JP2009256548A - Glass paste composition and method for manufacturing plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass paste composition excellent in sheet attack resistance, adhesiveness to glass ribs and sand-blast resistance, from which a plasma display panel can be manufactured efficiently, and to provide a method for manufacturing the plasma display panel by using the glass paste composition. <P>SOLUTION: This glass paste composition used for manufacturing a plasma display panel includes a (meth)acrylic copolymer, glass fine particles and a high-boiling point solvent, where the (meth)acrylic copolymer has a segment derived from a (meth)acrylic monomer having a hydroxy group, a segment derived from a (meth)acrylate monomer whose alcohol substituent has four or less carbons, and a segment derived from (meth)acrylonitrile. <P>COPYRIGHT: (C)2010,JPO&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. Moreover, it is related with the manufacturing method of the plasma display panel which uses this 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 contains a (meth) acrylic copolymer, glass fine particles and a high-boiling solvent, and the (meth) acrylic copolymer comprises a segment derived from a (meth) acrylic monomer having a hydroxyl group and an alcohol substituent. It is a glass paste composition having a segment derived from a (meth) acrylic acid ester monomer having 4 or less carbon atoms and a segment derived from (meth) acrylonitrile.
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. Moreover, there existed a problem that adhesiveness with a glass rib layer was bad and the baked glass paste composition and a glass rib layer were not fully integrated.
Therefore, as a result of further intensive studies, the present inventors have determined that a segment derived from a (meth) acrylic monomer having a predetermined hydroxyl group, a segment derived from a (meth) acrylic acid ester having an alcohol substituent with 4 or less carbon atoms, and Using a glass paste composition containing a (meth) acrylic copolymer having a segment derived from acrylonitrile or methacrylonitrile, a high boiling point solvent and glass fine particles as a resist material, sheet attack occurs during printing. It was found that the fired glass paste composition and the glass rib layer can be integrated without being cut in the sandblasting process, and the present invention has been completed.

In the present invention, (meth) acrylate means acrylate or methacrylate, and (meth) acryl means acryl or methacryl. (Meth) acrylonitrile means acrylonitrile or methacrylonitrile.
The glass paste composition of the present invention comprises a segment derived from a (meth) acrylic monomer having a hydroxyl group, a segment derived from a (meth) acrylic acid ester monomer having an alcohol substituent of 4 or less, and (meth) acrylonitrile. (Meth) acrylic copolymer having a segment derived from
In the present invention, by having a segment derived from the above (meth) acrylic monomer having a hydroxyl group, the hydroxyl group density is increased, exerts a strong interaction with the surface of the glass fine particles, and has high strength after solvent drying. A film can be formed. Thereby, the sandblast resistance, the adhesion to the glass rib, and the sheet attack resistance are also excellent.
Moreover, the segment originating in the (meth) acrylic acid ester monomer whose carbon number of the said alcohol substituent is 4 or less can become a starting point of decomposition | disassembly at the time of baking, and can make thermal decomposition good. Moreover, with respect to the segment derived from the (meth) acrylic monomer having a hydroxyl group, the resin glass has a small amount of a segment derived from a (meth) acrylic acid ester monomer having 4 or less carbon atoms in the alcohol substituent. Adhesion to fine particles is increased, and sandblast resistance is improved.
By having a segment derived from the (meth) acrylonitrile, rubber-like toughness is obtained, sandblast resistance is greatly improved, and a glass rib having a finer shape can be formed.

As the (meth) acrylic monomer having a hydroxyl group, it is preferable to use at least one selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and glycerol monomethacrylate. By using the (meth) acrylic monomer having such a combination of hydroxyl groups, the hydroxyl group density of the (meth) acrylic copolymer is increased, the intimacy with the glass is increased, and the dispersibility of the glass fine particles and the sandblast resistance are improved. It will be excellent.

