) containing a glass powder, a photosensitive resin and a solvent is produced, and the photosensitive glass paste composition is applied to the surface of the glass substrate 1 by screen printing or a blade coater or the like and dried. By forming the underlying photosensitive partition wall forming material film, exposing and developing the photosensitive partition wall forming material film to form a partition wall forming material layer, and subsequently firing the partition wall forming material layer to remove the organic material and sintering the glass powder. Method (photosensitive paste method).

(4) A paste-like composition (glass paste composition) containing a glass powder, a binder resin, and a solvent is produced, and the glass paste composition is applied to the surface of the glass substrate 1 by screen printing or a blade coater or the like and dried. Forming a partition wall forming material film, pressing the partition wall forming material film from above into a mold having a structure for forming a partition wall, and forming a partition wall forming material layer, and subsequently firing the partition wall forming material layer to form an organic material. Is removed to sinter the glass powder (press molding).

Here, as the binder resin constituting the glass paste composition, cellulose derivatives such as methyl cellulose, ethyl cellulose, and carboxymethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, urethane resin, melamine resin, and the like are known. Ethyl cellulose is said to be preferable from a viewpoint of the dispersibility of glass powder, the coating characteristic of a composition, the ease of combustion, etc. (for example, refer Unexamined-Japanese-Patent No. 6-321619).

In addition, the thickness of the barrier rib forming material layer formed on the glass substrate 1 is 1.3 to 2.0 times the thickness of the barrier rib 3 to be formed in consideration of the reduction of the film thickness due to the removal of the organic material in the firing process. In order to make the film thickness of the partition 3 into 100-150 micrometers, for example, it is necessary to form the partition formation material layer of about 130-300 micrometers in thickness.

On the other hand, when apply | coating the said glass paste composition by the screen printing method, the thickness of the coating film formed by one coating process is about 15-25 micrometers. For this reason, in order to make a partition formation material layer into a predetermined thickness, it is necessary to apply | coat repeatedly (multiprinting) the said glass paste composition to the surface of a glass substrate several times (for example, 10-20 times), Uniformity of the film thickness becomes difficult. The process is also grand.

Moreover, in the sand blasting method, the process lengthening by exposure, image development, blasting, etc., and generation | occurrence | production of the waste by a blast become a problem.

Moreover, also in the photosensitive paste method, an exposure and image development process are needed, and waste generation etc. become a problem.

In addition, in the press molding method, the process looks simple at first glance, but high precision management of the mold is required, and reliability is still low, such as the shape of the barrier rib forming material layer greatly affects the flatness of the glass substrate.

As a means to solve the above problems in forming the barrier rib forming material layer by the conventional method, the barrier rib is formed by UV curing while continuously extruding the photosensitive glass paste composition on the glass substrate by a special discharge nozzle. A manufacturing method of a PDP including a forming method (hereinafter referred to as a nozzle ejecting method) has been proposed.

In addition, according to the PDP manufacturing method including the nozzle ejection method, a partition having a high aspect ratio can be formed in a very simple process so as to be incomparable with the conventional method.

However, when the conventionally well-known photosensitive glass paste composition is applied to this nozzle discharge method, since the viscosity of a paste is low, shape changes, such as liquid flow of a paste, arise before UV hardening. Moreover, even if it uses a normal screen printing paste, since the viscosity is low and it is non-photosensitive, there existed a problem that shape retention by UV hardening after discharge from a nozzle cannot be performed.

In addition, from the standpoint of expressing good electrical characteristics in the partitions constituting the PDP, the partitions are required to have a high aspect ratio and shape uniformity.

Furthermore, a very simple process is required for the partition wall manufacturing method which comprises a PDP.

This invention is made | formed based on the above circumstances.

A first object of the present invention is to provide a photosensitive glass paste composition capable of forming a glass sintered body having a high aspect ratio.

A second object of the present invention is to provide a photosensitive glass paste composition capable of forming a glass sintered body having excellent shape uniformity.

