JPH10310451A - Glass paste composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. which has excellent dispersion stability of a glass powder, which does not cause aggregation of the powder with time and which is useful to obtain a film forming material layer having no film defects and excellent adhesion property with a glass substrate by incorporating a glass powder, a binder resin and a specified silane coupling agent. SOLUTION: This compsn. contains a glass powder (e.g. a mixture of 50 to 80 wt.% lead oxide, 5 to 20 wt.% boron oxide and 10 to 30 wt.% silicon oxide) preferably having 400 to 600 deg.C softening point, preferably by 100 pts.wt., a binder resin preferably comprising an acryl resin having 4,000 to 300,000 weight average mol.wt. calculated in terms of PS, and more preferably 10,000 to 200,000 (such as polybutylmethacrylate), preferably by 5 to 40 pts.wt., and a silane coupling agent expressed by the formula, preferably by 0.001 to 10 pts.wt. In the formula, (p) is 3 to 20, preferably 4 to 16, and (m), (n), (a) are each 1 to 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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.

[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 a binder resin constituting the glass paste composition, cellulose derivatives such as methylcellulose, ethylcellulose and carboxymethylcellulose, poly-α-methylstyrene, polyvinyl alcohol,
Polyvinyl butyral, polyethylene glycol, urethane-based resins, melamine-based resins, and the like are known, and among these, ethyl cellulose is preferred from the viewpoints of dispersibility of glass powder, coating properties of the composition, ease of combustion, and the like. (See, for example, JP-A-6-321719 and JP-A-2-124744).

[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 step of forming a dielectric layer on the surface of a substrate (hereinafter, also referred to as “dry film method”) has been proposed (see Japanese Patent Application No. 8-196304). According to such a manufacturing method, a dielectric layer having excellent film thickness uniformity and surface uniformity can be formed, and a composite film (a film-forming material layer formed on a supporting film) can be formed. Hereinafter, also referred to as a “transfer film”) is advantageous in that it can be wound and stored in a roll shape.

[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), However, there is a problem in that the formed film-forming material layer does not have sufficient flexibility, and when the transfer film is bent, minute cracks (cracks) are generated on the surface of the film-forming material layer. Further, since the film-forming material layer containing the cellulose derivative cannot exhibit sufficient adhesiveness (heat-adhesiveness) to the glass substrate, there is also 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 support film, transfer excellent in transferability (adhesion to a glass substrate) of a film forming material layer is achieved. It has been found that a film can be obtained.

However, in the glass paste composition containing an acrylic resin, the dispersion stability of the glass powder is insufficient, so that aggregates of the glass powder are generated in the composition over time, There is a new problem that sedimentation occurs and cake-like deposits are generated at the bottom of the storage container. 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. In addition, according to the composition in which the glass powder is settled and separated, an intended glass sintered body (dielectric layer) cannot be formed. In addition, when a glass paste composition containing an acrylic resin is applied on a support film to form a film forming material layer, the flexibility of the formed film forming material layer is still insufficient.

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 that does not contain an aggregate of glass powder and does not generate the aggregate over time. A third object of the present invention is to provide a glass paste composition having excellent storage stability that does not generate cake-like deposits at the bottom of a storage container. A fourth object of the present invention is to provide a glass paste composition which does not cause film defects such as streak-like coating marks, craters and pinholes on a film-forming material layer formed by drying a coating film. is there. The fifth of the present invention
The object of the invention is to sinter the obtained film forming material layer to obtain a glass sintered body having a high light transmittance (for example, PDP).
To provide a glass paste composition that can form a dielectric layer). A sixth object of the present invention is to provide a glass paste composition that can be suitably used for producing a transfer film. A seventh object of the present invention is to provide a glass paste composition capable of producing a transfer film provided with a film-forming material layer having excellent flexibility. An eighth 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). .

[0012]

The glass paste composition of the present invention contains (A) a glass powder, (B) a binder resin, and (C) a silane coupling agent represented by the following general formula (1). It is characterized by having been done.

