JP3226485B2 - Unglazed plate analog - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unglazed plate-like material mainly composed of clay such as sericite and kaolin, regardless of a large energy-consuming process.

[0002]

2. Description of the Related Art Conventionally, to obtain a molded product using a clay material, kneading with water and then sintering, or
Methods such as using water glass, Portland cement, and a thermosetting resin have been proposed and implemented. The sintering method can provide a strong sintered body,
It requires a temperature of one thousand and several hundred degrees, requires a great deal of energy, and consumes a great deal of fuel and power. The equipment will also be large. When water glass, Portland cement or the like is used (JP-A-57-88062, JP-A-58-225)
5) In the case of using water glass, it takes a long time to develop water resistance, and in the case of using cement, there is a problem of whitening that white precipitates appear when immersed in water. Also, the strength is significantly deteriorated. Since the artificial stone mainly composed of a thermosetting resin is mainly composed of an organic resin, its fire resistance is limited, and the appearance must be polished and glossy.

[0003]

An object of the present invention is to provide an interior or exterior material having excellent water resistance and fire resistance without using a clay material as a raw material and consuming a large amount of energy as in sintering. The purpose is.

[0004]

SUMMARY OF THE INVENTION The present invention provides a clay main material,
It is a molded product composed of a mixture of a resin liquid as an early strength developing agent and a dispersion of aluminum silicate as a lightening agent, and has a light weight that is excellent in water resistance and fire resistance without a whitening phenomenon. The feature is an unglazed plate analog. Further, the present invention is a molded article comprising a mixture of a clay main material, a resin liquid as an early strength developing agent, a dispersion of aluminum silicate as a lightening agent, and a pentaerythritol aqueous solution as a flow improver during mixing, The gist of the present invention is an unglazed plate analog which is excellent in water resistance and fire resistance and has a reduced weight without whitening.

More specifically, the unglazed plate analog of the present invention comprises 14 to 17 parts by weight of a 4% aqueous solution of polyethylene glycol in which 4 to 9% of aluminum silicate is dispersed, and 5 to 6 parts by weight of a 2% aqueous solution of pentaerythritol. Part, resin dispersion 1
A molded article from a mixture obtained by adding 40 to 60 parts by weight of a clay main material, preferably sericite or / and kaolin, to a composition solution of 1 to 29 parts by weight, It is a fire-retardant analog with excellent fire resistance and no whitening. The above-mentioned unglazed plate analog of the present invention is obtained by molding and drying the above mixture, and then drying the mixture at 110 ° C to 15 ° C.
It is manufactured by heating and curing between 0 ° C.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the main clayey materials include those mainly composed of mica clay minerals and those mainly composed of kaolin minerals. In the embodiments of the present invention, a clay raw material called sericite, kaolin or the like is used. As the resin liquid, a resin liquid having an early strength expression effect is used. For example, 60
~ 63% acrylic styrene emulsion (solid content 4
(7.5% product) and 7.8% 2-propanol-water dispersion containing 5.0-6.0% methylated melamine resin. If necessary for mixing and kneading, add an appropriate amount of water. The aluminum silicate dispersion contributes to the weight reduction of the final product.

[0007] 4% polyethylene glycol (PEG) #
A solution composed of 14 to 17 parts by weight of a 4 to 9% aluminum silicate dispersion in a 200 aqueous solution, 5 to 6 parts by weight of a 2% aqueous pentaerythritol solution, and 11 to 29 parts by weight of a resin solution are referred to as sericite, kaolin and the like. The resulting clay is mixed alone or in a mixture of 40 to 60 parts by weight, kneaded well, molded into a mold, or the like, and dried. After drying, it is cured by heating to 110 ° C to 150 ° C.

The outline of the production process is as follows: 4% aqueous PEG # 200 dispersion 14 containing 4 to 9% aluminum silicate
To 17 parts by weight, 2% pentaerythritol aqueous solution
Parts by weight, 10 to 29 parts by weight of a resin liquid having the composition described below, 40 to 60 parts by weight of a single or mixed clay material called sericite, kaolin, etc. is added thereto, and the mixture is kneaded well. I do. There is no restriction on the mixing ratio of the clay, and it is adjusted according to the required color tone and specific gravity. The apparent specific gravity is larger for kaolin alone and decreases with an increase in the ratio of sericite. The apparent specific gravity of the mixture is between 1.77 and 1.06, depending on the influence of other compositions.

