JPH10182919A - Composition for transparent dielectric layer, glass substrate with transparent dielectric layer formed by using the same, and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for transparent dielectric layer, having good adhesion to a glass substrate, further having adhesion even after a firing step, capable of forming a transparent dielectric layer having a constant thickness and high quality by a simple method and one step operation by including a polymethacrylate and a glass powder. SOLUTION: This composition for transparent dielectric layer comprises (A) 10-60wt.% polymethacrylate and (B) 40-90wt.% glass powder having 0.5-30μm average particle diameter based on the total weight of the components A and B. Preferably, the component A is polylauryl methacrylate, etc., the component B is PbO-B2 O3 -SiO2 -based glass, and ethanol, etc., are used as a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a transparent dielectric layer, and more particularly to a glass substrate having a transparent dielectric layer formed by using the composition, and a method for producing the glass substrate.

[0002]

2. Description of the Related Art Display devices include liquid crystal displays, electroluminescent displays, and plasma display panels. Each display material, the dielectric layer, requires a coating that is transparent, uniform, and smooth. Conventional coating methods include screen printing. This involves forming a dielectric layer by repeating the operation of coating and firing a resin containing glass powder on a substrate 3 to 8 times.

However, since this method is a so-called wet method, there is a limit to the film thickness that can be formed at a time, and it takes a long time to repeat the operation of volatilizing the solvent after coating the resin and coating the resin. In addition, there is a possibility that the solvent remains, which adversely affects the layer and increases the cost.

Accordingly, a dispersion containing a glass frit or a vitrizable substance is formed on a belt or a film to form a green sheet containing a glass frit or a vitrizable mineral, and the green sheet is placed on a ceramic substrate. There has been proposed a method of manufacturing a glazed ceramic substrate in which a glass layer is formed on a ceramic substrate by press-bonding and heating and melting and fixing the glass layer (Japanese Patent Application Laid-Open No. 61-22682).

However, according to this method, there is a problem that the adhesion between the green sheet and the ceramic substrate is weak. To improve this, there is a method of increasing the amount of the binder resin added or lowering the Tg of the binder resin. Conceivable. However, when the added amount of the binder resin is increased, the packing density of the glass frit decreases, so that pinholes are easily generated at the time of firing, and the T
When g is reduced, there is a problem that the strength of the green sheet is reduced and handling is difficult. Further, since the green sheet is pressed against the ceramic substrate by the binder resin, the adhesive strength is reduced before the binder resin disappears at the time of temperature rise in the subsequent firing step, and the edge of the glaze shrinks. Was.

Further, in order to solve these problems, a powder sheet containing glass frit and a binder as main components and, if necessary, an inorganic powder is added, and the powder sheet is coated via a pressure-sensitive adhesive layer. Coating methods have been proposed in which pressure lamination is performed on an object to be heated and then firing is carried out (JP-A-63-197640 and JP-A-64-73).
No. 086).

However, in these methods, first, it is necessary to separately provide an extra pressure-sensitive adhesive layer. This requires extra materials and their preparation,
Further, a step for providing this pressure-sensitive adhesive layer is further required, and complications in the manufacturing process have been inevitable.

Further, the pressure-sensitive adhesive layer is interposed between the ceramic substrate and the layer constituting the glass coating, and may be used in a case where the pressure-sensitive adhesive component is thermally decomposed in a subsequent firing step. In this case, it is sufficiently predicted that the decomposition gas generated thereby causes blistering or the like of the glass layer, thereby lowering the quality of the dielectric product such as transparency.

[0009]

SUMMARY OF THE INVENTION The present invention has good adhesion to a glass substrate without providing an extra pressure-sensitive adhesive layer, and still has adhesion even after a firing step. A composition for a transparent dielectric layer capable of forming a high-quality transparent dielectric layer of a certain thickness in a single operation on a glass substrate in a simple manner, a glass substrate having a transparent dielectric layer formed using this composition, and It is intended to provide a manufacturing method.

[0010]

In order to solve the above-mentioned problems, the present invention provides a method for producing polymethacrylic acid based on the total weight of polymethacrylic acid ester and glass powder having an average particle size of 0.5 to 30 μm. 10 to 60% by weight of ester and glass powder 40 to 90 having an average particle size of 0.5 to 30 μm
An object of the present invention is to provide a composition for a transparent dielectric layer, characterized in that the composition comprises a weight percent.

The present invention also relates to a polymethacrylic acid ester based on the total weight of the polymethacrylic acid ester and glass powder having an average particle size of 0.5 to 30 μm.
A transparent dielectric layer formed on a glass substrate using a composition for a transparent dielectric layer containing 60% by weight and 40 to 90% by weight of glass powder having an average particle size of 0.5 to 30 μm. It is to provide a layer-formed glass substrate.