A third object of the present invention is to completely decompose and remove the binder resin by firing treatment performed under relatively low temperature conditions (600 ° C. or lower), and to form a glass sintered body containing no organic substance derived therefrom. It is to provide a photosensitive glass paste composition.

A fourth object of the present invention is to provide a photosensitive glass paste composition capable of forming a glass sintered body which is suitable as a partition wall of a PDP.

A fifth object of the present invention is to provide a photosensitive glass paste composition capable of forming, for example, a partition of a PDP in a very simple process that has not been conventionally used.

1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel.

<Explanation of symbols for the main parts of the drawings>

1 glass substrate

2 glass substrates

3 bulkhead

4 transparent electrodes

5 bus electrode

6 address electrode

7 phosphor

8 Dielectric Layer

9 dielectric layer

10 Shield

The glass paste composition of this invention contains (A) glass powder, (B) polyfunctional (meth) acrylate, and (C) photoinitiator, using the cone rotational viscometer on 25 degreeC and 1 atmosphere conditions. The viscosity measured at 0.5 rpm of the cone is characterized in that the range of 100,000 to 3,000,000 cp.

<Action>

(1) By controlling the viscosity of the composition in a specific range, it is possible to form a glass sintered body (for example, PDP partition wall) having a high aspect ratio and excellent shape uniformity.

(2) By applying this composition to a nozzle discharge method, a glass sintered body (for example, a partition for PDP) can be formed by a very simple process that has not been obtained in the past.

Embodiments of the Invention

Hereinafter, the photosensitive glass paste composition of this invention is demonstrated in detail.

The photosensitive glass paste composition of this invention contains a glass powder, the polymer which has an unsaturated double bond, and (C) photoinitiator as an essential component, and is characterized by having a paste viscosity in the range of 100,000-3,000,000 cp.

If the composition has a viscosity of less than 100,000 cps, the liquid flow, planarization, or the like may occur between the paste and the exposure after the paste is discharged by the nozzle, and a high aspect ratio structure cannot be formed. Moreover, when paste viscosity exceeds 3,000,000 cp, handling property will fall, for example, the discharge property from a nozzle will worsen.

In the present invention, the viscosity is measured at 25 ° C. and 1 atm using a cone rotary viscometer RE-80U manufactured by AXAKYO CO., LTD. And using a rotor No. 7 at a cone rotation speed of 0.5 rpm. More preferably, the measured value when 1 minute has passed after the start of rotation using rotor No. 7 is defined as the viscosity of the composition. This is because the paste composition is often non-Newtonian.

<Glass powder>

As glass powder which comprises the composition of this invention, it is preferable that the softening point exists in the range of 400-600 degreeC.

In the case where the softening point of the glass powder is less than 400 ° C, the glass powder melts at a stage in which the organic material such as the binder resin is not completely decomposed and removed in the firing step of the barrier rib forming material layer by the composition. Part of the organic substance remains, and as a result, outgas is diffused into the panel, which may result in a reduction in the lifetime of the phosphor. On the other hand, when the softening point of glass powder exceeds 600 degreeC, since baking needs to be carried out at high temperature rather than 600 degreeC, distortion etc. are easy to generate | occur | produce in a glass substrate.

Specific examples of preferred glass powders include (1) lead oxide, boron oxide, silicon oxide and calcium oxide (PbO-B ₂ O ₃ -SiO ₂ -CaO-based) ② zinc oxide, boron oxide and silicon oxide (ZnO-B ₂ O ₃ -SiO _{2 type} ) ③ Lead oxide, boron oxide, silicon oxide, aluminum oxide (PbO-B ₂ O ₃ -SiO ₂ -Al ₂ O _{3 type} ) ④ Lead oxide, zinc oxide, boron oxide, silicon oxide (PbO-ZnO-B ₂ O ₃ -SiO ₂ ) ⑤ lead oxide, zinc oxide, boron oxide, silicon oxide, titanium oxide (PbO-ZnO-B ₂ O ₃ -SiO ₂ -TiO _{2 type} ) and the like can be exemplified. Moreover, you may mix and use inorganic oxide compound powders, such as aluminum oxide, chromium oxide, and manganese oxide, for these glass powders, for example.

