JPS63260838A - Glass powder adhesive sheet and production of substrate glazed ceramic using said sheet - Google Patents

Abstract

PURPOSE:To form a glazed layer having uniform thickness on a substrate in high precision and in high yield, by thermally bonding a sheet through a given thermoplastic resin layer formed on the surface of a glass powder molded sheet to a ceramic substrate under pressure and calcining. CONSTITUTION:A thermoplastic resin comprising a mixture of a substance showing pressure-sensitive adhesiveness at normal temperature and a thermally melting resin or a thermally reactive resin is prepared. A glass powder molded sheet consisting essentially of an organic binder having a thermal decomposition temperature lower than that of the thermoplastic resin and glass frit is formed. The thermoplastic resin layer is laminated to the surface of the glass powder molded sheet to form a glass powder adhesive sheet. The glass powder adhesive sheet is piled through the resin layer on the surface of a ceramic substrate, heated, pressurized and calcined to give a glazed ceramic substrate.

Description

[Detailed description of the invention] <Field of industrial application> The present invention relates to a glass powder adhesive sheet useful for manufacturing glazed ceramic substrates used for thermal heads, electronic circuit boards, etc., and a glazed ceramic substrate using the sheet. This relates to the manufacturing method.

<Prior art and its problems> A glazed ceramic substrate is one in which molten glass is uniformly and thinly formed on the surface of a ceramic substrate.
It is mainly used in thermal heads, hybrid ICs, etc.

The thin film circuit formed on the glazed ceramic substrate surface is 1
It is usually formed by patterning a thin film formed by a vacuum lidding method, sputtering method, etc. by photolithography.

Therefore, for the molten glass layer (glaze layer), the thickness and positional accuracy are important, but in order to improve the accuracy of one circuit, the surface flatness is especially important.

Hitherto, the glaze layer has generally been formed by applying a paste-like material made of glass frit and a vehicle to the surface of a ceramic substrate by screen printing and firing the paste.

However, with this method, it is difficult to form the desired thickness in a single operation.

It is complicated because it requires multiple coating operations, and the coating thickness is not accurate enough, and it also traps air bubbles during coating and makes the screen visible! !
The disadvantage is that surface defects occur due to the hardening.

Therefore, a method has recently been proposed in which a glass powder sheet containing glass frit and an organic binder as main components is pressed onto a ceramic substrate surface using a roller and then fired (Japanese Unexamined Patent Publication No. 61-22682). ).

In this proposed method, due to insufficient adhesion between the ceramic substrate and the molded glass powder sheet, the adhesion is lost before the organic binder disappears when the temperature is increased during the firing process, and the glaze is therefore lost. There is a disadvantage that the end of j■ shrinks and the thickness of the end becomes thicker. This drawback is not so much of a problem when glaze III is formed over the entire surface and the thickened edges are cut off, but it becomes a serious problem when the glaze layer is formed in a pattern.

Therefore, in order to increase the adhesion with the two-ceramic substrate, there are two methods: increasing the amount of organic binder added, and using a substance with a low glass transition temperature (T, !i') as the binder. The latter method reduces the packing density of the glass frit in the glass powder molded sheet, which tends to cause pinholes during firing, and the latter method reduces the physical strength of the molded sheet, making it difficult to handle. It was.

<Purpose of the Invention> The present invention provides a glass powder adhesive sheet that can form a glaze nodule of uniform thickness on the surface of a ceramic substrate with high accuracy and high yield, and that can be automated, and a method for manufacturing a glazed ceramic substrate using the sheet. In addition, it is an object of the present invention to provide the above-mentioned sheet and manufacturing method which does not cause an increase in hness due to shrinkage at the edges even when a glaze 1il is formed in a pattern.