Further, the present invention provides a method for preparing a polymethacrylic acid ester based on the total weight of polymethacrylic acid ester and glass powder having an average particle size of 0.5 to 30 μm.
A transparent dielectric layer-forming glass, comprising: forming a dry film of a mixture containing 40 to 90% by weight of a glass powder having an average particle size of 0.5 to 30% by weight and attaching to a glass substrate, followed by firing. It is to provide a method for manufacturing a substrate.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail.

The composition for a transparent dielectric layer of the present invention employs a specific polymer called polymethacrylic acid ester. Examples of the polymer include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, and the like. Polybutyl methacrylate, polybutyl methacrylate, isobutyl methacrylate, lauryl polymethacrylate, 2-ethylhexyl polymethacrylate, and the like are used, preferably lauryl polymethacrylate, 2-ethylhexyl polymethacrylate, and more preferably lauryl polymethacrylate. It is.

The present invention also employs a specific glass powder.
-B ₂ O ₃ -SiO ₂ based _{glass, Na 2 O-B 2 O} 3 -
SiO ₂ glass, BaO-CaO-SiO ₂ based _{glass, PbO-ZnO-B 2 O} 3 -SiO 2 based glass or the like is used, _{preferably, PbO-ZnO-B 2 O} 3 -S
iO ₂ -based glass and PbO-B ₂ O ₃ -SiO ₂ -based glass, more preferably PbO-ZnO-B ₂ O _3-
It is a SiO ₂ glass.

The average particle size of the glass powder is 0.1.
5 to 30 μm, preferably 2 to 15 μm
m, more preferably 3 to 10 μm. If the average particle size of the glass powder is 30 μm or more, it is difficult to melt, so that it becomes a crumple after firing, and if it is 0.5 μm or less, secondary aggregation after dispersion is undesirably caused.

The mixing ratio of the polymethacrylate and the glass powder is 10 to 60% by weight of the polymethacrylate and 40 to 90% by weight of the glass powder based on the total weight of the polymethacrylate and the glass powder. And preferably polymethacrylate 10
-30% by weight and 70-90% by weight of glass powder, more preferably 20-30% by weight of polymethacrylate and 70-80% by weight of glass powder. If the polymethacrylic acid ester is at least 60% by weight, foaming will occur during firing, and if it is at most 10% by weight, the effect of the pressure-sensitive adhesive will be reduced.

Examples of the solvent used for obtaining the dispersion of the polymethacrylic acid ester and glass powder used in the present invention include common organic solvents such as ethanol, butanol, toluene, benzene, methyl ethyl ketone, chloroform, dimethyl sulfoxide, and ethyl acetate. Can be used. Among these solvents, toluene, ethyl acetate and methyl ethyl ketone are particularly preferred. In addition, additives can be used as needed. As the additive, a crosslinking agent, a dispersant, a tackifier, and the like can be used as appropriate. Crosslinking agents, for the purpose of improving cohesion, etc., for example, there are isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, metal chelate-based crosslinking agents, and the like, dispersing agents, for example, surfactants, palmitic acid, There are fatty acids such as stearic acid and oleic acid, fatty acid esters, acrylic oligomers and the like. For the purpose of imparting tackiness, tackifiers include, for example, rosin ester type, hydrogenated rosin ester type, terpene phenol type, petroleum There are resin type, rosin phenol type and the like.

Further, other additives can be added as long as they do not adversely affect the quality of the transparent dielectric layer of the present invention.

In the present invention, the mixer for obtaining the dispersion is a ball mill or a wet pulverizer, which is operated under a closed condition to obtain a uniform dispersion of the polymethacrylate and the glass powder.

The uniform dispersion is coated on a plastic film as a carrier film using a coater to form a uniform layer having a thickness of 50 to 500 μm. Drying at 0 ° C. gives a dry film which also has a uniform thickness.
Thereafter, a plastic film, which is a protective film, is attached to the surface opposite to the attachment surface of the carrier film, and cured in this state for several days. Next, the protective film is peeled off and attached to a glass substrate. The polymethacrylic acid ester in the dry film of the present invention is not only a binder but also a pressure-sensitive adhesive, and exhibits an adhesive property, so that it can be accurately attached to a glass substrate by a simple attaching operation. After sticking, the carrier film is peeled off and fired in a firing furnace. The firing temperature is usually 500 to 1400 ° C, but in the present invention, it is particularly preferable to fire at 500 to 600 ° C.

[0022]

EXAMPLES Examples of the present invention will be described.
The present invention is not limited to this embodiment.