The effect on the apparent specific gravity is such that an increase in the resin liquid tends to increase the apparent specific gravity, and an increase in the aluminum silicate dispersion tends to decrease the apparent specific gravity. The composition of the resin liquid used here is an acrylic styrene emulsion having a solid content of 27.5%, 60 to 64%, preferably 62.5%,
It is a composition in which 5.0 to 6.0% of a methylated melamine resin is desirably dispersed in water, desirably 5.9%, and 7.0 to 8.0% of 2-propanol, desirably 7.8%. .

[0010] The amount of water added to facilitate kneading is
It is desirable that the amount be as small as possible in order to reduce the time for subsequent drying, but it increases as the proportion of sericite increases.
Water may be as much as 49 parts by weight per 0 parts by weight.

If the kneading is insufficient and the mixing is not uniform, the bending strength of the product will decrease. The slurry has thixotropy, and after filling in a mold, it can be swung to float and release mixed bubbles. After defoaming, the mixture is air-dried in a static state to reduce the weight by about 10% of the filling amount. Silicone release agents are less effective and it is desirable to use a film such as release paper on the bottom of the mold.

If air-dried overnight after release from the mold, the weight will be reduced by 30 to 40%. Rapid drying causes product warpage. After air drying, 50 ° C 60-90 minutes, 60 ° C 2 hours, 100 ° C
Dry for 1 hour. Following drying, the resin is crosslinked and cured by heating at 110 to 120 ° C for 6 hours, and at 150 ° C for 1 to 2 hours.

The heating temperature for the crosslinking can be selected between 110 and 150 ° C. The drying temperature and time are standard and can be changed depending on the thickness of the molded product and the degree of mixing with the clay. In general, rapid drying is not limited to the above description because the drying speed of the surface exceeds the moving speed of the internal evaporation and causes cracks and warpage.

[0014]

[Function] A clay-based material is mainly used, and a dispersion of aluminum silicate is added thereto to reduce the weight, and a small amount of a resin solution is added at 110 ° C. in order to quickly develop water resistance and bind.
Crosslinking and curing at a temperature of ~ 150 ° C to ensure strength. The water-soluble substance is excluded from the components to prevent the whitening phenomenon due to water wetting.

The molded product obtained by the above configuration is 60
Since the drying is performed at a temperature of about 100 ° C. and the heating is performed at 110 ° C. to 150 ° C., very little energy is consumed. When water glass or the like is used, the amount of energy is small, but it takes a long time for curing and aging, and it takes several tens of days to develop water resistance. In the present invention, the time required for all the steps is 5 to 6 days, and the water resistance is immediately exhibited. Furthermore, by contact with water,
Does not cause the phenomenon of whitening, which looks like white precipitates.

The addition of a 2% pentaerythritol solution has no effect on curing, but facilitates flow during mixing.

By adding the aluminum silicate dispersion, the apparent specific gravity of the product is reduced and the weight can be reduced. However, when this is added and kneaded in the form of a powder, the addition of the same amount of solid content results in a brittle product.

The amount of the resin in the constituent elements is such that it has excellent fire resistance as a minimum amount of preventing cracking and exhibiting water resistance. Despite being water-resistant due to the sandstone-like porosity of the surface, it does not condense to absorb moisture in humid environments. The mixing of the resin liquid, in combination with the aluminum silicate, enhances the development of water resistance, bending strength, and impact resistance. However, increasing the proportion of the resin increases bending strength and the like, but decreases flame resistance. Mixes exceeding 20% of the total volume (except for the water for kneading) will see the formation of smoke when the flame hits the end of the molded product. Similarly, when it reaches 29%, it shows flame resistance on the surface of the product, but carbonization is seen when it reaches the end.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to embodiments. The present invention is not limited by these examples.

