JPS58176167A - Formable composition for low temperature baking ceramics - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention Suitable for molding (especially injection molding) for main part BA, and after molding (
- The degreasing process (after forming the next molded product) can be carried out extremely well. The present invention relates to a composition for low-temperature fired porcelain.

General resin, phenolic side fat, polyester resin.

Known plastics such as Yuri 7m fat are moldable.

Excellent in chemical resistance and aging properties.

On the other hand, it has various drawbacks, such as being easily flammable and emitting a lot of toxic gas and smoke when burned.

On the other hand, the known ceramic and glass compositions.

They are obtained by firing, melting, and molding for long periods of time at high temperatures such as lθ/, 10°C or higher, but they require high-temperature treatment and therefore consume a large amount of fuel. It had the following drawback.

Furthermore, in recent years, research and development of low-melting base mineral compositions such as low-temperature fired pottery has been carried out.

However, these books require processes such as using calcined materials, performing a heat reaction followed by firing, or heating and forming them, and due to the complexity of the process, For some reason, I hated it.

Therefore, the applicant of this case is glass chi, ek aluminum,
If-T has conducted research on the amount of iron in the method of making low-temperature fired porcelain and ceramics using a composition consisting of a binder with a clay I'M component and a binder with a narrow color. Issued #/9.
33 fat No. 1 yx et al.
(See No. sq) The present invention is based on the results of his research and development.

To further explain the prior invention, even if the low-temperature fired porcelain composition is used as it is for injection molding, it is virtually impossible to mold it as it is due to the plasticity and fluidity of the composition. Or it was difficult.

Therefore, for the powder of the low-temperature fired porcelain composition.

Atactic polypyrene (ApP) is a polystyrene commonly used in ceramic injection molding.
), thermoplastic 11 fats, lubricants, plasticizers, and other organic materials are heated and kneaded to make pellets or powdered molding materials.
Subsequently, in the same way as plastic injection molding, the organic material is injected into the mold of a molding machine to create a molded product (-next molded product), and finally the organic material is decomposed and injected in a degreasing furnace for main firing. However, a method has been used in which the final molded product is hung.

However, although the polystyrene in the powdered molding material is good for imparting moldability, thermal decomposition occurs all at once during the degreasing process at high temperatures, for example, approximately 29θ℃ to 330℃. This has the disadvantage that it causes sagging, cracks, etc. after firing, making it impossible to obtain an excellent final product.

The present invention provides novel compositions that ameliorate or eliminate these drawbacks.

In other words, butyral resin is used in addition to polystyrene to prevent the organic material (% polystyrene) in the primary molded product from rapidly decomposing due to heating during degreasing.
The composition is such that after the butyral, which starts to thermally decompose around ℃, is decomposed and removed, the polystyrene starts to decompose continuously and stepwise.

That is, one aspect of the present invention is.

(at glass noble component...... q
θ~60 wt% (bl aluminum oxide...
...10~3θ sane (c) Clay component...
・・・・・・・・・・・・10~. 25 layers Tchi (DL knot)
Mixture・・・・・・・・・・・・・・・・・・ S~/
For every 100 parts by weight of the mixture (1) having the composition: (e) at least one thermoplastic resin selected from the group consisting of polystyrene, polyethylene, and polypropylene... ...6 to 20 parts by weight (S) Butyral resin.................................../
~ll l(g) Lubricant・・・・・・・・・・・・
It consists of a composition for low-temperature firing porcelain that has been formed by mixing .

Another aspect of the present invention is as follows.

(a) Glassy component・・・・・・・・・・・・q
O~601/jLtk% (b) Aluminum oxide...
・・・・・・lO～307jLM%(c) Clay component・
・・・・・・・・・・・・・・・・・・10～25Nk≠
(d) Binding agent・・・・・・・・・・・・・・・・・・
・! ;-1! ;Mixture having the composition of Yichichi<■>1
Further to the ooxx section.