Example 1 Dispersion material Polyuryl lauryl methacrylate 200 g Glass powder 800 g PbO-ZnO-B ₂ O ₃ -SiO ₂ Particle size 3-10 μm Ethyl acetate solvent 400 g Rosin-based resin tackifier 10 g The mixture was placed in a mixer and mixed for 30 minutes in a closed system to obtain a uniform dispersion.

This was applied onto a 75 μm-thick carrier film PET having a width of 500 m and a length of 200 m using a roll coater at a speed of 4 m / sec to a uniform thickness of 200 μm. Then, using a dryer, the temperature was 9
After drying at 0 ° C. for 2 minutes, a dry film having a uniform thickness of 50 μm was obtained. Then, a protective film (PET 38 μm) is applied to the surface opposite to the surface to which the carrier film is attached.
Was affixed and cured as it was for 7 days. Next, the protective film was peeled off on a glass substrate of SiO _{2 having} a width of 70 mm and a length of 150 mm, and was adhered to the glass surface.

The degree of adhesion of the dry film to the glass substrate at this time was 100 g / φ5 mm as measured by the probe tack method.

After the carrier film was peeled off, it was fired in an electric furnace at a firing temperature of 590 ° C. for 30 minutes. As a result, a transparent dielectric layer was formed on the glass substrate. The shape after firing, the shape of the adherend (float glass plate), the sedimentation of the glass after gluing,
And the film forming property was good. These properties are listed in Table 1.

Example 2 Dispersion Material Polyuryl lauryl methacrylate 300 g Glass powder 700 g PbO-ZnO-B ₂ O ₃ -SiO ₂ Particle size 3-10 μm Ethyl acetate solvent 400 g Rosin-based resin tackifier 10 g In the same manner, a dry film was produced, then adhered to the glass surface and then fired. The properties of the thus obtained are described in Table 1.

Example 3 Dispersion material Polyuryl lauryl methacrylate 100 g Glass powder 900 g PbO-ZnO-B ₂ O ₃ -SiO ₂ Particle size 3-10 μm Ethyl acetate solvent 400 g Rosin resin tackifier 10 g In the same manner, a dry film was produced, then adhered to the glass surface and then fired. The properties of the thus obtained are described in Table 1.

Example 4 Dispersion material Polyethyl 2-ethylhexyl methacrylate 200 g Glass powder 800 g PbO-ZnO-B ₂ O ₃ -SiO ₂ Particle size 3-10 μm Ethyl acetate solvent 400 g Rosin resin tackifier 10 g A dry film was produced in the same manner as in No. 1, and then adhered to the glass surface and baked. The properties of the thus obtained are described in Table 1.

Example 5 Dispersion material Polyuryl lauryl methacrylate 200 g Glass powder 800 g PbO-ZnO-B ₂ O ₃ -SiO ₂ Particle size 10-20 μm Ethyl acetate solvent 400 g Rosin-based resin tackifier 10 g In the same manner, a dry film was produced, then adhered to the glass surface and then fired. The properties of the thus obtained are described in Table 1.

Example 6 Dispersion Material Polyuryl lauryl methacrylate 200 g Glass powder 800 g PbO-ZnO-B ₂ O ₃ -SiO ₂ Particle size 0.5-5 μm Ethyl acetate solvent 400 g Rosin-based resin tackifier 10 g A dry film was produced in the same manner as in No. 1, and then adhered to the glass surface and baked. The properties of the thus obtained are described in Table 1.

Example 7 A dry film was produced from the same mixture as in Example 1 in the same manner as in Example 1, and then adhered to the glass surface.
Firing at 600 ° C. for 30 minutes. The properties of the thus obtained are described in Table 1.

Example 8 A dry film was produced from the same mixture as in Example 1 in the same manner as in Example 1, and then adhered to the glass surface.
Baking was further performed at 580 ° C. for 30 minutes. The properties of the thus obtained are described in Table 1.

Comparative Example 1 For comparison with the example, a dry film was produced in the same manner as in the example 1 except that the ratio of the resin to the glass powder was changed as follows, and then the dry film was formed on the glass surface. Affixed and fired. The properties of the thus obtained are described in Table 2.

Dispersion material Polyuryl lauryl methacrylate 700 g Glass powder 300 g PbO--ZnO--B ₂ O ₃ --SiO ₂ Particle size 3-10 μm Ethyl acetate solvent 400 g Rosin-based resin tackifier 10 g Comparative Example 2 For comparison with Example 2 Then, a dry film was produced in the same manner as in Example 1 with a composition in which the ratio of the resin to the glass powder was changed as described below, and then affixed according to the glass surface, followed by firing. The properties of the thus obtained are described in Table 2.