[0013]

Embedded image

(Wherein p is an integer of 3 to 20, m is 1 to 3)
, N is an integer of 1 to 3, and a is an integer of 1 to 3. )

[0015]

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, and a silane coupling agent 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> In the composition of the present invention, the binder resin is preferably an acrylic resin. Since the acrylic resin is contained as the binder resin, the formed film forming material layer has an excellent (heating) property with respect to the glass substrate.
Adhesiveness is exhibited. 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). . As such an acrylic resin, it is possible to bind a glass powder with an appropriate tackiness and to carry out a baking treatment (4
(00.degree. C. to 600.degree. C.). Such an acrylic resin includes a homopolymer of a (meth) acrylate compound represented by the following general formula (2), a copolymer of two or more (meth) acrylate compounds represented by the following general formula (2), And a copolymer of a (meth) acrylate compound represented by the following general formula (2) and a copolymerizable monomer.

[0018]

Embedded image

Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic compound. ]

Specific examples of the (meth) acrylate compound represented by the general formula (2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and 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, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Alkyl (meth) acrylates such as isostearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Rokishipuropiru (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3
Hydroxyalkyl (meth) acrylates such as -hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; phenoxyethyl (meth)
Phenoxyalkyl (meth) acrylates such as acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; 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 Recol (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl ( Examples thereof include cycloalkyl (meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate; benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Among these, in the above general formula (2), the group represented by R ² is preferably a group containing an alkyl group or an oxyalkyl group, and a particularly preferred (meth) acrylate compound is methyl (meth) acrylate. ,
Butyl (meth) acrylate, ethylhexyl (meth)
Acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate can be mentioned. The other copolymerizable monomer is not particularly limited as long as it is a compound copolymerizable with the above (meth) acrylate compound. For example, (meth) acrylic acid, vinyl benzoic acid, maleic acid, vinyl phthalic acid, etc. Unsaturated carboxylic acids; vinylbenzyl methyl ether, vinyl glycidyl ether,
Examples include a vinyl group-containing radically polymerizable compound such as styrene, α-methylstyrene, butadiene, and isoprene. In the acrylic resin constituting the composition of the present invention,
The amount of the copolymer component derived from the (meth) acrylate compound represented by the general formula (2) is usually 70% by weight or more, preferably 90% by weight or more, and more preferably 100% by weight.

The molecular weight of the acrylic resin constituting the composition of the present invention is preferably from 4,000 to 300,000, more preferably from 10,000 to 20 as a weight average molecular weight in terms of polystyrene by GPC.
0000. The content of the binder resin in the composition of the present invention is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the glass powder. If the ratio of the binder resin is too small, the glass powder cannot be securely bound and held.On the other hand, if the ratio is too large, a long time is required for the firing step or formation. The resulting glass sintered body (dielectric layer) may not have sufficient strength and film thickness.

<Silane Coupling Agent> The composition of the present invention is characterized in that it contains a silane coupling agent [saturated alkyl group-containing (alkyl) alkoxysilane] represented by the above general formula (1). have. In the above general formula (1), p indicating the number of carbon atoms of the saturated alkyl group is an integer of 3 to 20, preferably 4 to 16. Even if a saturated alkyl group-containing (alkyl) alkoxysilane having p less than 3 is contained, sufficient flexibility is not exhibited in the film-forming material layer formed by the obtained glass paste composition. On the other hand, the saturated alkyl group-containing (alkyl) alkoxysilane having a value of p exceeding 20 has a high decomposition temperature, and the organic substance (the silane derivative) is completely removed in the step of firing the film-forming material layer using the obtained glass paste composition. Since the glass powder is melted at a stage where it is not decomposed and removed, a part of the organic substance remains in the formed dielectric layer, and as a result, the light transmittance of the dielectric layer tends to decrease.

Specific examples of the silane coupling agent represented by the general formula (1) include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, and n-butyldimethylmethoxysilane.
Saturated alkyldimethylmethoxysilanes such as decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane and n-icosanedimethylmethoxysilane (a
= 1, m = 1, n = 1); n-propyldiethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane, etc. Saturated alkyldiethylmethoxysilanes (a =
1, m = 1, n = 2); saturated alkyldipropylmethoxy such as n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane Silanes (a = 1, m = 1, n = 3); n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n
Saturated alkyldimethylethoxysilanes (a = 1, m = 2, n = 1) such as hexadecyldimethylethoxysilane and n-icosanedimethylethoxysilane; n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-
Saturated alkyl diethyl ethoxy silanes (a = 1, m = 2, n = 2) such as hexadecyl diethyl ethoxy silane and n-icosane diethyl ethoxy silane; n-butyl dipropyl ethoxy silane, n-decyl dipropyl ethoxy silane , N-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane and other saturated alkyldipropylethoxysilanes (a = 1, m =
2, n = 3); saturated alkyldimethylpropoxysilanes such as n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, n-hexadecyldimethylpropoxysilane, and n-icosanedimethylpropoxysilane (A = 1, m = 3, n = 1); n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxy Saturated alkyldiethylpropoxysilanes such as silane (a = 1, m = 3, n = 2); n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n- Ikosan Saturated alkyl dipropyl propoxysilane such as propyl propoxysilane (a =
1, m = 3, n = 3);