(・) At least one thermoplastic resin selected from the group consisting of polystyrene, polyethylene, and 4-lipropylene...6 to 20 parts by weight (S)
Butyral resin・・・・・・・・・・・・・・・／−／
/#(g) Lubricant・・・・・・・・・・・・・・・
・・・・・・／-61(h) Plasticizer・・・・・・・
・・・・・・・・・・・・・・・1~6I is mixed. Consists of a low-temperature fired porcelain composition suitable for molding.

ri as the glassy component (a) used in the present invention.

Glass current is produced when glass products are broken during manufacture or cut off as unnecessary. Crushed glass is used. The glassy component is about 110 to
Use at a ratio of t, ots.

In the above range, the glassy component is about 4 AOS or less.
-t, not porcelain. This shows that the glassy component acts as a flux. Furthermore, if the glass content is less than about 1Os, there is a drawback that shrinkage during heat curing is large and dimensional accuracy is poor.

Next, the aluminum oxide (b) used in the present invention is usually alumina that is easily available in powder form on the market.

Realmina is used in a proportion of about 10 to 30%.

If the alumina component is used in a proportion below the lower limit lθ, the strength of the resulting product will be opaque and cannot be used for the various applications intended in the present invention. From this, it is understood that the alumina plays the role of a reinforcing agent (paste). Furthermore, if the amount of alumina used exceeds 3θ, it is not preferable because it will not be turned into porcelain by heat curing.

The clay component (C) used in the present invention is easily available on the market. Generally, soils with strong plasticity mainly consisting of fine alumina silicate materials (so-called clay minerals) can be used as the clay component. As is well known, its chemical composition can be roughly summarized as b Al32.
os-510,"-)1.o It is composed of a three-component system, and the larger the value of pAJ20./510., the more fire-resistant porcelain tends to be obtained.For these reasons, it is used in the present invention. What is the clay component?

It should be understood as a general term for soil that contains silicate mineral pipes and consists of fine particles with a diameter of about 0.0/wm or less. For example, kaolin,
bentonite, comb clay, gyrome clay, pie stone.

Concrete KT of Mayas Ia, sericite, mulberry 1 quartz, etc.
o can be opened.

In the present invention, the clay component is used in a ratio of about /θ to 2S. However, if less than about 1Os, which is the lower limit of this range, is used, the moldability will be poor and undesirable.

On the other hand, if more than 2I% is used, it cannot be fired at low temperatures, and therefore cannot be turned into porcelain at the temperature specified in the present invention.

From these facts, it is understood that clay is useful for improving moldability and dimensional stability.

In any case, it is desirable to mix it with the alkali in an appropriate ratio and adjust the curing temperature.

Next, in the present invention, a binder (
d) is used.

As the pre-setting stimulant used in the present invention, it is preferred to use phosphoric acid or a phosphate salt. As the phosphoric acid, known phosphoric acids such as metaphosphoric acid, birophosphoric acid, orthophosphoric acid, triphosphoric acid, tetraphosphoric acid, etc. can be used.

Because these phosphorus FIk are easily soluble in Jintong water V.

Naturally, it may be used in the form of an aqueous solution.

Further, the phosphates used in the present invention include alkali salts, alkaline earth salts, and aluminum salts of phosphoric acid.

As the alkali salt of phosphoric acid, it is preferable to use %VC sodium phosphate. Further, as the alkaline earth salt of phosphoric acid, it is preferable to use Fi and magnesium phosphate.

Further, the phosphate salts include the various salts mentioned above, and among them, sodium tetrapolyphosphate is preferably used.

Incidentally, the various compounds mentioned above can be used alone or in combination of two or more kinds.

