JP5280770B2 - Glass paste composition and method for producing plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass paste composition having an excellent sheet-attack resistance, an superior adhesiveness to a glass rib, and a superior sandblasting resistance, and allowing efficient manufacturing of a plasma display panel, and to provide a manufacturing method of a plasma display panel, using the glass paste composition. <P>SOLUTION: The glass paste composition is used to manufacture a plasma display and contains a (meth)acrylic copolymer, fine glass particles, and a high-boiling point solvent. The (meth)acrylic copolymer has, at a side-chain end thereof, a segment derived from a (meth)acrylate monomer having a hydroxyl group, and a glass transition temperature of -10&deg;C or lower. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a glass paste composition that is excellent in sheet attack resistance, adhesion to glass ribs, and sandblast resistance, and that can efficiently produce a plasma display panel. The present invention also relates to a method for producing a plasma display panel using the glass paste composition.

A plasma display panel (hereinafter also referred to as PDP) is an ultraviolet ray generated from a gas enclosed in a discharge space by causing plasma discharge between electrodes in a discharge space provided between the front glass substrate and the rear glass substrate. Is emitted to the phosphor in the discharge space.
On the rear glass substrate, a dielectric layer is formed on the electrode for the purpose of protecting the electrode from plasma, and a glass rib for coating the phosphor layer is formed on the surface. Further, in order to increase the surface area of the phosphor layer, the glass rib is formed into a concave stripe shape using sandblast. A substrate in which a dielectric layer and glass ribs are formed on the back glass substrate surface is called a back plate.

Conventionally, in the PDP production process, as disclosed in Patent Document 1, first, a dielectric layer paste having an ethyl cellulose resin as a binder is applied to the surface of a back glass substrate, dried, and then heated to degrease. The dielectric layer is formed by firing. Further, a low melting point glass is dispersed on the surface of the dielectric layer using acrylic resin, ethyl cellulose resin or the like as a binder resin, and a paste containing a solvent is applied and dried. Thereafter, a dry film resist (hereinafter also referred to as DFR) is laminated, exposed to light, developed with alkaline water, dried by heating, formed into a concave stripe shape using sandblast, and the DFR remaining on the ribs is then washed with alkaline water. The glass ribs were formed by washing and heating, degreasing and baking.
As the DFR used in such a production process, for example, as disclosed in Patent Document 2, a DFR having sandblast resistance is used.

However, in the conventional PDP production process, since the adhesion between the glass rib and the DFR is low, when processing a thin glass rib, the DFR is easily peeled off from the tip of the glass rib during sandblasting, and it is difficult to process the thin rib. There was a problem.
In addition, such a method requires steps such as DFR exposure, development, removal, and drying, and has a problem in that the back plate manufacturing efficiency is very poor. Furthermore, as a process of removing DFR, a combustion process or an alkali cleaning process is required, resulting in an increase in the manufacturing cost of the back plate and a decrease in manufacturing efficiency.
JP-A-11-349348 JP 2004-126073 A

An object of this invention is to provide the glass paste composition which is excellent in sheet attack resistance, adhesiveness with a glass rib, and sandblasting resistance, and can manufacture a plasma display panel efficiently in view of the said present condition. Moreover, it aims at providing the manufacturing method of the plasma display panel which uses this glass paste composition.

The present invention is a glass paste composition used for the production of a plasma display, comprising an acrylic polymer or a methacrylic polymer , glass fine particles and a high-boiling solvent, wherein the acrylic polymer or the methacrylic polymer has side chain terminals. Segment derived from an acrylate monomer having a hydroxyl group or a methacrylate monomer having a hydroxyl group at the side chain end, and a segment derived from an acrylate monomer having a hydroxyl group at the side chain end or a methacrylate monomer having a hydroxyl group at the side chain end A glass paste composition having a content of 70 to 100% by weight and a glass transition temperature of −10 ° C. or lower.
The present invention is described in detail below.

