JPH10324541A - Glass paste composition - Google Patents

Abstract

(57) [Problem] To provide a glass paste composition having excellent dispersion stability of glass powder. Provided is a glass paste composition capable of forming a film forming material layer having no film defects and a dielectric layer having a high light transmittance. Provided is a glass paste composition having excellent coating properties on a support film.
Provided is a glass paste composition capable of producing a transfer film excellent in transferability of a film forming material layer. SOLUTION: This is a glass paste composition containing a glass powder, a binder resin and a solvent, wherein the binder resin contains an acrylic resin having a hydrophilic functional group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a glass paste composition, and more particularly, to a glass paste composition that can be suitably used for forming a dielectric layer of a plasma display panel.

[0002]

2. Description of the Related Art Recently, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type plasma display panel (hereinafter, also referred to as “PDP”). In FIG. 1, reference numerals 1 and 2 denote glass substrates arranged opposite to each other, and reference numeral 3 denotes a partition. A cell is defined by the glass substrate 1, the glass substrate 2 and the partition 3. 4 is a bus electrode fixed to the glass substrate 1, 5 is an address electrode fixed to the glass substrate 2, 6 is a fluorescent substance held in a cell, and 7 is a surface of the glass substrate 1 so as to cover the bus electrode 4. The formed dielectric layer 8 is a protective film made of, for example, magnesium oxide. The dielectric layer 7 is formed of a glass sintered body and has a thickness of, for example, 20 to 50 μm.

As a method for forming the dielectric layer 7, a paste-like composition (glass paste composition) containing glass powder, a binder resin and a solvent is prepared, and the glass paste composition is glass-screened by a screen printing method. A method is known in which a film-forming material layer is formed by applying the film-forming material to the surface of a substrate 1 and drying, and then the film-forming material layer is baked to remove organic substances and sinter glass powder.

Here, as the binder resin constituting the glass paste composition, cellulose derivatives such as methylcellulose, ethylcellulose and carboxymethylcellulose, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, urethane resin, melamine resin and the like are known. Among them, ethyl cellulose is considered to be preferable from the viewpoint of the dispersibility of the glass powder, the coating characteristics of the composition, the easiness of combustion, and the like (for example, see JP-A-6-321819).

[0005] The thickness of the film forming material layer formed on the glass substrate 1 is determined by taking into account the reduction in film thickness accompanying the removal of organic substances in the firing step. It is necessary to be about 1.3 to 2.0 times the thickness,
For example, in order to set the thickness of the dielectric layer 7 to 20 to 50 μm, it is necessary to form a film forming material layer having a thickness of about 30 to 100 μm. On the other hand, when the glass paste composition is applied by a screen printing method, the thickness of a coating film formed by one application treatment is about 15 to 25 μm. Therefore, in order to make the film-forming material layer have a predetermined thickness, the glass paste composition needs to be repeatedly applied (multiple printing) a plurality of times (for example, 2 to 7 times) to the surface of the glass substrate. There is.

However, in the case of forming a film forming material layer by multiple printing using a screen printing method,
The dielectric layer formed by firing the film forming material layer does not have a uniform thickness (for example, the tolerance is within ± 5%). This is due to the multiple printing by the screen printing method,
This is because it is difficult to uniformly apply the glass paste composition to the surface of the glass substrate, and the larger the application area (panel size) and the greater the number of applications, the greater the degree of variation in the thickness of the dielectric layer. Will be large. Then, in the panel material (glass substrate having the dielectric layer) obtained through the application process by the multiple printing, the dielectric characteristics due to the film thickness variations occur in the plane, and the dielectric characteristics vary. This causes display defects (luminance unevenness) in the PDP. Further, in the screen printing method, the mesh shape of the screen plate may be transferred to the surface of the film forming material layer, and the dielectric layer formed by firing such a film forming material layer has a smooth surface. Inferior to