Means for Solving the Problems In order to solve the problems of the prior art, the inventors of the present invention have conducted intensive research and found that a glass powder molded sheet exhibits good adhesion to the surface by heating and pressing. The inventors discovered that the desired glazed ceramic substrate could be obtained by forming a thermoplastic resin layer by laminating, thermo-compressing it to the ceramic substrate surface through the resin mt-layer, and firing it.This led to the completion of the present invention. This is what we have come to.

That is, two aspects of the present invention are a glass powder adhesive sheet in which a thermoplastic resin layer is laminated on the surface of a glass powder molded sheet containing glass frit and an organic binder as main components, and a glass powder adhesive sheet in which a thermoplastic resin layer is laminated on the surface of a ceramic substrate. After overlapping via /il and heating and pressurizing.

The present invention relates to a method for manufacturing a glazed ceramic substrate to be fired.

According to the present invention, since the adhesive sheet is constructed by laminating a glass powder molded sheet molded to a uniform thickness and a thermoplastic resin layer having a uniform thickness, the adhesive sheet is laminated on the ceramic substrate surface. Even when the sheet is fired, the sheet does not shrink during the firing process, and the desired pattern can be obtained with high precision. Furthermore, in the production of glazed ceramic substrates, it is possible to obtain a composite of the sheet and the substrate by overlapping the adhesive sheet and the ceramic substrate and continuously subjecting them to heating and pressing conditions such as between heated rolls. This makes it possible to automate production lines.

<Structure and operation of the invention> The glass powder adhesive sheet of the present invention comprises a glass powder molded sheet containing glass frit and an organic binder as main components;
It is composed of a thermoplastic resin layer.

As the glass frit, coating glass such as Pb0-BzOs-8to2 glass, Na*0-8
20s-3tCh glass, BBaO-CaO-8t
o glass, etc., and one or more types of these can be used, and if necessary, those having different grades in terms of heat resistance, coefficient of thermal expansion, etc. can be used.

The organic binder is used in an appropriate amount to maintain the shape of the glass frit in the form of a sheet, and although it varies depending on the specific gravity and particle size of the glass frit, it is usually 5 to 40 parts by weight per 100 parts by weight of the glass frit. Parts by weight, preferably in the range of 8 to 30 parts by weight. The amount of binder is 5?
! It is undesirable to use less than 100% because the physical strength of the glass powder molded sheet decreases and handling becomes poor.
If the amount exceeds 40 parts by weight, gas release may be poor and foaming may occur as a result, which is not preferable.

Examples of organic binders include hydrocarbon resins, vinyl resins, acetal resins, and acrylic resins.

Examples include synthetic polymers such as styrene resins, polyester resins, and polyurethane resins, and semi-synthetic polymers such as cellulose resins, but acrylic resins are preferred because they have particularly good thermal decomposition properties. It is.

As mentioned above, the glass powder molded sheet is mainly composed of glass frit and an organic binder, but in order to improve the dispersibility of the glass frit in the organic binder, surfactants, fatty acid, fatty acid M, etc. Dispersants such as esters, fish oils, acrylic oligomers (molecules -1,130,000 or less) are added in an amount of 0.01 to 100 parts per 100 parts of glass frit.
It can be added in an amount of 10 parts by weight, preferably 0.1 to 2 parts by weight.

The type of sheet described is 1, for example, glass frit.

By uniformly mixing an organic binder, a solvent, and optionally additives such as a dispersant, antifoaming agent, and mold release agent using a ball mill and casting using a doctor blade, A sheet having the desired thickness accuracy is produced. Slurry formulation before casting.

It is desirable to apply a defoaming treatment using a conventional method to prevent air bubbles from forming inside the sheet.

The glass powder adhesive sheet of the present invention is applied to the surface of the glass powder molded sheet formed as described above.

It is manufactured by laminating thermoplastic resin layers.

The resin layer exhibits the desired adhesive property by heating and pressurizing the ceramic substrate, and usually has a thickness of 1 to 100 μm, preferably 5 to 50 μm. If it is less than 1μ, the desired adhesiveness cannot be obtained.
If it exceeds 100μ, the amount of pyrolysis gas generated during firing will increase and the outer B of the glaze layer will be inhibited.