In the present invention, # bond axis is used with 5-is% 1111 axis. If less than Sqb is used within the above range, the product will not become porcelain, and the strength of the resulting product will be poor. On the other hand, 1s
If more than qb is used, the resulting product will become sticky and the water absorption rate will further increase! Undesirable. The mixture consisting of the components (a) to (d) is dry mixed using a known one-luminous mill or a moving mill. In addition, the above component (a
The mixture consisting of ) to (d) is the main component of the porcelain obtained by completely firing the composition of the present invention (hereinafter referred to as mixture (1) for convenience). In order to increase the heat fluidity and plasticity of the composition during firing or firing, the composition of the present invention further contains the following components (.) to (g) and (h). The above mixture (I) is about /
-! ;Adjust to a particle size of 0μ5IIL. If necessary, a coloring agent may be further added to the mixture (1) of the present invention to improve II aggregability.

In the present invention, in order to impart heat fluidity during injection molding to the mixture (1) consisting of powder having 1K grains, the (.) component, namely polystyrene, d! ! From the group consisting of polyethylene, and polypropylene.

Next, mix at least one thermoplastic resin.

The addition amount IIi is 6 to 20 parts by weight per 100 parts by weight of the mixture.
The rate shall be 1 child's division. In the above range, if the amount is less than 6 parts by weight, the heating fluidity during injection molding will be lost, and therefore the uniformity of molding will be reduced.
It is not possible to obtain a molded product.

- If more than 2,011 parts are used, degreasing becomes difficult (and therefore the degreasing time becomes longer), and at the same time the degreasing process (
It has the disadvantage that it rapidly decomposes at a temperature of about 290 to 330°C, causing blisters, cracks, etc.

In the present invention, component (a), that is, butyral resin (
polyvinyl butyral). Suitable butyral resins have a butyralization degree of Sg to 75 mob. Such a butyral resin starts to be thermally decomposed at around 170° C., and before the component (·) starts to be thermally decomposed, #1 is decomposed and removed. In the present invention, the butytailed resin is used.

It is used at a ratio of /-ii parts by weight to 00 parts by weight of mixture (1). In the above range, if the amount of resin A is less than 1 part by weight of 111 weight, the degreasing time will take a long time, resulting in the disadvantage that blisters, blemishes, etc. will appear in the molded product. On the other hand, if more than 11 parts by weight is used, the heat softening property becomes large and deformation occurs, and internal cracks (blisters) tend to occur during degreasing.

In the present invention, we further take into consideration the mold releasability from the mold release machine,
(g) Mixing the ingredients, i.e. lubricants. As the lubricant,
Stearic acid, paraffin wax.

Hydrocarbon waxes such as whale wax and wood wax are used.

The amount used is 1 to 700 parts by weight of the mixture (■).
The ratio is bx*m. In the above proportion.

If the amount used is less than the lower limit of 1 xit part, there will be no mold release effect. In other words, a product with an excellent bottom shape cannot be obtained.

On the other hand, if the amount is more than 6 parts by weight, the heat softening property will increase.

Therefore, deformation occurs during degreasing.

In another embodiment of the invention, component (i), a plasticizer, is further used. The above-mentioned (・) component and (
It is used to impart plasticity 1 to the ingredients.

As the plasticizer C, almost all commercially available products can be used. %, in the degreasing process, it is necessary to have a boiling point that is sufficient to evaporate and volatilize, such as DBP, DOP.
etc. are suitable for use. The amount of the plasticizer used is a sufficient amount to impart plasticity to the components (e) and (?), specifically, 1-6"IL per 100 parts by weight of the mixture (I).
Used in Dobe's proportions. When used in the above range at a ratio of 11 parts or less, the softening of the (e) fi and (f) components becomes an opaque component, and as a result, the additive V effect of the components (e) and (f) becomes an opaque component. Tend. On the contrary, Ajiti*
f! If the amount is higher than AS, the cooling solidification properties of the molded product will deteriorate, and the shape of the mold will become more rapid, resulting in the product being more susceptible to discoloration.

As explained above, one brother Akira VJ mixed machine (1) 100JK
This is a novel composition in which components (e) to (g) or (·) to (fi) are blended at a predetermined ratio of 1 part of irises to tSK.