As a means for solving the above-mentioned problems in the case where the film-forming material layer is formed by the screen printing method, the present inventors apply a glass paste composition on a supporting film, dry the coating film, and dry the coating film. Forming a film forming material layer on the support film, transferring the film forming material layer formed on the support film to the surface of the glass substrate to which the electrodes are fixed, and baking the transferred film forming material layer to form the glass forming material layer. A method of manufacturing a PDP including a method of forming a dielectric layer on a surface of a substrate (hereinafter, referred to as “dry film method”) has been proposed (see Japanese Patent Application No. 8-196304). Here, as an example of the transfer step in the dry film method, a composite film (hereinafter, referred to as “transfer film”) in which a film-forming material layer is formed on a support film is placed on the surface (electrode fixing surface) of a glass substrate. After the superposition, the heating roller is moved on the transfer film so that the film forming material layer is heated and adhered to the surface of the glass substrate, and then the support film is transferred from the film forming material layer adhered and fixed to the surface of the glass substrate. Can be mentioned. According to the PDP manufacturing method including such a dry film method, it is possible to form a dielectric layer having excellent film thickness uniformity and surface uniformity. Further, according to this manufacturing method, it is advantageous in that the transfer film, which is a material for forming the dielectric layer, can be wound into a roll and stored.

[0008]

However, when a glass paste composition containing a conventionally known resin such as a cellulose derivative is applied onto a support film to form a film-forming material layer (to produce a transfer film), Since the film forming material layer constituting the transfer film does not have sufficient adhesiveness (heat adhesiveness) to the glass substrate, there is a problem that it is difficult to transfer the film from the support film to the surface of the glass substrate.

In response to such a problem, the present inventors have
By preparing a glass paste composition containing an acrylic resin as a binder resin and applying the glass paste composition on a supporting film, the transfer properties of the film forming material layer (the heat bonding of the film forming material layer to the glass substrate). It was found that a transfer film having excellent properties was obtained.

However, acrylic resins are generally
The glass paste composition containing such an acrylic resin is inferior in affinity (wettability) with glass powder, cannot disperse the glass powder stably, and contains the glass powder in the composition. Aggregates are easily formed. Then, in the film-forming material layer formed by applying the glass paste composition containing the aggregate of the glass powder, a film defect such as a streak-like coating trace, a crater, and a pinhole caused by the aggregate occurs. Would. Further, a glass paste composition in which dispersion stability of glass powder is insufficient is applied to form a film forming material layer, and a glass sintered body (dielectric layer) formed by firing this film forming material layer Is liable to be turbid due to the remaining minute bubbles, so that the dielectric layer does not have sufficient transparency (high light transmittance).

The present invention has been made based on the above circumstances. A first object of the present invention is to provide a glass paste composition having excellent dispersion stability of glass powder. A second object of the present invention is to provide a glass paste composition containing no aggregate of glass powder. A third object of the present invention is to provide a glass paste composition that does not cause film defects such as streak-like coating marks, craters and pinholes in a film-forming material layer formed by drying a coating film. is there. A fourth object of the present invention is to provide a glass paste composition capable of forming a glass sintered body having a high light transmittance (for example, a dielectric layer of PDP) by firing the obtained film forming material layer. To provide. A fifth object of the present invention is to provide a glass paste composition that can be suitably used for producing a transfer film. A sixth object of the present invention is to provide a glass paste composition capable of producing a transfer film excellent in transferability of a film-forming material layer (heat adhesion of the film-forming material layer to a glass substrate). . Seventh of the present invention
An object of the present invention is to provide a glass paste composition having excellent coating properties on a support film.

[0012]

The glass paste composition of the present invention comprises (A) a glass powder, (B) a binder resin containing an acrylic resin having a hydrophilic functional group, and (C) a solvent. It is characterized by containing. In the glass paste composition of the present invention, the polarity term of the surface tension of the binder resin is preferably in the range of 1 to 13 dyn / cm. Further, the binder resin preferably has a surface tension in a range of 30 to 50 dyn / cm.