Example 1 4 to 9% silica silicate was added to a 4% aqueous polyethylene glycol solution.
Aluminum silicate dispersion liquid in which ruminium is dispersed 13.9
Parts by weight, 4.6 parts by weight of a 2% pentaerythritol solution, 19.9 parts by weight of a resin solution, and 15.2 parts by weight of water are stirred and mixed.
To this, 46.3 parts by weight of sericite was added and kneaded to obtain a slurry close to a paste. The slurry-like composition is poured into a mold, shaken and defoamed, allowed to stand, and air-dried. When about 10% of the filling amount is reduced by evaporation and solidified, it is released from the mold and further air-dried. When the evaporation loss exceeds 30% [summer (7
40 hours at the end of the month).
Dry at 0 ° C for 4 hours and 100 ° C for 4 hours. 1 after drying
The end point when the product was heated at 50 to 160 ° C. for 2 hours and dried at 60 ° C. as a product was a point at which the entire surface became visually uniform gray white visually. About 20 minutes were spent raising the temperature from 60 ° C to 100 ° C. It took about 20 minutes to raise the temperature from 100 ° C to 150 ° C. The product has an apparent specific gravity of 1.45,
Obtained in the form of a white sandstone-like plate, there is no change such as whitening and softening after immersion in water for 72 hours. The surface does not change when the flame strikes, but when the edge is put into the flame, a little smoke is emitted. The flexural strength of a method in which one end of the plate is fixed and the weight is hung on the other end does not break at a moment up to 10,600 cm · g / cm ² .

Example 2 16.1 parts by weight of the same aluminum silicate dispersion as in Example 1, 5.5 parts by weight of a 2% pentaerythritol solution, 16.5 parts by weight of a resin solution, and 2.8 parts by weight of water were stirred and mixed. Then, 55.0 parts by weight of kaolin is added, kneaded and filled into a mold as a paste. After shaking and defoaming, 5 hours after standing, the filling amount was changed from 91.1 g to 84.0 g, and when the evaporation loss reached 7.8%, the mixture was removed from the mold and air-dried. The atmosphere was between 50C and 56C during these 5 hours. After 39 hours, 60 ° C for 90 minutes, 88 ° C for 6 hours, 104 to 106 ° C
Each heating for 1 hour drying took 20 minutes to raise the temperature.
Subsequent to drying, the product was crosslinked and cured at 158 ° C. for about 30 minutes for 2 hours to obtain a product. The product was obtained in the form of a plate of 59.1 g with a white brown color and an apparent specific gravity of 1.60. The water resistance remains unchanged after 72 hours of immersion in water, and the flame resistance does not emit smoke even when exposed to flame. The bending strength is 8640 cm · g / cm ² , which is slightly lower than that of Example 1, but does not hinder practical use. The impact resistance is cracked at the beginning by dropping from a height of 60 cm with a weight of 1,000 g at a thickness of 10 mm.

Example 3 1.5 parts by weight of the same aluminum silicate dispersion as in Example 1; 5 parts by weight of a 2% pentaerythritol solution;
8.5 parts by weight are stirred and mixed, and 50 parts by weight of kaolin is added thereto and kneaded to form a paste. This paste was treated in the same manner as in Example 2 to obtain a product. The product had an apparent specific gravity of 1.50 and a weight of 51.50 parts by weight obtained as a brown sandstone plate.
Equivalent to 8 parts by weight. The water resistance is the same as in the above examples, but the flame resistance is such that the ends are carbonized when exposed to a flame, and become brittle after being heated red. Moment 15469cm in bending strength test
・ Does not bend or break at g / cm ² . Impact resistance is 1,
A 12 mm thick plate with a weight of 000 g is cracked by falling from a height of 45 cm.

Example 4 Same aluminum silicate dispersion as in Example 1 15.0 parts by weight, 2% pentaerythritol solution 5 parts by weight, resin solution 2
1.5 parts by weight and 5 parts by weight of water are stirred and mixed, and 30.0 parts by weight of kaolin and 20.6 parts by weight of sericite are added and kneaded to form a paste. After filling in the mold, air-dry overnight (18 hours after rocking and defoaming) and remove from the mold. After air drying for 49 hours, 5 hours at 60 ° C, then spend 20 minutes at 100 ° C
And dried for 6 1/2 hours. Then, the temperature was raised to 150 ° C. over 25 minutes and crosslinked and cured for 90 minutes to obtain a product. The product is a brownish white plate with an apparent specific gravity of 1.39 sandstone. This takes a long time to dry due to the mixing of kaolin and sericite. The bending strength is 12,111 cm · g / cm ² , and the water resistance is the same as that of the above embodiment. Flame resistance is brittle after glowing with some smoke generation.