N-propylmethyldimethoxysilane, n
Saturated alkylmethyldimethoxysilanes such as -butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane (a = 2, m = 1,
n = 1); n-propylethyldimethoxysilane, n-
Saturated alkylethyldimethoxysilanes such as butylethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, and n-icosaneethyldimethoxysilane (a = 2, m = 1, n
= 2); saturated alkylpropyldimethoxysilanes such as n-butylpropyldimethoxysilane, n-decylpropyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane (a = 2, m = 1, n = 3) Saturated alkylmethyl such as n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecylmethyldiethoxysilane, n-icosanemethyldiethoxysilane Diethoxysilanes (a = 2, m = 2, n = 1); n
Saturated alkylethyldiethoxysilanes such as -propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane and n-icosaneethyldiethoxysilane ( a = 2, m = 2, n = 2); n
Saturated alkylpropyldiethoxysilanes such as -butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanopropyldiethoxysilane (a =
2, m = 2, n = 3); n-propylmethyldipropoxysilane, n-butylmethyldipropoxysilane, n-
Saturated alkylmethyldipropoxysilanes such as decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane (a = 2, m = 3, n = 1); n-propylethyl Saturated alkylethyldipropoxysilanes such as dipropoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxysilane, n-hexadecylethyldipropoxysilane, and n-icosaneethyldipropoxysilane (a = 2 , M = 3, n = 2); n-
Saturated alkyl propyl dipropoxy silanes such as butyl propyl dipropoxy silane, n-decyl propyl dipropoxy silane, n-hexadecyl propyl dipropoxy silane, n-icosane propyl dipropoxy silane (a = 2, m = 3, n = 3);

Saturated alkyltrimethoxysilanes such as n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane and n-icosanetrimethoxysilane (a = 3 , M = 1); saturated alkyltriethoxysilanes such as n-propyltriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane ( a = 3, m = 2); saturated alkyl tripropoxy such as n-propyl tripropoxy silane, n-butyl tripropoxy silane, n-decyl tripropoxy silane, n-hexadecyl tripropoxy silane, and n-icosane tripropoxy silane Silanes (a = 3, m = ) And the like can be illustrated, these may be used alone or in combination of two or more.

Of these, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-butyltrimethoxysilane
Butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-butyltripropoxysilane, n
-Decyltripropoxysilane, n-hexadecyltripropoxysilane and the like are particularly preferred.

The above general formula (1) in the composition of the present invention
As the content ratio of the silane coupling agent represented by,
It is preferably 0.001 to 10 parts by weight, more preferably 0.001 part by weight, based on 100 parts by weight of the glass powder.
1 to 5 parts by weight. If the proportion of the silane coupling agent is too small, the effect of improving the dispersion stability of the glass powder and the effect of improving the flexibility of the formed film-forming material layer cannot be sufficiently exhibited. On the other hand, when this ratio is excessive, the viscosity increases with time when the obtained glass paste composition is stored, or a reaction occurs between the silane coupling agents, thereby lowering the light transmittance after firing. It may cause.

<Solvent> The composition of the present invention usually contains a solvent. As the solvent, an affinity with glass powder, good solubility of a binder resin, can impart a suitable viscosity to the glass paste composition, and can be easily evaporated and removed by drying. Is preferred. Specific examples of such a solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone and cyclohexanone; n-pentanol, 4-methyl-2
Alcohols such as pentanol, cyclohexanol and diacetone alcohol; ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether;
Alkyl esters of saturated aliphatic monocarboxylic acids such as n-butyl acetate and amyl acetate; ethyl lactate, lactic acid-n-
Lactic acid esters such as butyl; ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and ethyl-3-ethoxypropionate; More than one species can be used in combination. The content of the solvent in the composition of the present invention is preferably 5 to 50 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the glass powder, from the viewpoint of maintaining the viscosity of the composition in a suitable range. It is 10 to 40 parts by weight.