Therefore, almost all known mixing means can be used for the above-mentioned distribution.

L and N, which have been thoroughly mixed with a mixer or the like, are kneaded with a kneader or the like while being heated using a heating method to obtain a low-temperature fired porcelain composition tube suitable for molding.

The composition was further extruded in sheet form at 9-R, a,
*Cut extruded into a shape and then cut to a specified size.

Alternatively, it can be used in the form of pellets or even powder.

In the present invention, these are put into an injection molding machine and injected into a mold while being heated to form a next molded product.

The shaped product is then removed from the mold and placed in a degreasing furnace.

i! The temperature is gradually increased from warm to 400℃.
Degrease at high temperature before and after.

Through this degreasing step, the composition of the present invention contains (・
) to (- and (h) The W components are slowly degreased in the order of their boiling points.

Various known furnaces can be used as the degreasing furnace.
It is especially desirable to use an electric furnace.

The temperature increase rate is approximately room temperature ~/SO℃: 2θ ~ 23;℃/hrtso℃
~-i! 00 'C: J ~j' ”C/h
At r-θθ℃~30o: ri~/θ”C/hr3
00° C. to QOO”C: 10 to 1!”C/hr.

These heating rates f are merely a guideline, and it is not our intention to add ii1.In the conventional technology, the temperature is raised and heated over several tens to hundreds of hours, so 1 The composition of the present invention makes it possible to significantly shorten the degreasing time.

The degreased molded product is then slowly cooled down to room temperature by IP. Of course, without cooling, heat curing (main firing)
'Ik You may go.

As the heat curing means, a conventional heating furnace such as #'i, a tunnel kiln, a shuttlecock kiln, etc. is used. Also generally about 6
It is carried out in the range of 3θ to 7sθ°C. The heating time depends exclusively on the heating degree, but is, for example, about 700° C. for about 30 minutes to 2 hours.

Because the composition of the present invention can be fired at such low temperatures, it has a low shrinkage rate upon firing and high dimensional accuracy. Motsu.

The compositions of the invention are also suitable for injection molding and therefore for mass production molding of products.

8 shots below! A will be explained using an example.

Column 11H Production of mixture glass (cullet) II (by weight) Aluminum oxide 23 Clay / II binding
Mixture (monoaluminum phosphate l.

0.7 and tetrapolyline Mix 1 cup of acid soda 9.3 hardware) Colorant (red iron) Amount of color The above ingredients were thoroughly stirred and mixed to obtain a mixture (1).

Preparation of the composition of the present invention The following components were further added to the above mixture (IIK) in the following proportions.

Mixture (I) / 00 parts by weight I Listerene Resin IQ, Zastearin Gorge 3.6 D I P! , then mix thoroughly in a blender, and then in a kneader.
In! Thoroughly kneaded on rOc. The obtained kneaded product Fi was made into pellets of 3 to 5 m/m, and then the injection temperature/rOC1 injection pressure lt/cn? The material was injection molded at a mold temperature of 3 S° C. into a plate-shaped body measuring 7 mm in diameter.

The molded product was then heated from room temperature to 1-θC at a heating rate of 20C/hr and from 1soc to 200C at 3.1. C/hr
, 200C to 300T:): 7. θC/hr,
30θt:' ~37! up to rc, /2. ! rc/h
It was done at a rate of r. The obtained molded product has cracks,
Please make sure there are no defects such as blisters or deformations.

Next, the molded body was heated up to 70θC at 30θC/hr.
Firing (honkyo-sei) was performed at a temperature increase rate of .

There were no cracks or the like on the surface of the product.

Production of Example Mixture 111 Glass (cullet) 50% Aluminum oxide 0 Clay 10%
Mixture 70 weight - Base agent 3 (aluminum oxide: chloride chloride mixture) The above components were sufficiently stirred and mixed to obtain a mixture il+.