[0013]

[Action]

(1) Since the acrylic resin is contained as the binder resin, the formed film forming material layer exhibits excellent heat adhesion to the glass substrate. Therefore, when the composition of the present invention is applied on a support film to produce a transfer film, the resulting transfer film has excellent transferability of the film-forming material layer (transferability to a glass substrate). . (2) Since the acrylic resin constituting the composition of the present invention has a hydrophilic functional group, it is excellent in wettability (affinity) with glass powder having a hydrophilic surface. Therefore,
In the composition of the present invention, the glass powder can be dispersed stably and does not form an aggregate of the glass powder. Thereby, a film defect or the like does not occur in a film forming material layer formed by applying the composition of the present invention, and furthermore, by firing the film forming material layer, a glass firing material having a high light transmittance is obtained. A unity can be formed. (3) By defining the polarity term of the surface tension in the binder resin in a specific range (1 to 13 dyn / cm), the composition of the present invention containing the binder resin can stably disperse the glass powder. And excellent coating characteristics for a support film (for example, a PET film subjected to a release treatment).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the glass paste composition of the present invention will be described in detail. The glass paste composition of the present invention contains glass powder, a binder resin containing an acrylic resin having a hydrophilic functional group, and a solvent as essential components.

<Glass powder> Constituting the composition of the present invention
As a glass powder, its softening point is 400-600 ° C.
Those within the range are preferred. Softening point of glass powder is 4
When the temperature is lower than 00 ° C., a film forming material using the composition
In the baking process of the material layer, organic substances such as binder resin are completely
The glass powder melts at a stage where it is not completely decomposed and removed.
Some organic substances remain in the formed dielectric layer
As a result, the light transmittance of the dielectric layer tends to decrease.
You. On the other hand, when the softening point of the glass powder exceeds 600 ° C.
Must be fired at a temperature higher than 600 ° C.
The glass substrate is likely to be distorted. Suitable glass powder
Specific examples of powders include lead oxide, boron oxide,
I (PbO-B_TwoO_Three-SiO_TwoMixture),
Zinc oxide, boron oxide, silicon oxide (ZnO-B_TwoO_Three
-SiO_TwoMixture), lead oxide, boron oxide, acid
Silicon oxide, aluminum oxide (PbO-B_TwoO_Three-Si
O_Two-Al_TwoO_ThreeSystem), lead oxide, suboxide
Lead, boron oxide, silicon oxide (PbO-ZnO-B _TwoO
_Three-SiO_TwoSystem) can be exemplified.
You.

<Binder Resin> The composition of the present invention comprises, as a binder resin, an acrylic resin having a hydrophilic functional group
It is called "hydrophilic acrylic resin". )). Here, "hydrophilic functional group"
Examples thereof include a hydroxyl group; an alkoxyl group such as a methoxyl group and an ethoxyl group; a carboxyl group; and a sulfonic acid group.

As the hydrophilic acrylic resin constituting the composition of the present invention, a (meth) acrylate having a hydrophilic functional group [hereinafter referred to as a “hydrophilic group-containing (meth) acrylate”. And a copolymer having two or more hydrophilic group-containing (meth) acrylates, one or more hydrophilic group-containing (meth) acrylates, and having no hydrophilic functional group ( Copolymer with one or more meth) acrylates, containing hydrophilic group (meth)
A copolymer of one or more acrylates and one or more other copolymerizable unsaturated monomers, one or more hydrophilic group-containing (meth) acrylates, One or more (meth) acrylates having no hydrophilic functional group and one of the other copolymerizable unsaturated monomers
And a copolymer of two or more species. The above-mentioned copolymers constituting the hydrophilic acrylic resin may be any of a random copolymer, a block copolymer, a graft copolymer, and an alternating copolymer.
Further, the above-mentioned (co) polymers constituting the hydrophilic acrylic resin have an appropriate tackiness and can bind the glass powder, and the film forming material is calcined (at 400 ° C.).
To 600 ° C.).

Examples of "hydrophilic group-containing (meth) acrylate" as a constituent monomer of the hydrophilic acrylic resin include, for example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)
Hydroxyalkyl (meth) acrylates such as acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; ethylene glycol monomethyl (meth) acrylate, ethylene glycol monoethyl (meth) acrylate, glycerol (meth) acrylate (Meth) acrylates containing a hydroxyl group such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2
-Alkoxyalkyl (meth) acrylates such as propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate and 2-methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxy Polyalkylenes such as polypropylene glycol (meth) acrylate , And the like recall (meth) acrylate.