The minimum with preferable content of the (meth) acryl monomer which has the said hydroxyl group in the said (meth) acryl copolymer is 30 weight%, and a preferable upper limit is 70 weight%. When the content of the (meth) acrylic monomer having a hydroxyl group is less than 30% by weight, the strength of the resulting film becomes insufficient, and when the content of the (meth) acrylic monomer having a hydroxyl group exceeds 70% by weight. The selection range of the solvent becomes narrow, and the process suitability is not satisfied. A more preferred lower limit is 50% by weight, and a more preferred upper limit is 65% by weight.

Among the above (meth) acrylic monomers having a hydroxyl group, it has a segment derived from 2-hydroxyethyl methacrylate because it has better thermal decomposability than 2-hydroxyethyl acrylate and glycerol monomethacrylate. It is preferable.

Examples of the (meth) acrylic acid ester monomer having 4 or less carbon atoms in the alcohol substituent include methyl methacrylate, methyl acrylate, and isobutyl methacrylate. The addition of these monomers serves as a starting point for thermal decomposability and reduces decomposition residues, and the hydroxyl group increases the adhesion to the glass particles and increases the sandblast resistance. Among the (meth) acrylic acid ester monomers having 4 or less carbon atoms in the alcohol substituent, methyl methacrylate and isobutyl methacrylate are particularly preferable.

The preferable lower limit of the content of the segment derived from the (meth) acrylic acid ester monomer having 4 or less carbon atoms in the alcohol substituent is 5% by weight, and the preferable upper limit is 30% by weight. When the content of the segment derived from the (meth) acrylic acid ester monomer having 4 or less carbon atoms of the alcohol substituent is less than 5% by weight, the effects such as low-temperature decomposability and sandblast resistance are not sufficiently exhibited, When the content of the segment derived from the (meth) acrylic acid ester monomer having 4 or less carbon atoms in the alcohol substituent exceeds 30% by weight, the sandblast resistance may be lowered. The more preferable lower limit of the content of the segment derived from the (meth) acrylic acid ester monomer having 4 or less carbon atoms in the alcohol substituent is 10% by weight, and the more preferable upper limit is 20% by weight.

The minimum with preferable content of the segment derived from the said (meth) acrylonitrile is 5 weight%, and a preferable upper limit is 30 weight%. When the content of the segment derived from the (meth) acrylonitrile is less than 5% by weight, the effect of toughening the binder resin is not sufficiently exhibited, and the content of the segment derived from the (meth) acrylonitrile is 30% by weight. If it exceeds%, the decomposition residue during sintering may increase.

The (meth) acrylic copolymer is a copolymer other than a segment derived from a (meth) acrylic monomer having a hydroxyl group, a (meth) acrylic acid ester monomer having an alcohol substituent of 4 or less, and a (meth) acrylonitrile. It may have segments derived from possible (meth) acrylic monomers.
Examples of the copolymerizable (meth) acrylic monomer include glycidyl methacrylate and glycidyl acrylate, acrylic acid, methacrylic acid, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, and n. -Stearyl (meth) acrylate, benzyl (meth) acrylate, etc. are mentioned. Of these, a (meth) acrylic monomer having 10 or less carbon atoms is preferable, and polyalkylene oxide (meth) acrylate is more preferable because it is excellent in decomposability.

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the (meth) acrylic copolymer depends on the glass transition temperature of the (meth) acrylic copolymer, but the preferred lower limit is 5000. The preferred 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 the (meth) acrylic copolymer having a glass transition temperature higher than room temperature, the 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) acryl copolymer 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 copolymer is less than 5% by weight, the glass fine particles may not be sufficiently dispersed, which may cause problems in printability. If the coal content exceeds 45% by weight, the thermal decomposability may be adversely affected.

The minimum with a preferable glass transition temperature of the said (meth) acryl copolymer is -50 degreeC, and a preferable upper limit is 120 degreeC. When the glass transition temperature of the (meth) acrylic copolymer is less than -50 ° C, a problem may occur during sandblasting. In addition, since a large amount of resin is required to obtain a viscosity that can be applied, it takes time for degreasing and baking.
When the glass transition temperature of the (meth) acrylic copolymer exceeds 120 ° C., the solubility in a solvent may deteriorate.