As a result of intensive studies, the inventors of the present invention performed screen printing on a glass rib layer after drying a glass paste composition instead of DFR in a conventional method of performing exposure, development, etc. after laminating DFR, As a result, it is possible not only to omit the step of exposing and developing the resist to form a pattern and the step of removing the resist after sandblasting, but also to sinter the glass paste composition while leaving it on the glass rib layer. Thus, it has been found that it can be formed as a part of the glass rib layer, and the manufacturing process can be greatly simplified.
However, when the conventional glass paste composition is used in such a method, there has been a problem that a sheet attack occurs in the glass rib layer and a problem that the portion of the glass paste composition is cut in the sandblasting process.

Therefore, as a result of further intensive studies, the inventors of the present invention contain a (meth) acrylic (co) polymer having a segment derived from a (meth) acrylate monomer having a hydroxyl group at the side chain end, a high boiling point solvent, and glass fine particles. By using the glass paste composition to be used as a resist material and keeping the glass transition temperature of the (meth) acrylic (co) polymer within a predetermined range, a sheet attack may occur during printing or it may be cut in a sandblasting process. The present inventors have found that a glass paste composition can be obtained in which the layer made of the glass paste composition does not peel off, and the present invention has been completed.

The glass paste composition of the present invention contains a (meth) acrylic (co) polymer having a segment derived from a (meth) acrylate monomer having a hydroxyl group at a side chain end.
In this invention, the hydroxyl group density of the said (meth) acrylic (co) polymer is raised by having the segment derived from the (meth) acrylate monomer which has a hydroxyl group at the said side chain terminal, and between the surfaces of a glass microparticle It exhibits a strong interaction and can form a high-strength film after solvent drying. As a result, the sandblast resistance, the adhesion to the glass rib, and the sheet attack resistance are also excellent.
In addition, (meth) acrylate in this invention means an acrylate or a methacrylate.

As the (meth) acrylate monomer having a hydroxyl group at the end of the side chain, at least one selected from the group consisting of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate is preferably used. By using a (meth) acrylate monomer having a hydroxyl group at the end of the side chain in such a combination, the hydroxyl density of the (meth) acrylic (co) polymer is increased, and the adhesion to the glass fine particles can be enhanced. Moreover, the glass transition temperature of the obtained (meth) acrylic (co) polymer can be suppressed to −10 ° C. or lower, and the glass paste composition of the present invention can be dispersed in glass fine particles, sandblasted, and applied to the glass rib layer. Adhesiveness is excellent.

Among the (meth) acrylate monomers having a hydroxyl group at the end of the side chain, the glass transition temperature of the resulting (meth) acrylic (co) polymer is lower, and the adhesiveness to the glass rib layer is improved. It is preferable to use 4-hydroxybutyl acrylate from the viewpoint of having a high boiling point organic solvent.

The minimum with preferable content of the segment derived from the (meth) acrylate monomer which has a hydroxyl group in the said side chain terminal in the said (meth) acrylic (co) polymer is 70 weight%, and a preferable upper limit is 100 weight%. When the content of the segment derived from the (meth) acrylate monomer having a hydroxyl group at the side chain terminal is less than 70% by weight, the strength of the film obtained using the glass paste composition of the present invention becomes insufficient.

The upper limit of the glass transition temperature (Tg) of the (meth) acrylic (co) polymer is −10 ° C.
When a glass paste composition is used instead of DFR, a segment derived from a (meth) acrylate monomer having a hydroxyl group at the side chain end in the (meth) acrylic (co) polymer, for example, 2-hydroxyethyl (meth) The resin containing the acrylate segment has good sandblast resistance, but has a problem that the glass paste composition layer is partially peeled from the glass rib layer in the sintering step after sandblasting. As a result, stress was concentrated on the interface due to the difference in linear expansion coefficient with the glass rib layer due to heating during sintering. On the other hand, by setting the glass transition temperature of the (meth) acrylic (co) polymer to −10 ° C. or less, the stress at the coating interface can be relaxed and strong adhesion to the glass rib layer can be achieved. For example, it has become possible to improve the yield in the manufacture of the back plate.
When the glass transition temperature exceeds −10 ° C., the adhesiveness with the glass rib layer is lowered, and thus the glass paste composition is peeled in the step of printing and drying the glass paste composition on the glass rib layer. A preferable upper limit of the glass transition temperature is −20 ° C. Moreover, the minimum with said preferable glass transition temperature is -100 degreeC. If the glass transition temperature is less than −100 ° C., problems may occur during sandblasting. In addition, since a large amount of (meth) acrylic (co) polymer is required to obtain a viscosity that allows coating, time may be required for degreasing and firing.