The resin layer is preferably formed by VC, in which a resin previously formed into a film or sheet by a conventional method is superimposed on a glass powder molded sheet and then heated and pressed. Activate it using heat such as a burner and layer it with I\1
It may be provided by melt coating or spray coating.

In addition, the resin jIJ is more expensive than organic binders when used for purposes such as punching out a glass powder adhesive sheet into a desired shape and then stacking it on the surface of a ceramic substrate to form a patterned glaze layer on the substrate. It is necessary to use a thermal 0JIi resin having a thermal decomposition temperature. If the resin layer is formed of a thermoplastic resin with a thermal decomposition rate of 8 degrees lower than that of the organic binder, a thick layer due to shrinkage will occur at the end of the patterned glaze layer, which will impede the flatness of the glaze layer. This is because it will be done. However, if the glaze layer is formed on the entire surface and the edges can be cut and removed,
As long as the adhesive state during firing is maintained, the high or low thermal decomposition temperature is not necessarily the only problem. Of course, even in the case of forming a glaze layer on the entire surface, it is preferable to select the high or low thermal decomposition temperature as in the case of forming patterned glaze #.

There are no particular restrictions on the materials constituting the thermoplastic resin layer, as long as they can exert the desired adhesion to the ceramic substrate when heated and pressurized, either alone or in a mixture or reaction system of two or more. It's something that doesn't exist. An example of this is polyethylene.

Ethylene copolymer, ethylene-propylene rubber.

Hydrocarbon resins such as polyisobutylene, petroleum resins, and terpene resins; acrylic resins such as polyacrylic esters, polymethacrylic esters, and polyacrylamide; diene resins such as prbutadiene and polyisoprene; vinyl acetate and polyvinyl 7-cetal resins Resin, polyether resin, polyester resin, -urethane resin 1
Acrylic pressure-sensitive adhesives consisting of a (meth)acrylic acid ester and a vinyl thread binder having a functional group copolymerizable with the ester; Pressure-sensitive adhesives at room temperature such as resin-based pressure-sensitive adhesives such as polyvinyl ether-based pressure-sensitive adhesives, or rubber-based pressure-sensitive adhesives such as neoprene rubber-based pressure-sensitive adhesives, iso- and brene-based pressure-sensitive adhesives. A mixture of a substance exhibiting the above and a hot-melt resin is particularly preferable because it has less sticky feeling and can be easily adjusted in position during bonding.

The heat-melting resin is not particularly limited as long as it has a melting point of 50°C or higher (preferably 200°C or lower), and includes, for example, rosin, modified rosin, and esterified products thereof, phenolic resins, rosin, and Alkylphenol-modified xylene resins, terpene-phenol resins, thermoreactive types with functional groups such as 5-epoxy resins, or α
Alternatively, any non-functional type such as β-pinene polymer, aliphatic hydrocarbon resin, coumaron indene resin, styrene resin, aromatic petroleum resin, and acrylic acid ester copolymer can be used.

Is the thermofusible resin pressure-sensitive adhesive at room temperature? Substance shown 1
00f! It can be added in a range of 50 to 200 parts by weight, and if it is less than 50 parts by weight, no effect can be expected, and if it exceeds 200 parts by weight, the flexibility of the thermoplastic resin m will decrease and it will become brittle. It is undesirable.

One preferred combination of a substance exhibiting pressure-sensitive adhesive properties at room temperature and a heat-melting resin is a composition comprising the acrylic pressure-sensitive adhesive and the heat-reactive type resin; By doing so, an addition reaction occurs under heating either directly or via a crosslinking agent, thereby increasing the thermal decomposition temperature during firing and producing a craze layer with a good appearance.