The polymerization method of the (meth) acrylic copolymer is not particularly limited, and examples thereof include methods used for the polymerization of ordinary (meth) acrylic monomers. For example, free radical polymerization method, living radical polymerization method, iniferter weight Examples thereof include a combination method, an anionic polymerization method, and a living anion polymerization method.

The glass paste composition of the present invention contains glass fine particles.
Is not particularly restricted but the composition of the glass powder, for example, silicate glass, lead _{glass, CaO-Al 2 O 3 -SiO} 2 type inorganic _{glass, MgO-Al 2 O 3 -SiO} 2 type inorganic glass, LiO ₂ -Al ₂ O ₃ -SiO ₂ system various glasses such as inorganic glass. 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 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. 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, and as a solvent whose dielectric constant is 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, For example, the said (meth) acryl copolymer, glass microparticles | fine-particles, and a high boiling-point solvent are mentioned specifically, for example. Examples of the method include stirring with other components added as necessary using a three-roll mill or the like.

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 2 L separable flask equipped with a stirrer, cooler, thermometer, hot water bath and nitrogen gas inlet, 5 parts by weight of methyl acrylate (MA), 90 parts by weight of 2-hydroxyethyl methacrylate (HEMA), acrylonitrile (AN) 5 parts by weight, dodecyl mercaptan as a chain transfer agent, and 100 parts by weight of an industrial alcohol as an organic solvent were 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 resin. 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 resin thus obtained was subjected to solvent substitution with the solvent described in Table 1, compounded so as to have the composition ratio in Table 1, and dispersed with a high-speed disperser. A vehicle composition was prepared.

For the obtained vehicle composition, BL-25 (manufactured by Nikko Chemical Co., Ltd.) as a nonionic surfactant, glass fine particles having an average particle diameter 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 2-6, Comparative Examples 1-4)
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, HEA represents 2-hydroxyethyl acrylate, IBMA represents isobutyl methacrylate, GLM represents glycerol methacrylate, MMA represents methyl methacrylate, BA represents butyl acrylate, MAN represents methacrylonitrile, and LMA represents lauryl methacrylate. .

<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. By drying in an oven at 150 ° C. for 60 minutes and removing the solvent, a sample having a printed image with a width of 30 μm was obtained.
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 following evaluation was performed to quantitatively evaluate the resistance to sand blasting.
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 embedded with brass wires.
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.
In addition, since peeling occurred in the glass paste compositions obtained in Comparative Examples 2 and 4 in “(2) Substrate adhesion”, the peel strength was set as a reference value, and the determination was not performed.
○ Peel test force is 0.9N or more x Peel test force is less than 0.9N

(4) Sinterability The glass paste compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 4 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 Table 2, in the vehicle composition and the glass paste composition obtained in the examples, good results were obtained.
On the other hand, Comparative Examples 1 and 3 had poor sandblast resistance, and Comparative Example 2 with a large amount of acrylonitrile added had poor sinterability and many decomposition residues remained.

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 (7)

A glass paste composition used for manufacturing a plasma display,
(Meth) acrylic copolymer, glass fine particles and high boiling point solvent,
The (meth) acrylic copolymer includes a segment derived from a (meth) acrylic monomer having a hydroxyl group, a segment derived from a (meth) acrylic acid ester monomer having an alcohol substituent having 4 or less carbon atoms, and (meth) A glass paste composition comprising a segment derived from acrylonitrile. The glass paste composition according to claim 1, wherein the content of the segment derived from the (meth) acrylic monomer having a hydroxyl group in the (meth) acrylic copolymer is 30 to 70% by weight. The content of a segment derived from a (meth) acrylic acid ester monomer having 4 or less carbon atoms in an alcohol substituent in the (meth) acrylic copolymer is 5 to 30% by weight or 2. The glass paste composition according to 2. The glass paste composition according to claim 1, 2, or 3, wherein the content of the segment derived from (meth) acrylonitrile in the (meth) acrylic copolymer is 5 to 30% by weight. The glass paste composition according to claim 1, 2, 3, or 4, 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, 4, or 5, 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, 5 or 6 is formed on the glass rib precursor with a predetermined pattern. A step of 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 firing the glass rib precursor. A method for manufacturing a plasma display panel.