The (meth) acrylic (co) polymer has segments derived from other copolymerizable (meth) acrylate monomers in addition to segments derived from (meth) acrylate monomers having a hydroxyl group at the side chain end. It may be.
Examples of other copolymerizable (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and glycidyl. (Meth) acrylate, (meth) acrylic acid, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, and the like. Of these, alkyl (meth) acrylate monomers having 10 or less carbon atoms are preferred because of their excellent decomposability.

The preferred lower limit of the content of the segment derived from the other (meth) acrylate monomer in the (meth) acrylic (co) polymer is 5% by weight, and the preferred upper limit is 30% by weight. When the content of the segment derived from the other (meth) acrylate monomer is less than 5% by weight, the effect of including the segment derived from the other (meth) acrylate monomer is insufficient, and the other (meta) ) If the content of the segment derived from the acrylate monomer exceeds 30% by weight, the strength of the film obtained using the glass paste composition of the present invention becomes insufficient.

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the (meth) acrylic (co) polymer depends on the glass transition temperature of the (meth) acrylic (co) polymer, A preferable lower limit is 5000, and a preferable upper limit is 200,000. If the weight average molecular weight is less than 5,000, sufficient viscosity cannot be obtained in the glass paste composition of the present invention. If the weight average molecular weight exceeds 200,000, stringiness and the like are deteriorated, and handling properties during printing are deteriorated. May be extremely bad. In a (meth) acrylic (co) polymer having a glass transition temperature higher than room temperature, a more preferable upper limit of the weight average molecular weight is 100,000.
In addition, the measurement of the number average molecular weight by polystyrene conversion can be obtained by performing GPC measurement using, for example, a column LF-804 manufactured by SHOKO as a column.

Although it does not specifically limit as content of the said (meth) acrylic (co) polymer in the glass paste composition of this invention, A preferable minimum is 5 weight% and a preferable upper limit is 45 weight%. If the content of the (meth) acrylic (co) polymer is less than 5% by weight, the fine glass particles may not be sufficiently dispersed, which may cause problems in printability. When the content of the (co) polymer exceeds 45% by weight, the thermal decomposability may be adversely affected.

The polymerization method of the (meth) acrylic (co) polymer is not particularly limited, and examples thereof include methods used for polymerization of ordinary (meth) acrylate monomers. For example, free radical polymerization method, living radical polymerization method, ini Examples include a furter polymerization method, an anionic polymerization method, and a living anion polymerization method.

The glass paste composition of the present invention contains glass fine particles.
It is not particularly restricted but the composition of the glass powder, for example, silicate glass, lead glass, zinc glass, boron _{glass, CaO-Al 2 O 3 -SiO} 2 type inorganic _{glass, MgO-Al 2 O 3 -SiO} 2 Examples of the glass include various inorganic glasses and LiO ₂ —Al ₂ O ₃ —SiO ₂ inorganic glasses. In particular, a low melting point glass having a melting point of 600 ° C. or lower is preferable.

Further, inorganic fine particles other than glass may be used in combination with the glass fine particles.
The inorganic fine particles are not particularly limited. For example, copper, silver, nickel, palladium, alumina, zirconia, titanium oxide, barium titanate, alumina nitride, silicon nitride, boron nitride, BaMgAl ₁₀ O ₁₇ : Eu, Zn ₂ SiO ₄ : Phosphor such as Mn, (Y, Gd) BO ₃ : Eu, carbon black, coloring fine particles such as dyes and pigments, metal complexes, and the like.

The content of the glass fine particles and inorganic fine particles in the glass paste composition of the present invention is not particularly limited, but a preferred lower limit is 10% by weight and a preferred upper limit is 80% by weight. When the content of the glass fine particles and inorganic fine particles is less than 10% by weight, the viscosity may not be sufficiently obtained, and since there are many resins with respect to the glass fine particles, there may be an adverse effect during sandblasting. If the content of the glass fine particles and inorganic fine particles exceeds 80% by weight, it may be difficult to disperse the glass fine particles.