The “(meth) acrylate having no hydrophilic functional group” as a constituent monomer of the hydrophilic acrylic resin includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (Meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth)
Acrylate, isooctyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl Alkyl (meth) acrylates such as (meth) acrylate and isostearyl (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, etc. Black alkyl (meth) acrylate; (meth) acrylic acid dimethylaminoethyl ester, tetrahydrofurfuryl (meth) acrylate,
(Meth) acrylamide, (meth) acrylonitrile, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, butylene glycol di (meth)
Examples include acrylate, propylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. The “other copolymerizable unsaturated monomer” that can be used as a constituent monomer of the hydrophilic acrylic resin is not particularly limited as long as it is a compound copolymerizable with the above (meth) acrylate compound.
Unsaturated carboxylic acids such as (meth) acrylic acid, vinylbenzoic acid, maleic acid, vinylphthalic acid; vinylbenzyl methyl ether, vinyl glycidyl ether,
Examples include vinyl group-containing radically polymerizable compounds such as styrene, α-methylstyrene, butadiene, and isoprene. The binder resin constituting the composition of the present invention may contain another polymer within a range compatible with the hydrophilic acrylic resin. Examples of the other polymer include one or more (co) polymers of the above-mentioned “(meth) acrylate having no hydrophilic functional group”, and the above-mentioned “other copolymerizable unsaturated monomer”. ) One or more (co) polymers of
Copolymers of one or more of the above-mentioned "(meth) acrylates having no hydrophilic functional group" and one or more of the other copolymerizable unsaturated monomers And the like are preferred.

The binder resin constituting the composition of the present invention preferably has a surface tension having a polarity term in the range of 1 to 13 dyn / cm. The value of the polar term of the surface tension is 1 dy
A binder resin having a molecular weight of less than n / cm becomes hydrophobic, and the wettability (affinity) with glass powder having a hydrophilic surface is reduced. When such a binder resin is used, it is difficult to prepare a composition having excellent dispersion stability of glass powder, and a film defect or the like occurs in a film forming material layer formed by the composition. This may occur, or the glass sintered body (dielectric layer) formed by firing the film-forming material layer of the composition may not have sufficiently high light transmittance. On the other hand, the value of the polarity term of the surface tension is 13d.
A binder resin exceeding yn / cm exhibits extremely high hydrophilicity, and a glass paste composition containing such a binder resin is converted into a support film having a hydrophobic surface (for example, a PET film subjected to release treatment). Film) is difficult to apply. By setting the value of the polarity term of the surface tension in the binder resin to 1 to 13 dyn / cm, the obtained glass paste composition has the dispersion stability of the glass powder,
It has both excellent coating properties for the support film. The polarity term of the surface tension in the binder resin can be adjusted by changing the type and content of the hydrophilic group in the binder resin. The value of the surface tension (polar term + dispersion term) of the binder resin is 30 to 50 dyn / c.
m is preferably in the range.

The molecular weight of the binder resin constituting the composition of the present invention is 10,000 to 15 as a weight average molecular weight in terms of polystyrene by GPC (eluent: THF).
It is preferably 0.000, more preferably 4
It is 0000 to 100,000.

The content of the binder resin in the composition of the present invention is 5 to 4 parts by weight based on 100 parts by weight of the glass powder.
0 parts by weight, more preferably 10 parts by weight.
To 30 parts by weight. If the proportion of the acrylic resin is too small, the glass powder cannot be bound and held reliably. On the other hand, if this ratio is excessive, a long time is required for the firing step, or the formed glass sintered body (dielectric layer) may not have sufficient surface smoothness.