In the glass paste composition of the present invention, in addition to the above essential components, various additives such as a tackifier, a plasticizer, a surface tension regulator, a stabilizer, an antifoaming agent and a dispersant are optional. It may be contained as a component. As an example of a preferred glass paste composition, as a glass powder, 100 parts by weight of a mixture composed 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, and polybutyl methacrylate ( Acrylic resin)
A composition containing 30 parts by weight, 0.1 to 10 parts by weight of n-decyltrimethoxysilane (silane coupling agent), and 10 to 50 parts by weight of propylene glycol monomethyl ether (solvent) as essential components may be mentioned. it can.

The composition of the present invention is prepared by kneading the above-mentioned glass powder, binder resin, solvent and optional components using a kneader such as a roll kneader, a mixer, a homomixer, a ball mill or a bead mill. Can be. The composition of the present invention prepared as described above is a paste-like composition having fluidity suitable for application,
The viscosity is usually from 1,000 to 30,000 cp, preferably from 3,000 to 10,000 cp.

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.

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

[0035]

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 70 wt%, boron oxide 10 _{wt%, PbO-B 2 O 3} -Si having a composition of silicon oxide 20 wt%
Acrylic resin (polystyrene conversion by GPC) obtained by copolymerizing 100 parts of an O ₂ -based mixture (softening point 500 ° C.) and butyl methacrylate (70% by weight) and methyl methacrylate (30% by weight) as a binder resin Weight average molecular weight: 80,000, hereinafter referred to as "acrylic resin A") 20 parts, 1 part of n-butyltrimethoxysilane as a silane coupling agent, and 20 parts of propylene glycol monomethyl ether as a solvent are kneaded using a disperser. Thus, a composition of the present invention having a viscosity of 5,000 cp was prepared.

(2) Evaluation of Storage Stability of Composition The composition of the present invention prepared in the above (1) was housed in a container, and the container was left in a constant temperature bath at 40 ° C. for 30 days. Next, when the bottom of the container was observed, no cake-like deposits or the like were observed at all, and the composition was excellent in storage stability.

(3) Production of transfer film: A support film (width 400 mm, length 30 m, thickness 38 μm) made of polyethylene terephthalate (PET), which has been prepared by subjecting the composition of the present invention prepared in the above (1) to release treatment. ) Was applied using a blade coater.
The solvent was removed by drying at 5 ° C. for 5 minutes, thereby producing a transfer film having a 50 μm-thick film-forming material layer formed on a support film.

(4) Evaluation of Transfer Film: The surface state of the film-forming material layer of the transfer film produced in the above (3) was observed using a microscope. No film defects such as craters and pinholes were observed. Even when the transfer film was bent, no cracks (bending cracks) occurred on the surface of the film-forming material layer, and the film-forming material layer had good flexibility.

(5) Transfer of the film forming material layer: manufactured in the above (3) such 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.

(6) Firing the film-forming material layer (forming the dielectric layer): The glass substrate on which the film-forming material layer has been transferred and formed according to the above (5) is placed in a firing furnace, and the temperature in the furnace is set to room temperature. To 550 ° 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.

(7) Evaluation of dielectric layer: The thickness (average thickness and tolerance) of this dielectric layer was measured to be 30 μm ±
The thickness was in the range of 0.5 μm, and the uniformity of the film thickness was excellent. In addition, 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 measured to be 92%. It was confirmed that the composition had excellent transparency.

<Examples 2 to 9> A glass paste composition of the present invention was prepared in the same manner as in Example 1 except that the silane coupling agent 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. To the dielectric layer (thickness 30μm ±
0.5 μm).

For each of the compositions according to Examples 2 to 9, the storage stability of the composition (presence or absence of cake-like deposits at the bottom of the storage container) was determined in the same manner as in Example 1.
The surface condition of the film-forming material layer formed by the composition (the presence or absence of film defects such as glass powder agglomerates, streaky coating marks, craters and pinholes), and the flexibility of the film-forming material layer (when bent) Of the film-forming material layer was evaluated for transferability (heat adhesion to a glass substrate), and the light transmittance of the formed dielectric layer was measured. Table 1 shows the results.