The glass paste composition of the present invention contains a high boiling point solvent.
The high boiling point solvent preferably has a boiling point of 150 ° C. or higher and lower than 300 ° C. If the boiling point is less than 150 ° C., the solvent will volatilize when the glass paste composition of the present invention is applied, so the viscosity may change and stable coating may not be possible, and the boiling point is 300 ° C. or higher. And after coating, a great deal of time and heat energy may be required at the stage of drying the solvent in the paste. More preferably, it is 280 degrees C or less.

The high boiling point solvent preferably has a specific gravity of 1.0 or more and less than 1.35. If the specific gravity deviates from this range, a sheet attack may occur, and the rib layer may be destroyed or coating may be difficult. Here, the specific gravity means the ratio of the density of water at 4 ° C. or 20 ° C. to the density of the solvent at 20 ° C. or 25 ° C. (Editor: Asahara Teruzo, “Solvent Handbook”, Kodansha, January, 1996 20) Day 14).

The high boiling point solvent having a boiling point of 150 ° C. or more and less than 300 ° C. and a specific gravity of 1.0 or more and less than 1.35 is not particularly limited. For example, diols such as propylene carbonate, diethylene glycol, propane diol, butane diol, One-terminal acetates of diols such as diethylene glycol monoethyl ether acetate and ethylene glycol diacetate, methyl salicylate, ethyl lactate, diethylene glycol monomethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, 2- (benzyloxy) ethanol, 2-phenoxyethanol , 2- (methoxymethoxy) ethanol, triethylene glycol monomethyl ether, triethylene glycol, diethylene glycol monobutyl acetate, diethylene glycol Nobutyl ether acetate, phenoxy acetate, phenoxyethyl acetate, 2-butoxyethyl acetate, 2-ethoxyethyl acetate, 2-methoxyethyl acetate, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, N-methylacetamide, acetamide, N, N-dimethylformamide, N-methylformamide, formamide and the like can be mentioned.
Especially, since it is hard to produce a sheet attack, it is preferable that a dielectric constant is 25 or more, As a solvent with a dielectric constant of 25 or more, ethylene glycol, propylene glycol, butanediol, diethylene glycol, propylene carbonate, γ-butyrolactone, Examples include dimethyl sulfoxide, N-methylpyrrolidone, N-methylacetamide, acetamide, N, N-dimethylformamide, N-methylformamide, formamide and the like. In particular, ethylene glycol, propylene glycol, butanediol, propylene carbonate, and γ-butyrolactone are preferable because they have low toxicity and can be dried at 200 ° C. or lower. In addition, these solvents may be used independently and 2 or more types may be used together.

Although it does not specifically limit as content of the said high boiling point solvent in the glass paste composition of this invention, A preferable minimum is 15 weight% and a preferable upper limit is 48 weight%. When the content of the high boiling point solvent is less than 15% by weight, the paste viscosity is high and the printability is deteriorated. If the content of the high-boiling solvent exceeds 48% by weight, the viscosity necessary for printing may not be ensured.

The glass paste composition of the present invention may contain an adhesion promoter.
The adhesion promoter is not particularly limited, but an aminosilane-based silane coupling agent is preferably used.
Examples of the aminosilane-based silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N -Phenyl-3-aminopropyltrimethoxysilane and the like.
In addition to the aminosilane-based silane coupling agent, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, which are glycidylsilane-based silane coupling agents Etc. may be used. As other silane coupling agents, dimethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane and the like can also be suitably used. These may be used alone or in combination of two or more.

The glass paste composition of the present invention preferably contains a nonionic surfactant for the purpose of promoting leveling after coating.