<Solvent> The solvent constituting the composition of the present invention has good affinity for glass powder and good solubility of the binder resin, and can impart an appropriate viscosity to the glass paste composition. Preferably, it can be easily evaporated and removed by drying. As a particularly preferred solvent, the standard boiling point (boiling point at 1 atm) is 10
Ketones, alcohols and esters having a temperature of 0 to 200 ° C. (hereinafter, these are referred to as “specific solvents”) can be exemplified. Specific examples of such a specific solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetone alcohol Ether ethers 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 acids such as n-butyl acetate and amyl acetate Alkyl esters; lactate esters such as ethyl lactate and n-butyl lactate; methyl cellosolve acetate, ethyl cellosolve acetate;
Propylene glycol monomethyl ether acetate,
Examples thereof include ether esters such as ethyl-3-ethoxypropionate.
Methyl butyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate,
Ethyl-3-ethoxypropionate and the like are preferred.
These specific solvents can be used alone or in combination of two or more. Specific examples of the solvent other than the specific solvent include turpentine, ethyl cellosolve, methyl cellosolve, terpineol, butyl carbitol acetate, butyl carbitol, isopropyl alcohol,
Benzyl alcohol and the like can be mentioned.

The content of the solvent in the composition of the present invention is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the glass powder from the viewpoint of maintaining the viscosity of the composition in a suitable range. More preferably, it is 10 to 40 parts by weight. Further, the content ratio of the specific solvent to all the solvents is preferably 50% by weight or more, more preferably 70% by weight or more.

The glass paste composition of the present invention contains, in addition to the above essential components, a dispersant, a tackifier, a plasticizer,
Various additives such as a surface tension modifier, a stabilizer, an antifoaming agent, and a dispersant may be contained as optional components. As an example of a preferred glass paste composition, as a glass powder, a mixture 100 of 50 to 80% by weight of lead oxide, 5 to 20% by weight of boron oxide, and 10 to 30% by weight of silicon oxide
Parts by weight and a butyl methacrylate / 2-hydroxypropyl methacrylate copolymer (copolymerization ratio: 90/10,
A composition containing 10 to 30 parts by weight of a hydrophilic acrylic resin) and 10 to 50 parts by weight of propylene glycol monomethyl ether (solvent) as essential components can be given. The composition of the present invention comprises the above glass powder, a binder resin and a solvent and optional components, a roll kneader, a mixer,
It can be prepared by kneading using a kneader such as a homomixer. The composition of the present invention prepared as described above is a paste-like composition having fluidity suitable for application.

The composition of the present invention can be particularly preferably used for producing a transfer film. This transfer film is a composite material composed of a support film and a film-forming material layer formed on the support film, and used in a process of forming a dielectric layer by a dry film method. Here, the viscosity of the glass paste composition (the composition of the present invention) to be subjected to the step of applying to the support film by the dry film method is preferably from 1,000 to 20,000.

The supporting film constituting the transfer film includes:
It is preferable that the resin film has heat resistance and solvent resistance and is flexible. When the support film has flexibility, the composition of the present invention can be applied by a roll coater, and the film-forming material layer can be stored and supplied in a rolled state. Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose. As the thickness of the support film, for example, 20 to
100 μm.

The film forming material layer constituting the transfer film includes:
The composition can be formed by applying the composition of the present invention on the support film, drying the coating film and removing a part or all of the solvent. As a method of applying the composition of the present invention on a support film, it is preferable that a method can efficiently form a large (for example, 20 μm or more) coating film having excellent thickness uniformity, Specifically, a coating method using a roll coater, a coating method using a blade coater, a coating method using a curtain coater, a coating method using a wire coater, and the like can be preferably mentioned. The surface of the support film to which the composition of the present invention is applied is preferably subjected to a release treatment. Thereby, in the step of transferring to the glass substrate, the operation of peeling the support film can be easily performed. Further, the transfer film may be provided with a protective film layer on the surface of the film forming material layer. Examples of such a protective film layer include a polyethylene terephthalate film, a polyethylene film, and a polyvinyl alcohol-based film.

As described above, the composition of the present invention can be particularly preferably used in producing a transfer film by forming a film-forming material layer on a support film, but is not limited to these uses. Instead, a conventionally known method for forming a film-forming material layer, that is, the composition is directly applied to the surface of a glass substrate by a screen printing method or the like, and the film is dried to form a film-forming material layer. The method can also be suitably used. Here, it is preferable that the viscosity of the glass paste composition (the composition of the present invention) to be subjected to the step of coating the glass substrate by the screen printing method is 10,000 to 200,000.