Example 5 16.1 parts by weight of the same aluminum silicate dispersion as in Example 1, 5.5 parts by weight of a 2% pentaerythritol solution, 16.5 parts by weight of a resin solution, and 7.1 parts by weight of water were stirred and mixed. Then, 54.9 parts by weight of kaolin is added and kneaded to form a paste. The paste was filled in a mold, defoamed, and air-dried. After 24 hours, the paste was removed from the mold, dried at 40 to 50 ° C. for 8 hours, and left overnight. Then spend 1 hour 30 minutes and 70 minutes at 70 ° C for 1 hour.
It dried at 00 degreeC for 1 hour. Next, it was crosslinked and cured at 110 to 119 ° C for 6 hours to obtain a product. The product is a brownish white plate with an apparent specific gravity of 1.32. A test piece was cut out from this product and the test result showed that the bending strength was 8,007 cm.
g / cm ² , impact resistance was 10 mm thick, and it was cracked by a 400 g weight when dropped from a height of 55 cm. The water resistance is the same as that of the above embodiment, and the flame resistance slightly emits smoke when glowing red, but does not change in the previous state.

Example 6 17.0 parts by weight of the same aluminum silicate dispersion as in Example 1, 5.8 parts by weight of a 2% pentaerythritol solution, 14.6 parts by weight of a resin solution, and 4.2 parts by weight of water were stirred and mixed. Then, 58.4 parts by weight of kaolin is added and kneaded to form a paste. This paste was filled in a mold and processed in the same manner as in Example 4 to obtain a product. The product is brownish white with an apparent specific gravity of 1.45.
It becomes a sandstone-like plate. Flexural strength is 5025cm · g / cm
² , Impact resistance is 45cm with 10mm thickness and 400g weight
Cracked by falling from the height. Water resistance and flame resistance were measured in Example 5.
It was similar to the product.

Example 7 17.0 parts by weight of the same aluminum silicate dispersion as in Example 1, 5.8 parts by weight of a 2% pentaerythritol solution, 11.7 parts by weight of a resin solution, and 7.0 parts by weight of water were stirred and mixed. Then, 58.5 parts by weight of kaolin is added and kneaded to form a slurry close to a paste. The mold is filled with a soft silicone resin plate with a natural sandstone pattern at the bottom. After defoaming, remove from the mold 3 hours after standing still. Air drying 19 hours, 30 ° C-40
5 hours at 60 ° C., 2 hours at 60 ° C., 1 hour at 95 ° C., 1 hour and a half at 100 ° C., and then 14.8 hours at 150 ° C. for 1 and a half hours after crosslinking and curing.
mx 14.8 cm, thickness 8 mm to 10 mm, weight 212.
5 g of product are obtained. The weight at the time of filling is 336.9 g, and the evaporation loss is 37%. The product became a brownish sandstone-like tile.

[0027]

As is apparent from the above-described embodiment, according to the present invention, a product can be obtained at a relatively low temperature of a maximum temperature of 150 ° C. For this reason, the energy cost required for manufacturing can be significantly reduced. The obtained product is rich in water resistance and fire resistance, and the impact resistance, bending strength and specific gravity can be adjusted according to the application. The appearance is sandstone, giving a soft feel and a graceful decoration.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C04B 33/00-33/36

Claims (5)

(57) [Claims] 1. A molded product comprising a mixture of a main clay material, a resin solution as an early strength developing agent, and a dispersion of aluminum silicate as a lightening agent, wherein the whitening phenomenon is excellent in water resistance and fire resistance. An unglazed plate analog, characterized in that it is lighter without any. 2. The unglazed plate analog according to claim 1, wherein the mixture contains an aqueous solution of pentaerythritol as a flow improver during mixing. 3. The above mixture is a mixture of 14 to 17 parts by weight of a 4% aqueous solution of polyethylene glycol in which 4 to 9% of aluminum silicate is dispersed, and a 2% aqueous solution of pentaerythritol.
3. An unglazed plate analog according to claim 2, wherein the composition comprises from 6 to 6 parts by weight and from 11 to 29 parts by weight of the resin dispersion, and from 40 to 60 parts by weight of the clay main material. 4. The unglazed plate analog according to claim 1, 2 or 3, wherein the main clayey material comprises sericite and / or kaolin. 5. After molding and drying the mixture,
An analog of the unglazed plate according to any one of claims 1 to 4, which is produced by heat-curing at a temperature between 150C and 150C.