The nonionic surfactant is not particularly limited, but is preferably a nonionic surfactant having an HLB value of 10 to 20. Here, the HLB value is used as an index representing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed. For example, saponification value of an ester-based surfactant Is H and the acid value of the fatty acid constituting the surfactant is A, the HLB value is represented by 20 (1-S / A). Specifically, those obtained by adding an alkylene ether to a fatty chain are preferable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and the like are preferably used. In addition, although the said nonionic surfactant has good thermal decomposability, since the thermal decomposability of a glass paste composition may fall when it adds in large quantities, the preferable upper limit of content is 5 weight%.

It does not specifically limit as a manufacturing method of the glass paste composition of this invention, A conventionally well-known stirring method is mentioned, Specifically, for example, the said (meth) acryl (co) polymer, glass microparticles, and a high boiling point are mentioned. The method of stirring a solvent and the other component added as needed with a 3 roll mill etc. is mentioned.

As an application of the glass paste composition of the present invention, a ceramic paste composition using a ceramic powder, a phosphor paste composition using a phosphor powder, and a conductive powder are used instead of the dispersed glass fine particles. It can also be used as a green sheet when a conductive paste composition, glass powder or ceramic powder is used. By using for such a use, it can superpose with the green sheet which used ethyl cellulose as binder resin, and can simultaneously degrease and bake.
In other words, taking advantage of the fact that no sheet attack occurs, the process of drawing a pattern with a conductive paste on a green sheet, which had previously required an individual sintering process, the process of covering the dielectric paste on the electrode sheet, and the rib sheet In addition, it is possible to simplify the process of screen printing the phosphor paste.
Also, it can be applied when combining different printing methods, such as printing phosphor paste by ink jet on unsintered ribs, printing electrodes by offset printing, and screen printing dielectric layer. it can. For example, the process of drawing a sandblast resist pattern by a photolithography process is replaced with screen printing.

The glass paste composition of the present invention can also be used as a dielectric layer forming paste. Since the dry film obtained from the glass paste composition of the present invention does not cause sheet attack with a commonly used solvent, after applying the dielectric layer forming paste, the degreasing and firing steps are not performed, and the glass rib layer forming step In this case, the layer (dielectric precursor layer) made of the dielectric layer forming paste is not broken by the solvent sheet attack of the solvent rib paste. Further, since it has extremely excellent sand blast resistance, the dielectric layer is not destroyed even when the rib layer is dried and then subjected to sand blast treatment without firing and cutting. Thereby, it is not necessary to perform a degreasing | defatting and a baking process in multiple times, and it becomes possible to simplify a manufacturing process.

The method for producing a plasma display panel of the present invention comprises forming a glass rib precursor layer by applying a glass paste and drying, and then applying the glass paste composition of the present invention onto the glass rib precursor layer in a predetermined pattern. Printing and drying, a step of forming a concave shape on the glass rib precursor by sandblasting, and a step of heating and degreasing and baking the glass rib precursor.

As described above, the plasma display panel manufacturing method of the present invention is screen-printed using the glass paste composition of the present invention instead of the dry film resist (DFR) conventionally used as a resist material. In addition, since the glass ribs having a fine pattern can be formed without performing the resist exposure and development process, the manufacturing process can be greatly simplified. In addition, since it is not necessary to perform a resist removal step such as alkali washing after the step of forming the concave shape, the plasma display panel can be manufactured efficiently. In addition, the yield is improved, and a plasma display panel with higher accuracy can be manufactured.
In addition, about each process, operation similar to the manufacturing method of the conventional plasma display panel is performed except performing printing and drying using the glass paste composition of this invention, and eliminating a resist image development and removal process. be able to. The glass paste for forming the glass rib is not particularly limited as long as it does not easily react with the solvent contained in the glass paste composition of the present invention, and conventionally known ones can be used.

ADVANTAGE OF THE INVENTION According to this invention, the glass paste composition which is excellent in sheet | seat attack resistance, adhesiveness with a glass rib, and sandblasting resistance, and can manufacture a plasma display panel efficiently can be provided. Moreover, the manufacturing method of the plasma display panel which uses this glass paste composition can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
In a 2L separable flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, 100 parts by weight of 2-hydroxyethyl acrylate (2-HEA), dodecyl mercaptan as chain transfer agent, industrial as organic solvent 100 parts by weight of alcohol for mixing was mixed to obtain a monomer mixture.