[0030]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the following, “parts” indicates “parts by weight”. Preparation of <Example 1> (1) Glass paste composition: as glass powder, lead oxide 60 wt%, boron oxide 10 _{wt%, PbO-B 2 O 3} -Si having a composition of silicon oxide 30 wt%
100 parts of an O ₂ -based mixture (softening point: 550 ° C.), hydrophilic acrylic resin obtained by copolymerizing butyl methacrylate (90% by weight) and 2-hydroxypropyl methacrylate (10% by weight) as a binder resin (Polystyrene equivalent weight average molecular weight by GPC: 85,000, surface tension: 35 dyn / cm, polar term of surface tension: 3 dy)
n / cm) 23 parts and propylene glycol monomethyl ether 20 parts as a solvent were kneaded with a disperser to prepare a composition of the present invention having a viscosity of 4,500 cp.

(2) Production of transfer film (evaluation of coating characteristics): A support film (400 mm wide, 400 mm long) made of polyethylene terephthalate (PET) which has been subjected to a mold release treatment of the composition of the present invention prepared in the above (1). 30m, thickness 3
8 μm) using a roll coater, a uniform coating film could be formed on the entire surface of the support film. Next, the formed coating film was dried at 100 ° C. for 5 minutes to remove the solvent.
A transfer film having a 0 μm film-forming material layer formed on a support film was manufactured.

(3) Evaluation of transfer film: The surface state of the film-forming material layer of the transfer film produced in the above (2) was observed using a microscope. No film defects such as craters and pinholes were observed.

(4) Transfer of the film-forming material layer: manufactured in the above (2) so that the surface of the film-forming material layer is brought into contact with the surface of the glass substrate for a 20-inch panel (the fixed surface of the bus electrode). The transfer films thus obtained were overlapped, and the transfer film was thermocompression-bonded with a heating roll. Here, as the pressing conditions, the surface temperature of the heating roll is 110 ° C., and the roll pressure is 3 k.
g / cm ² , and the moving speed of the heating roll was 1 m / min.
After the completion of the thermocompression bonding, the support film was peeled off from the film forming material layer. As a result, the film-forming material layer was transferred to and adhered to the surface of the glass substrate.

(5) Firing the film-forming material layer (forming a dielectric layer): The glass substrate on which the film-forming material layer is transferred and formed by the above (4) is placed in a firing furnace, and the temperature in the furnace is set to room temperature. To 570 ° C at a rate of 10 ° C / min.
By baking for 30 minutes in the temperature atmosphere, a dielectric layer made of a glass sintered body was formed on the surface of the glass substrate.

(6) Evaluation of dielectric layer: The thickness (average thickness and tolerance) of the dielectric layer was measured to be 15 μm ±
The thickness was in the range of 1 μm, and the film thickness was excellent in uniformity. Also, five panel materials made of a glass substrate having a dielectric layer were prepared in this way, and the light transmittance (measurement wavelength: 600 nm) of the formed dielectric layer was 83 to 86%. , And having good transparency. Table 1 summarizes the above results.

<Examples 2 to 5> A glass paste composition of the present invention was prepared in the same manner as in Example 1 except that the hydrophilic acrylic resin (constituent monomer) was changed according to the formulation shown in Table 1. . Next, a transfer film was produced in the same manner as in Example 1 except that each of the obtained glass paste compositions was used. Thereafter, in the same manner as in Example 1 except that each of the obtained transfer films was used, the transfer of the film-forming material layer and the baking treatment of the film-forming material layer were performed to obtain the surface of the glass substrate for a 20-inch panel. A dielectric layer (15 μm ± 1 μm in thickness) was formed on the substrate.