The glass powder adhesive sheet constructed in this way is superimposed on the surface of a ceramic substrate such as alumina, beryllia, steatite, forsterite, or zirconia via a thermoplastic resin m'e, and after heating and pressing, the glass powder adhesive sheet is The frit is fired at a temperature equal to the softening temperature of the air, creating a glazed ceramic substrate. The temperature during firing is 500-1400℃
is common.

At this temperature, the organic binder and the thermal IJJffi resin layer disappear. Since the glass powder dressing sheet of the present invention is preformed as described below, it can be defined to have a uniform thickness. Since the defoaming operation can be easily performed, highly reliable sheets can be provided.

Further, since the thermoplastic resin layer is provided, strong adhesion to the ceramic substrate can be obtained by heating and pressing, and the firing operation is easy, and a good glazed ceramic substrate can be obtained.

Furthermore, if the thermal decomposition temperature of the thermoplastic resin layer is set higher than that of the organic binder, during the firing process, some of the binder disappears due to thermal decomposition and the glass powder molded sheet becomes ventilated, and later thermal decomposition occurs. In order to easily pass the decomposition gas of the thermoplastic resin layer,
A flat glaze I that does not cause blistering on the molded sheet.
11 can be formed, and the temperature at which the thermoplastic resin layer disappears due to thermal decomposition progresses and loses its adhesive strength.

The molded sheet is now in a powdered state, and in that state, 11M of glass frit! It has the advantage that the craze layer does not warp or shrink because it starts.

<Examples> Examples of the present invention will be shown below. Is the part of the sentence the weight part?
means.

Examples BaO-CaO-8iO2 glass (softening point: 850°C, 325 mesh under) was used as the glass frit, 100 parts of the glass frit, 12 parts of the organic binder shown in Table 1, 1 part of oleic acid as a dispersant, and toluene. 2
After mixing 4 parts of methyl ethyl ketone and 16 parts of methyl ethyl ketone in a ball mill at room temperature, the mixture was cast onto a polyester film using a doctor blade, and the thickness after drying was 130 mm.
A glass powder molded sheet of μm size was obtained.

On the other hand, a film-like material having a thickness of 20 μm was prepared by adjusting the thermal 0J plastic resin shown in Table 1 by a conventional method, and this was superimposed on the surface of the glass powder molded sheet and pressurized or heated. Lamination 1 A glass powder adhesive sheet of the present invention was obtained.

Next, an alumina substrate with a purity of 96.0% was prepared as a ceramic substrate, and the glass powder adhesive sheet was laminated on the surface of this substrate via a thermoplastic resin and bonded by heating and pressing at 100°C. This bonded product'60 at 1400℃
After holding for 1 minute, the temperature was increased at a rate of 10°C/min to 127°C.
A graze ceramic substrate was obtained by holding at 0° C. for 120 minutes.

Table 1 The temperature in parentheses indicates the end temperature of thermal decomposition.

As is clear from the examples described above, the glazed ceramic substrate produced using the glass powder adhesive sheet 14 of the present invention has a good appearance and a flat surface.

Representative Goro Kamai

Claims (1)

[Claims] 1) A glass powder adhesive sheet comprising a thermoplastic resin layer laminated on the surface of a glass powder molded sheet containing glass frit and an organic binder as main components. 2) The glass powder adhesive sheet according to claim 1, wherein the thermoplastic resin layer is composed of a mixture of a substance exhibiting pressure-sensitive adhesive properties at room temperature and a thermofusible resin. 3) The glass powder adhesive sheet according to claim 2, wherein the heat-melting resin is a heat-reactive resin. 4) The glass powder adhesive sheet according to claim 1, wherein the thermoplastic resin layer has a thermal decomposition temperature higher than that of the organic binder. 5) A glass powder adhesive sheet, which is made by laminating a thermoplastic resin layer on the surface of a glass powder molded sheet containing glass frit and an organic binder as main components, is superimposed on the surface of the ceramic substrate via the resin layer, and heated. A method for manufacturing glazed ceramic substrates that is fired after pressing.