The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated until the hot water bath boiled with stirring. A solution obtained by diluting the polymerization initiator with alcohol was added. Further, an alcohol solution containing a polymerization initiator was added several times during the polymerization.

Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. This obtained the alcohol solution of the (meth) acrylic (co) polymer. The obtained polymer was analyzed by gel permeation chromatography (GPC) using a column LF-804 manufactured by SHOKO as a column, and the weight average molecular weight in terms of polystyrene was as shown in Table 1.
The alcohol solution of the (meth) acrylic (co) polymer thus obtained was subjected to solvent substitution with the solvent described in Table 1, and blended so that the composition ratio in Table 1 was obtained. A vehicle composition was prepared by dispersing the mixture.

With respect to the obtained vehicle composition, BL-25 (manufactured by Nikko Chemical Co., Ltd.) as a nonionic surfactant, glass fine particles having an average particle size of 2.0 μm (SiO ₂ 32.5%, B ₂ O ₃ 20 0.5%, ZnO 18%, Al ₂ O ₃ 10%, BaO 3.5%, Li ₂ O 9%, Na ₂ O 6%, SnO ₂ 0.5%) Were added so as to obtain the composition ratio described in 1. to obtain a glass fine particle-dispersed paste. Then, it knead | mixed enough using the high-speed stirring apparatus, it processed until it became smooth with a 3 roll mill, and produced the glass paste composition.

(Examples 2-4, Comparative Examples 1-2)
A vehicle composition and a glass paste composition were prepared in the same manner as in Example 1 except that the monomer mixing ratio was changed as shown in Table 1. In Table 1, 2-HEA represents 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 4-HBA represents 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.), MA represents methyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), MMA represents methyl methacrylate (manufactured by NOF Corporation), 2-HPA represents 2-hydroxypropyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.), and n-BA represents n-butyl acrylate (manufactured by NOF Corporation).

<Evaluation>
The following evaluation was performed about the vehicle composition obtained by the Example and the comparative example, and the glass paste composition. The results are shown in Tables 1 and 2.

(Production of evaluation substrate)
Ethylcellulose (manufactured by Sigma-Aldrich, STD100) was dissolved in a terpineol solution to prepare an ethylcellulose-containing vehicle composition having a resin solid content of 16%. Next, a glass frit having a softening point of about 550 ° C. and an ethylcellulose-containing vehicle composition were mixed so that the glass frit was 50% by weight and the ethylcellulose-containing vehicle composition was 50% by weight, and then kneaded with a high-speed stirrer. The glass paste was produced by processing until it became smooth using a roll mill.
The obtained glass paste was applied to a 15 cm × 15 cm soda glass substrate using an applicator, and dried in a 120 ° C. oven for 30 minutes to prepare an evaluation substrate on which a glass layer was formed.

(1) One drop of the vehicle composition produced in Examples and Comparative Examples was applied to a substrate for sheet attack resistance evaluation using a dropper and dried in an oven at 150 ° C. for 60 minutes to remove the solvent. Thereafter, the state of the glass layer of the evaluation substrate was observed using a microscope and evaluated according to the following criteria.
○ There was no crack in the glass layer and there was no change in the surrounding dense dry film × No crack was seen in the glass layer due to dissolution of ethyl cellulose resin

(2) The glass paste compositions obtained in Examples and Comparative Examples were printed on an evaluation substrate using a screen plate having a substrate adhesion line & space of 30/600 μm. An evaluation sample A having a printed image with a width of 30 μm was obtained by drying at 150 ° C. for 60 minutes in an oven and removing the solvent.
The obtained sample was immersed in a 5% by weight solution of Na ₂ CO ₃ for 5 minutes, taken out, dried in an oven at 120 ° C. for 30 minutes, and observed for peeling of the cured printed image. It was evaluated with.
○ Peeling did not occur × Peeling occurred