Dispersion Material Polyuryl lauryl methacrylate 50 g Glass powder 950 g PbO-ZnO-B ₂ O ₃ -SiO ₂ Particle size 3-10 μm Ethyl acetate solvent 400 g Rosin-based resin tackifier 10 g Comparative Example 3 For comparison with Example 3 Then, change the particle size of the glass powder,
A dry film was produced in the same manner as in Example 1 with the composition shown below, and was then adhered to the glass surface and fired. The properties of the thus obtained are described in Table 2.

Dispersion material Polyuryl lauryl methacrylate 200 g Glass powder 800 g PbO-ZnO-B ₂ O ₃ —SiO ₂ Particle size> 30 μm Ethyl acetate solvent 400 g Rosin-based resin tackifier 10 g Comparative Example 4 For comparison with Example 4 , By changing the particle size of the glass powder,
A dry film was produced in the same manner as in Example 1 with the composition shown below, and was then adhered to the glass surface and fired. The properties of the thus obtained are described in Table 2.

Dispersion material Polyuryl lauryl methacrylate 200 g Glass powder 800 g PbO-ZnO-B ₂ O ₃ -SiO ₂ Particle size <0.5 μm Ethyl acetate solvent 400 g Rosin-based resin tackifier 10 g The results of Examples and Comparative Examples were Tests and judgment methods are shown below for each evaluation item in Tables 1 and 2 shown below.

Shape after firing The surface shape of the formed transparent dielectric layer after firing was visually checked.

A: Good B: Almost good C (foaming): Resin foams at the time of baking and there is a portion without a dielectric layer C (Yuzu skin): Glass powder cannot be completely melted and the surface of the dielectric layer is smooth The probe tack was measured by a method according to ASDM D2979.

Settled glass after gluing The dispersion in which the glass and the resin were mixed was allowed to stand, and the ease of settling of the glass was visually checked.

A: good B (slightly settled when left for a long time): slightly settled, but returned to a good state by re-stirring B (slightly secondary coagulation): slightly secondary-coagulated, but returned to a good state by re-stirring C (Sedimentation): Sedimentation starts immediately after stirring and considerable re-stirring time is required if left for a long period of time. C (Secondary agglomeration): A glass film that causes secondary agglomeration and requires re-dispersion along with re-agitation. The film forming property of the mixture of glass and resin formed into a functional dry film was confirmed by a sensory test.

A: good B: almost good C (no film-forming property): shape of a fired adherend (float glass plate) that cannot be formed into a dry film and has no cohesive force ( firing glass plate) The degree of deformation of the float glass plate) was visually checked.

A: Good overall evaluation The above test was comprehensively evaluated.

A: good B: almost good (usable) C: bad (unusable)

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

As described above, according to the present invention,
It can be used for the dielectric layer, which is the display material of the display device, and has good adhesion to the glass substrate, especially without any extra pressure-sensitive adhesive layer, and without special pressure bonding or heating. In a simpler method, a high-quality transparent dielectric layer having a constant thickness can be provided on a glass substrate by a single operation. According to the present invention, such a composition for a transparent dielectric layer,
It becomes possible for the first time to provide a glass substrate on which a transparent dielectric layer is formed using the composition and a method for producing a glass substrate on which a transparent dielectric layer is formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 23/31

Claims (3)

[Claims] 1. A polymethacrylic acid ester having an average particle diameter of 0.5 to 30 μm, based on the total weight of the polymethacrylic acid ester and a glass powder having an average particle diameter of 0.5 to 30 μm. Glass powder of 40 to 90
A composition for a transparent dielectric layer, comprising: 2. 10 to 60% by weight of a polymethacrylic acid ester and an average particle size of 0.5 to 30 μm, based on the total weight of the polymethacrylic acid ester and glass powder having an average particle size of 0.5 to 30 μm. Glass powder of 40 to 90
A transparent dielectric layer-formed glass substrate, wherein a transparent dielectric layer is formed on a glass substrate using a composition for a transparent dielectric layer containing about 10% by weight. 3. A polymethacrylic acid ester having an average particle diameter of 0.5 to 30 μm and a polymethacrylic acid ester having an average particle diameter of 0.5 to 30 μm based on the total weight of the polymethacrylic acid ester and the glass powder having an average particle diameter of 0.5 to 30 μm. Glass powder of 40 to 90
What is claimed is: 1. A method for producing a glass substrate having a transparent dielectric layer, comprising: forming a dry film of a mixture containing a weight percent of the mixture, attaching the mixture to a glass substrate, and firing the mixture.