<Multifunctional (meth) acrylate>

Multifunctional (meth) acrylates have a role as binding resin in the composition. As a specific example of the said (meth) acrylate, Di (meth) acrylates of alkylene glycols, such as ethylene glycol and propylene glycol: Di (meth) acrylates of polyalkylene glycols, such as polyethyleneglycol and polypropylene glycol; Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxy polybutadiene, both terminal hydroxy polyisoprene and both terminal hydroxy polycaprolactone; Poly (meth) acrylates of trivalent or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, dipentaerythritol; Poly (meth) acrylates of polyalkylene glycol adducts of trivalent or higher polyhydric alcohols; Poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediols; Oligos, such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spiran resin (meth) acrylate ( And meth) acrylates. These may be used alone or in combination of two or more thereof.

The content rate of the said polyfunctional (meth) acrylate is 10-50 weight part normally with respect to 100 weight part of glass powder, Preferably it is 20-40 weight part. If it is less than 10 parts by weight, the photosensitivity is insufficient and it is difficult to maintain a rib shape. If it exceeds 50 parts by weight, the viscosity characteristic of the paste is deteriorated, which tends to adversely affect the ejectability from the nozzle.

<Photoinitiator>

Specific examples of the photopolymerization initiator used in the present invention include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2, 2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 '-(methylthio) phenyl] -2-morpholino-1-propaneone, 2-benzyl-2-dimethylamino-1- (4 Carbonyl compounds such as -morpholinophenyl) -butan-1-one; Azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde; Organic peroxides such as organic sulfur compounds such as mercaptan disulfide, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and paramethane hydroperoxide; 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6-bis Trihalo methanes such as (trichloromethyl) -1,3,5-triazine; Imidazole dimers such as 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, and the like. It can be used in combination of 2 or more type.

The content rate of the said photoinitiator is 5-30 weight part normally with respect to 100 weight part of polyfunctional (meth) acrylates, Preferably it is 10-20 weight part. If it is less than 5 parts by weight, the photosensitivity is insufficient and it is difficult to maintain the rib shape. If it exceeds 30 parts by weight, the remaining initiator tends to adversely affect the firing.

The composition of the present invention contains, as an optional component, other binding resins, solvents, dispersants, tackifiers, surface tension regulators, stabilizers, plasticizers, adhesion aids, antihalation agents, storage stabilizers, antifoam agents, antioxidants, ultraviolet absorbers, fillers. And various additives such as phosphors, pigments, and dyes.

As the solvent optionally contained in the composition of the present invention, it is preferable that the affinity with the glass powder and the solubility of the binder resin are good, and the photosensitive glass paste composition can be easily evaporated and removed by drying and calcining while providing proper viscosity. . Moreover, ketones, alcohols, and esters (henceforth, these are called a "specific solvent") whose standard boiling point (boiling point in 1 atmosphere) are 100-200 degreeC as an especially preferable solvent are mentioned.

As a specific example of such a specific solvent, Ketones, such as a diethyl ketone, a methyl butyl ketone, a dipropyl ketone, cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetone alcohol; Ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Saturated aliphatic monocarboxylic acid alkyl esters such as acetic acid-n-butyl and amyl acetate; Lactic acid esters such as ethyl lactate and lactic acid-n-butyl; Ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and ethyl-3-ethoxypropionate, and the like can be exemplified. Diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, ethyl-3-ethoxypropionate, and the like are preferable. These specific solvents can be used individually or in combination of 2 or more types.

Specific examples of solvents other than the specific solvents include terebin oil, ethyl cellosolve, methyl cellosolve, terpineol, butyl carbitol acetate, butyl carbitol, isopropyl alcohol, benzyl alcohol, and the like.

As a content rate of the solvent in the composition of this invention, it is preferable that it is 50 weight part or less with respect to 100 weight part of glass powder from a viewpoint of maintaining the viscosity of a composition in a preferable range, More preferably, it is 10 weight part or less.