For each of the compositions according to Examples 2 to 5, in the same manner as in Example 1, the coating properties on the support film, the surface condition of the film forming material layer formed by the composition, and the film forming material layer The transferability of the sample (heat adhesion to a glass substrate) was evaluated, and the light transmittance of the formed dielectric layer was measured. Here, the coating properties on the support film were determined to be "good" when the composition could be formed on the entire surface of the support film without repelling the composition on the surface of the support film. The surface condition of the film forming material layer is “good” when there is no film defect such as agglomerates of glass powder, streak-like coating traces, craters, and pinholes.
It was determined. The transferability of the film-forming material layer was determined to be “good” when all of the film-forming material layer was transferred to and adhered to the surface of the glass substrate. Table 1 shows the above results.

<Comparative Example 1> Lead oxide 6 was used as the glass powder.
100 parts of a PbO—B ₂ O ₃ —SiO ₂ system mixture (softening point: 550 ° C.) having a composition of 0% by weight, 10% by weight of boron oxide and 30% by weight of silicon oxide, butyl methacrylate (80% by weight) as a binder resin %) And n-lauryl methacrylate (20% by weight) obtained by copolymerizing an acrylic resin (weight average molecular weight in terms of polystyrene by GPC: 80,000, surface tension: 38 dyn / cm, polarity term of surface tension: A comparative composition having a viscosity of 4,000 cp was prepared by kneading 23 parts of 0 dyn / cm) and 20 parts of methyl isobutyl ketone as a solvent using a disperser. When the thus prepared comparative composition was applied on a support film in the same manner as in Example 1, a uniform coating film could be formed on the entire surface of the support film. Next, the formed coating film was dried at 100 ° C. for 5 minutes to remove the solvent, thereby producing a transfer film having a 30 μm-thick film-forming material layer formed on a support film. When the surface state of the film-forming material layer was observed using a microscope for the transfer film thus manufactured, a crater,
Film defects such as pinholes were observed. Next, the transfer film was superimposed on the surface of the glass substrate for a 20-inch panel (the surface on which the bus electrode was fixed) so that the surface of the film forming material layer was in contact with the transfer film. And thermocompression-bonded with a heating roll. After the completion of the thermocompression bonding, the support film was peeled off from the film forming material layer. As a result, the film-forming material layer was transferred to and adhered to the surface of the glass substrate. The glass substrate on which the film-forming material layer was transferred and formed as described above was subjected to a baking treatment under the same baking conditions as in Example 1 to form a dielectric layer made of a glass sintered body on the surface of the glass substrate. . When the film thickness (average film thickness and tolerance) of this dielectric layer was measured, it was 15 μm ±
It was in the range of 1 μm. Further, in this manner, five panel materials made of a glass substrate having a dielectric layer were prepared, and the light transmittance of the formed dielectric layer (measurement wavelength 600 n
m) was 70 to 75% and was poor in transparency. And when the said dielectric layer was observed using the microscope, many fine air bubbles remained. Table 1 summarizes the above results.

[0039]

[Table 1]

[0040]

According to the composition of the present invention, the following effects can be obtained. (1) Since the composition of the present invention contains a hydrophilic acrylic resin having excellent affinity for glass powder, the composition has excellent dispersion stability of glass powder, No agglomerates are formed. (2) It is possible to form a uniform film forming material layer without film defects. (3) A film-forming material layer having excellent adhesion to a glass substrate can be formed. (4) A glass sintered body having a high light transmittance can be formed. The glass sintered body is suitable as a dielectric layer of PDP. (5) It can be suitably used for the production of a transfer film. (6) Transferability of film forming material layer (transferability to glass substrate)
It is possible to produce a transfer film excellent in quality. (7) By defining the polarity term of the surface tension in the binder resin in a specific range, excellent coating characteristics can be obtained even for a support film having a hydrophobic surface (for example, a PET film subjected to a release treatment). Will have.

[Brief description of the drawings]

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Glass substrate 3 Partition wall 4 Bus electrode 5 Address electrode 6 Phosphor 7 Dielectric layer 8 Protective layer

 ────────────────────────────────────────────────── ─── Continued from the front page (72) Inventor Atsushi Kumano 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd.

Claims (1)

[Claims] 1. A glass paste composition comprising (A) glass powder, (B) a binder resin containing an acrylic resin having a hydrophilic functional group, and (C) a solvent.