(3) Sandblast resistance The glass paste compositions obtained in the Examples and Comparative Examples were coated on a 15 cm × 15 cm soda glass substrate on an evaluation substrate using an applicator at a setting of 5 mils. The glass substrate B for evaluation was obtained by drying in an oven at 150 ° C. for 60 minutes.
For the obtained substrate for evaluation B, Fuji Seisakusho was used as an abrasive under the pressure of 0.04 MPa using a sandblasting machine (Pneuma Blaster SMC-1ADE-401) manufactured by Fuji Seisakusho on the glass layer. A rib partition wall was formed by sandblasting with a spray rate of 200 g / min using a PDP sandblasting medium S9 # 1200. The thing which the damage | wound produced in the dielectric surface with the microscope was set to x, and the thing which did not produce the damage was set to (circle).
In addition, the following evaluation was performed in order to quantitatively evaluate the difficulty of shaving by sandblasting.
A brass wire with a diameter of 300 μm is fixed to the center of the slide glass with a cellophane tape so that both ends are not lifted from the evaluation substrate, and the glass paste compositions obtained in Examples and Comparative Examples are applied at a setting of 6 mils. It was dried in an oven at 150 ° C. for 60 minutes to remove the solvent and heated to obtain a cured glass powder film C embedded with a brass wire.
Then, a test was performed to peel the brass wire at a pulling speed of 200 mm / min using a slide jig with a brass peeling angle of 90 ° in a tensile tester, and the resistance value required for forming the groove was quantified. Evaluation based on the criteria.
○ Peel test force is 0.9N or more x Peel test force is less than 0.9N

(4) Sintering properties The glass paste compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were applied to a glass substrate using an applicator at a setting of 5 mils, and a blast oven set at 150 ° C. The glass substrate was produced by drying for 30 minutes. The produced glass substrate was baked for 30 minutes in an electric furnace set at 600 ° C., and the state of organic residue was confirmed by visually checking the baked color, and evaluated according to the following criteria.
○ Colorless △ Light yellow color × Brown brown color

As shown in Tables 1 and 2, for Examples 1 to 4 and Comparative Example 2 in which the glass transition temperature of the (meth) acrylic (co) polymer is −10 ° C. or less, good results in the substrate adhesion test was gotten. However, in the sandblast test, good results were obtained in Examples 1 to 4, whereas Comparative Example 2 using a (meth) acrylate monomer having a hydroxyl group at a position other than the end of the side chain had insufficient strength. Met.

ADVANTAGE OF THE INVENTION According to this invention, the glass paste composition which is excellent in sheet | seat attack resistance, adhesiveness with a glass rib, and sandblasting resistance, and can manufacture a plasma display panel efficiently can be provided. Moreover, the manufacturing method of the plasma display panel which uses this glass paste composition can be provided.

Claims (6)

A glass paste composition used for manufacturing a plasma display,
Containing an acrylic polymer or methacrylic polymer , glass fine particles and a high boiling point solvent,
The acrylic polymer or the methacrylic polymer has a segment derived from an acrylate monomer having a hydroxyl group at a side chain end or a methacrylate monomer having a hydroxyl group at a side chain end ,
The content of the segment derived from the acrylate monomer having a hydroxyl group at the side chain end or the methacrylate monomer having a hydroxyl group at the side chain end is 70 to 100% by weight,
A glass paste composition having a glass transition temperature of −10 ° C. or lower. The acrylate monomer having a hydroxyl group at the end of the side chain is at least one selected from the group consisting of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. Glass paste composition. The acrylic polymer or methacrylic polymer further contains a segment derived from another acrylate monomer or methacrylate monomer , and the content of the segment derived from the other acrylate monomer or methacrylate monomer is 5 to 30% by weight. The glass paste composition according to claim 1 or 2. 4. The glass paste composition according to claim 1, wherein the high boiling point solvent has a specific gravity of 1.0 or more and less than 1.35. The glass paste composition according to claim 1, 2, 3, or 4, wherein the high boiling point solvent has a dielectric constant of 25 or more. After forming a glass rib precursor by applying and drying a glass paste, the glass paste composition according to claim 1, 2, 3, 4 or 5 is formed in a predetermined pattern on the glass rib precursor. And a step of forming a concave shape on the glass rib precursor by sand blasting, and a step of heating and degreasing and baking the glass rib precursor. A method of manufacturing a plasma display panel.