Moreover, it is preferable that the content rate of the specific solvent with respect to the total solvent is 50 weight% or more, More preferably, it is 70 weight% or more.

The composition of the present invention can be prepared by kneading the glass powder, the binder resin, the photopolymerization initiator and any component by using a kneader / disperser such as a roll kneader, a mixer, a homo mixer, a sand mill, a planetary stirring disperser, or the like. have.

The composition of the present invention produced as described above is a pasty composition having fluidity suitable for application.

The composition of the present invention can be particularly preferably used to form a partition wall forming material layer mainly by a nozzle ejection method as described above to produce a partition wall of a plasma display, and the like, but is not limited to such a use. It can also use suitably also for the formation method of the formed film forming material layer.

<Plasma display panel>

The plasma display panel of the present invention is characterized in that partition walls and the like are formed using the photosensitive glass paste composition of the present invention.

As an example of a partition formation method, the photosensitive glass paste composition of this invention is discharged on a board | substrate by the nozzle ejection method, and the method of baking after exposing and hardening continuously is mentioned.

As discharge conditions, discharge nozzles of 0.1 to 1 MPa and discharge speeds of 0.2 to 20 mm / sec are used, for example, using nozzles having dimensions substantially equal to the rib shape.

In addition, it does not specifically limit as a radiation irradiation apparatus used for exposure, For example, the exposure apparatus etc. which are used when manufacturing a semiconductor and a liquid crystal display device are used. In addition, as radiation used for exposure, an ultraviolet-ray etc. are used preferably, for example.

Moreover, as temperature of a baking process, it is necessary that it is the temperature which the organic substance in a composition vanishes, and is 400-600 degreeC normally. Moreover, baking time is 10 to 60 minutes normally.

The partition formed by the manufacturing method of this invention divides the horizontal direction of the display cell (display unit) of a panel generally. The magnitude | size of the horizontal pitch of the display cell divided by the partition is 0.10-1.00 mm, for example.

Dimensions, such as the cross-sectional shape, width, height of a partition, the space | interval of a partition, etc. can be suitably selected according to the characteristic of the target plasma display panel.

Specifically, the width of the bottom surface in the cross-sectional shape of the partition wall is 10 to 300 µm, the height is 10 to 500 µm, and the separation distance of the partition wall is 50 to 1000 µm, and the width of the electrode disposed between the partition walls is 50 to 500. [Mu] m. In a particularly typical example, the width of the bottom surface in the cross-sectional shape of the partition wall is 50 µm, the height is 150 µm, the separation distance of the partition wall is 300 µm, and the width of the electrode disposed between the partition walls is 100 µm.

Hereinafter, although the Example of this invention is described, this invention is not limited by these. (In addition, "part" shows a "weight part" below.

In addition, the evaluation method in an Example is as follows.

〔Viscosity〕

The viscosity of the photosensitive glass paste composition was measured using the cone rotational viscometer "RE-80U" (Tokyo Sangyo Co., Ltd. product). In addition, the rotor used rotor No. 7, the rotation speed of the cone was set to 0.5 rpm, and the measured value when 1 minute passed after the start of rotation was defined as the viscosity of the paste composition.

(Bulk wall shape)

The dimension and aspect ratio of the manufactured partition were calculated | required using the non-contact three-dimensional shape measuring apparatus "NH-3" (made by Ryo Co., Ltd.). In addition, the scanning electron microscope was used for the observation of a more detailed property.

<Example 1>

(1) Preparation of Photosensitive Glass Paste Composition:

As a glass powder, _{PbO-B 2 O 3 -SiO 2} -Al 2 O 3 -TiO 2 based glass powder 100 (DTA softening transition ℃ 460, manufactured by Asahi Glass Co., Ltd.) made of a, a mean particle diameter of 1.3 ㎛ unit By kneading 30 parts of polyepoxyacrylate (bisphenol A diglycidyl ether acrylic acid adduct) as a binder resin having an unsaturated double bond / 10 parts of 1-hydroxycyclohexyl-phenyl-ketone as a photopolymerization initiator by using a dispersing group To prepare a composition of the present invention, the viscosity is 600,000 cp.