Mixture (I) 700 parts by weight? Liethylene IQ Butyral resin 3.6 (Butyralization degree Atmo15k) Wood Wax
Ko, da C1, O, P, 2.
No. 11 and below, the method of Example 1 was followed to obtain a product.

Example 3 'Production of mixture...Glass (cullet) 172wt.
Al2nium oxide 2 to clay 1% by weight
Binder colorant 3 (acid f hyflom) Each of the above i components was optically mixed to obtain a mixture il+.

Production mixture (I) of the composition of the present invention / 0 ON amount N Pripropylene Depteral resin! , 7 Nochu Raarafin Wax 3.0D, O, P,
Hereinafter, a product was obtained by following the treatment method of Example 1.

Example mixture (I) 100 parts by weight Polystyrene g, s Butyral resin 3.6 Stearic acid 3.6 However, the mixture port I used in Example 1 was used.

A product was obtained by using the above ingredients according to the recipe of Example 1.

The products obtained in Example 2 to Tei above are deformed and Kirengana (
It was by far the best.

Comparative Example/Mixture (1) /θ01it part Styrene resin 6 Butyral resin 13 Stearic acid 3.6 D, 8. P, ,2,'f
(However, the mixture * +1+ was excluded and 11! The one used in Example 1 was used.

When this composition was treated according to the recipe of Example 1,
During the degreasing process, thermal deformation occurred and, in addition, blistering occurred inside the product.

Comparative Example Mixture (I) / 00 parts by weight Styrene 22 Buderal resin 3. Hiroshi weight part stearic acid
i, 3 D, B, P, / , 5 However, the mixture (11 used was the one used in Example 1).

When this composition was processed according to the recipe of Example 1, cracks were generated in the facial oiling process.

When we examined the superior products, we found that they require degreasing time of 5 hours or more.

Claims (1)

[Claims] ill (a) Glassy component ......
...qθ~l, 01Xk whisper (b) aluminum oxide...
......lθ ~ 30 skewers - (cl clayey component...
・・・・・・・・・・・・・・・・・・／θ～-5 Densumiman (
d) Binding agent・・・・・・・・・・・・・・・
... Composition 1 of 5-151m mixture (1)l
θθm! ′ in addition to the part. (・) At least one thermoplastic resin selected from the group consisting of polystyrene, polyethylene, and polypropylene...6-20] Lil1W6 (f) Butyral resin...・・・・・・・・・／〜／／
I (g) Lubricant・・・・・・・・・・・・・・・
.../~ 61 is mixed. A composition for low-temperature fired porcelain that has been subjected to molding. +21 Butyralization degree of butyral resin is 5g to 7
Claims (1:
A composition for low-temperature firing porcelain that has been molded 10 times as described above. (3) Claims characterized in that the lubricant is stearic acid (a composition for low-temperature fired porcelain suitable for molding according to item 11). +41 (a) Glassy component...・
...qθ~60 heavy duty-(b) aluminum oxide...
...10-30 weight 11S (C) clay component...
・・・・・・・・・・・・・1O〜2511饅(d) Binder ・・・・・・・・・・・・・・・ 5-13
%-11T. A mixture (1) having a composition of 100% by weight [. (e) At least one thermoplastic resin selected from the group consisting of polystyrene, /IJ ethylene, and polypropylene...6 to 20 parts by weight (f) Butyral resin...・・・・・・/-//1(g) slip
Agent・・・・・・・・・・・・・・・・・・・・・
~ 6I(h)′ Plasticizer・・・・・・・・・・・・
・・・・・・・・・L ~ 6I is mixed and fired at low temperature suitable for molding @Fukuyo Kumihomono. (5) The degree of butyralization of butyral resin! rg~
Claims (4) characterized in that it is 7S molti
A composition for low-temperature firing porcelain suitable for molding according to item 1. (61) A composition for low-temperature fired porcelain suitable for 5V cedar, characterized in that the lubricant is stearic acid.