Comparative Example 1 A comparative glass paste composition was prepared in the same manner as in Example 1 except that the silane coupling agent was not used, according to the formulation shown in Table 2, and the composition was prepared. A transfer film is manufactured using the transfer film, and the film forming material layer is transferred and baked using the transfer film, so that a dielectric layer (thickness: 30 μm ± 1) is formed on the surface of a glass substrate for a 20-inch panel. .5 μm)
Was formed. Example 1 of the composition according to Comparative Example 1
In the same manner as above, when the storage stability of the composition was evaluated,
A cake-like hard deposit was observed at the bottom of the storage container, and this composition was inferior in storage stability. When the surface state of the film-forming material layer formed using the composition was observed using a microscope, the surface state was 20 to 100 μm.
A large number of glass powder aggregates and craters having the aggregates as nuclei were observed. Further, this transfer film has poor flexibility, and when the transfer film is bent, cracks (bending cracks) occur on the surface of the film-forming material layer, and the film-forming material layer does not have good flexibility. Did not. According to the transfer film according to Comparative Example 1, the film forming material layer constituting the transfer film can be transferred to the surface of the glass substrate, and the dielectric layer formed through the baking treatment of the film forming material layer can be transferred. The light transmittance was 90%. Table 2 summarizes the above results.

<Comparative Example 2> According to the formulation shown in Table 2, n
A glass paste composition for comparison was prepared in the same manner as in Example 1 except that 1 part of trimethylmethoxysilane was used instead of -butyltrimethoxysilane, and a transfer film was produced using the composition. By transferring the film-forming material layer using the transfer film and performing a baking process, a dielectric layer (thickness: 30 μm ± 1.0 μm) was formed on the surface of a glass substrate for a 20-inch panel.
When the storage stability of the composition according to Comparative Example 2 was evaluated in the same manner as in Example 1, no cake-like deposits were observed, and the composition was excellent in storage stability. Was what it was. In addition, when the surface state of the film-forming material layer formed by the composition was observed using a microscope, no film defects such as agglomerates of glass powder, streaky coating marks, craters, and pinholes were found. . However, this transfer film has poor flexibility, and when the transfer film is bent, cracks (bending cracks) occur on the surface of the film forming material layer, and the film forming material layer does not have good flexibility. Did not. According to the transfer film according to Comparative Example 2, the film forming material layer constituting the transfer film can be transferred to the surface of the glass substrate, and the dielectric layer formed through the firing treatment of the film forming material layer can be transferred. The light transmittance was 92%. Table 2 summarizes the above results.

<Comparative Example 3> According to the formulation shown in Table 2, n
Example 1 except that 1 part of n-tetracosanetrimethoxysilane was used instead of -butyltrimethoxysilane.
In the same manner as above, a glass paste composition for comparison is prepared, a transfer film is manufactured using the composition, and the transfer of the film-forming material layer and the baking treatment are performed using the transfer film. , Dielectric layer (thickness 30μm ± 1.0μm) on the surface of glass substrate for 20 inch panel
Was formed. When the storage stability of the composition of Comparative Example 3 was evaluated in the same manner as in Example 1, no cake-like deposits were observed, and the composition was excellent in storage stability. Was what it was. In addition, when the surface state of the film-forming material layer formed by the composition was observed using a microscope, no film defects such as agglomerates of glass powder, streaky coating marks, craters, and pinholes were found. . Even when the transfer film according to Comparative Example 3 is bent, no crack (bending crack) occurs on the surface of the film forming material layer, and the film forming material layer has good flexibility. The film forming material layer constituting this was transferred to the surface of the glass substrate. However, the light transmittance of the dielectric layer formed through the baking treatment of the film forming material layer was 70%, which was inferior in transparency. Table 2 summarizes the above results.