(2) Formation of partition wall forming material layer:

Using the said composition, the partition molding material layer was produced on the glass substrate by the nozzle discharge method. That is, the composition was continuously discharged from a special nozzle, and cured by irradiating i-ray (ultraviolet light having a wavelength of 365 nm) from an ultra-high pressure mercury lamp. Here, the irradiation amount was 500 mJ / cm ² .

(3) Firing treatment of partition wall forming material layer and evaluation of partition wall:

The glass substrate in which the partition formation material layer manufactured by said (2) was formed is arrange | positioned in a baking furnace, the temperature in a baking furnace is heated up to 580 degreeC at the temperature increase rate of 10 degree-C / min from normal temperature, and it is 10 minutes in 580 degreeC temperature atmosphere. By baking over, the partition which consists of glass sintered compacts was formed in the surface of a glass substrate.

As a result of visual observation of the properties of the partition, no crack, peeling from the substrate, or the like was confirmed.

As a result of measuring the shape of the partition, it was found that an ideal structure having a high aspect ratio of 40 μm in width and 130 μm in height was formed. Moreover, the shape uniformity was excellent from the detailed measurement. The evaluation results are shown in Table 1 below.

<Examples 2 and 3 and Comparative Examples 1 and 2>

According to the prescription shown in Table 1, except having changed the composition ratio of glass powder, binder resin, and a photoinitiator, it carried out similarly to Example 1, and manufactured the photosensitive glass paste composition and comparative photosensitive glass paste composition of this invention.

Then, the partition molding material layer was produced like Example 1 except having used each of the obtained photosensitive glass paste compositions.

Then, the baking process of the partition molding material layer was performed like Example 1 except having used each of the obtained partition molding material layers, and the partition was manufactured on the glass substrate surface for 20 inch panels.

For each of the compositions according to Examples 2 and 3 and Comparative Examples 1 and 2, the handling properties such as the ejection from the nozzle were examined, the properties of the formed partition walls were observed, and the shape of the partition walls was measured.

The above results are shown in Table 1.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Furtherance Glass powder 100 100 100 100 100 Bound resin 30 28 32 40 25 Photoinitiator 10 10 10 10 10 Viscosity (cp) 600,000 1 million 400,000 50,000 4 million Handleability Good Good Good Slightly bad Extremely bad Bulkhead Good Good Good Slightly bad Slightly bad Bulkhead width (㎛) 40 30 50 100 30 Bulkhead height (㎛) 130 130 130 50 130 Aspect ratio height height height lowness height Shape uniformity Good Good Good Extremely bad Bad

According to the composition of the present invention, the following effects are exerted.

(1) By controlling the viscosity of the composition in a specific range, it is possible to form a glass sintered body (for example, PDP partition wall) having a high aspect ratio and excellent shape uniformity.

(2) By using this composition, the binder resin can be completely decomposed and removed by a calcination process performed under relatively low temperature conditions (600 ° C. or less), and a glass sintered body containing no organic substance derived therefrom can be formed. .

(3) By using this composition, the glass sintered compact suitable as a partition of PDP can be formed.

(4) By applying this composition to a nozzle ejection method, a glass sintered body (for example, a partition for PDP) can be formed by a very simple process that has not been conventionally obtained.

Claims (3)

(A) glass powder, (B) polyfunctional (meth) acrylate, and (C) photoinitiator, and the viscosity measured at the cone rotation speed of 0.5 rpm using the cone rotational viscometer on conditions of 25 degreeC and 1 atmosphere A photosensitive glass paste composition, characterized in that 100,000 to 3,000,000 cp. The photosensitive glass paste composition of Claim 1 used for forming a panel member by a nozzle discharge method. The panel member formed using the photosensitive glass paste composition of Claim 1 is provided, The plasma display panel characterized by the above-mentioned.