<Comparative Example 4> According to the formulation shown in Table 2, n
N- (2-aminoethyl) 3-aminopropyltrimethoxysilane 0.5 instead of -butyltrimethoxysilane
A glass paste composition for comparison was prepared in the same manner as in Example 1 except that a part was used, a transfer film was manufactured using the composition, and a film-forming material layer was formed using the transfer film. Was transferred and baked to form a dielectric layer (thickness: 30 μm ± 1.5 μm) on the surface of a glass substrate for a 20-inch panel. When the storage stability of the composition according to Comparative Example 4 was evaluated in the same manner as in Example 1, no cake-like deposit was observed, and the composition was excellent in storage stability. Was what it was. When the surface state of the film-forming material layer formed by the composition was observed using a microscope,
No film defects such as glass powder agglomerates, streaky coating marks, craters and pinholes were observed. Further, even when the transfer film according to Comparative Example 4 is bent, no cracks (bending cracks) occur on the surface of the film forming material layer, and the film forming material layer has good flexibility. The film forming material layer constituting this was transferred to the surface of the glass substrate. However, the light transmittance of the dielectric layer formed through the baking treatment of the film forming material layer was 60%, which was inferior in transparency. Table 2 summarizes the above results.

<Comparative Example 5> According to the formulation shown in Table 2, n
A glass paste composition for comparison was prepared in the same manner as in Example 1 except that 1 part of 3-glycidoxypropyltrimethoxysilane was used instead of -butyltrimethoxysilane, and the composition was used. A transfer film is manufactured by using the transfer film, and the film forming material layer is transferred and baked using the transfer film, so that a dielectric layer (thickness: 30 μm ± 1.
0 μm). When the storage stability of the composition of Comparative Example 5 was evaluated in the same manner as in Example 1, no cake-like deposits were observed, and this composition was excellent in storage stability. Was what it was. Also,
When the surface state of the film-forming material layer formed by the composition was observed using a microscope, an aggregate of glass powder,
No film defects such as streak-like paint marks, craters and pinholes were found. However, this transfer film has poor flexibility, and when the transfer film is bent, cracks (bending cracks) occur on the surface of the film forming material layer, and the film forming material layer does not have good flexibility. Did not. According to the transfer film of Comparative Example 5, the film forming material layer constituting the transfer film could be transferred to the surface of the glass substrate, but the dielectric film formed through the baking treatment of the film forming material layer was used. The light transmittance of the layer is 70%,
The transparency was poor. Table 2 summarizes the above results.

Comparative Example 6 Lead oxide 7 was used as the glass powder.
100 parts of a PbO—B ₂ O ₃ —SiO ₂ mixture (softening point: 500 ° C.) having a composition of 0% by weight, boron oxide 10% by weight, and silicon oxide 20% by weight, and ethyl cellulose (polystyrene conversion by GPC) as a binder resin (Weight average molecular weight of 300,000) and 20 parts of α-terpineol as a solvent were kneaded using a dispersing machine to prepare a comparative glass paste composition having a viscosity of 50,000 cp. Was used to produce a transfer film. Example 1 of the composition according to Comparative Example 6
In the same manner as above, when the storage stability of the composition was evaluated,
No cake-like deposits were observed, and the composition was excellent in storage stability. In addition, when the surface state of the film-forming material layer formed by the composition was observed using a microscope, no film defects such as agglomerates of glass powder, streaky coating marks, craters, and pinholes were found. . However, this transfer film has poor flexibility, and when the transfer film is bent, cracks (bending cracks) occur on the surface of the film forming material layer, and the film forming material layer does not have good flexibility. Did not. Further, using this transfer film, an attempt was made to transfer the film-forming material layer to the surface of the glass substrate under the same pressure bonding conditions as in Example 1, but the film-forming material layer could not be transferred. Table 2 summarizes the above results.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

According to the composition of the present invention, the following effects can be obtained. (1) The composition of the present invention is excellent in dispersion stability of glass powder, and does not generate aggregates of glass powder. (2) The composition of the present invention has excellent storage stability. Even when the composition of the present invention is stored for a long period of time, the glass powder does not settle and deposit on the bottom of the container. (3) A uniform film forming material layer without film defects can be formed. (4) A film-forming material layer having excellent adhesion to a glass substrate can be formed. (5) A glass sintered body (dielectric layer of PDP) having high light transmittance can be formed. (6) It can be suitably used for the production of a transfer film. (7) A film-forming material layer having excellent flexibility can be formed on a support film. (8) Transferability of film forming material layer (transferability to glass substrate)
It is possible to produce a transfer film excellent in quality.

[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, and (C) a silane coupling agent represented by the following general formula (1). Embedded image (In the formula, p is an integer of 3 to 20, m is an integer of 1 to 3, n is an integer of 1 to 3, and a is an integer of 1 to 3.)