JPS58208149A - Opaline frit for dry casting - Google Patents

Abstract

PURPOSE:To obtain opaline frit having superior performance, by using the 1st group of components consisting of specified amounts of SiO2, ZrO2, TiO2, B2O3 and an alkali metallic oxide and the 2nd group of components consisting of a fluorine component and oxides including P2O5 as principal components. CONSTITUTION:This opaline frit for a dry casting is composed essentially of the 1st group of components consisting of, by weight, SiO2, 2-15% ZrO2, 12-25% TiO2 (SiO2+ZrO2+TiO2=50-80%), 5-30% B2O3 and 5-30% alkali metallic oxide and the 2nd group of components consisting of a fluorine component and oxides including P2O5. The amount of each of the fluorine component and P2O5 is 0.5-10pts.wt. per 100pts.wt. of the 1st group of components. The oxides in he 2nd group are Al2O3, ZnO, MgO, CaO, BaO and SrO besides P2O5.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is mainly applicable to dry-type tsubamono.)1. This relates to milky white frit.

Conventionally, so-called Totetsu Rokutsurou, which is a cast iron surface coated with a glass layer, has been widely used as a material for bathtubs, wash basins, sinks, etc. As a raw material for the glass layer of this type of cast iron enamel, a milky white frit containing a zircon component or an antimony component (zircon, fq also L<1 dimension antimony based milky white frit) is generally used. In the above-mentioned 7 important applications, chemical resistance such as acid resistance and alkali resistance, hot water resistance, and thermal shock resistance are required, and from the viewpoint of appearance, uniform opalescent color development is required. Alternatively, antimony-based milky white frit has poor thermal shock resistance; 1. It is also less opalescent. If the glass layer is made thicker in order to obtain uniform opalescence, the thermal shock resistance will be even worse. In order to improve these drawbacks of the Schifflecon or antimony milk white frit, a method has been proposed in which seven zircon or antimony milk white frits with different thermal expansion coefficients are prepared and used depending on the part of the product. It goes without saying that methods such as ('I) will only unnecessarily complicate the manufacturing process. In addition, zircon-based opalescent furi-nod also has the disadvantage of poor acid resistance and cannot be used with acidic detergents.

In order to improve the drawbacks of the above-mentioned zircon-based or antimony-based milky white frit, a milky white frit (titanium-based milky white frit) containing a titanium molecule i02f has been developed (Japanese Patent Publication No. 4B-31737). Titanium-based milky white frit has zircon-based mori, < has superior milky whiteness than antimony-based milky white frit, and a product with uniform milky white properties can be obtained. It cannot be said that the impact resistance is still satisfactory.

Therefore, chemical resistance is essential in this industry.

There has been a demand for the development of an opalescent powder I77) that is excellent in hot water resistance, P impact resistance, and opalescence properties, that is, has excellent overall performance.

The present invention aims to meet the above needs.

For the above-mentioned purpose, the present inventor paid particular attention to titanium-based opalescent frit, and completed the present invention through intensive research to improve the above-mentioned drawbacks of said 717 frit. However, the milky white 7 liters of the present invention are 8i02 and 2.0 to +5.
0 wt% ZrO2 and 12.0-25.0 wt% T
The total amount with iu2 is 50.0 to 85.0% by weight, B
2O3 5.0-30.0iit%, #j Hi'IL
207); A mixture of a first component group consisting of 5.0 to 30.0 parts (herein R is an alkali metal) and a second component group consisting of a vitreous substance containing a fluorine component and P2O5 It is mainly based on

The invention will be explained in detail below.

1st Fy, minutes are 8i02 and 2.0 as mentioned above.
~15.0 wt% ZrO2, 12.0~25.0 wt% chisel i02, total weight 50.0~85.0 wt%, B2O3 5.0~30.0 wt%, Oyohi R2
It consists of 5.0 to 30.0% by weight of carbon. Z
rU2 is involved in hot water resistance and acid resistance of the glass layer.1. Therefore, when the ZrO2 content is 2% by weight (hereinafter simply referred to as %), the hydrothermal properties of the product seen are remarkable.

If it exceeds 15%, #acidity will deteriorate. 'rio2! d The opalescence of the calla suri.

It is involved in impact resistance and hot water resistance, and if it is less than 12%, it will cause opalescence,
Impact resistance becomes inferior, but if it exceeds 25%, hot water resistance deteriorates. Furthermore, 8i07°TiO and ZrO
If the total amount of 2 is less than 5096, the acid resistance and hot water resistance will be significantly lowered, and if it exceeds 85%, the 7 lift will become significantly dissolvable and will lose its practicality. B2O3 is involved in the easy solubility of 7L, so if B2O3 is less than 5%, 7L becomes dissolvable and the opalescence also decreases, but 30%
If it exceeds -M (aqueous and alkali resistance will be significantly deteriorated).

As mentioned above, the second losing group is 1, which contains fluorine components and P2O.
The fluorine component may be contained in an amount of 0.5 to 10.0 parts by weight and 0.5 to 10.0 parts by weight per 1%<100 parts by weight of P2O5. desirable. What p, t, y)...Elements and P2O5 are involved in thermal shock resistance and whiteness12, and if these components are less than 0.5 parts by weight (hereinafter simply referred to as parts), good whiteness cannot be obtained. Although it is difficult, if it exceeds 100 copies, it seems to have a negative effect on the perforation performance.

The second component group is Al2O3, ZnOlMgO and/or CaO, ,1-4ao and/or Vi8rO? These components supplement the properties of the above-mentioned essential components, and Al 2031''i is particularly preferred in this respect.In the second component group, Al 203 is added to 100 parts of the first component group. It is desirable that the amount of ZnO be less than 100 parts, and the amount of Lφ and/or CaO be less than 5 parts.If the temperature is outside the above range, the smoothness of the glass surface will be lost as the firing temperature increases. Furthermore, the second generation group is within the range of 5.0 to 30 parts with respect to 100 parts of the first component group, and 1% is the smoothness V.
This results in even more desirable results. Also BaO and/
Alternatively, if SrO exceeds 10 parts, it tends to have an adverse effect on hot water resistance and acid resistance. Furthermore, ZnO, NbzO and C
The total molecular weight of aO, BaO, and 8rO is 5.0 to 25.0
If it is within the range of 1-1, it is 2) (more desirable for water and acid resistance).

Other than the above #1 composition, the milky white frit of the present invention + (, is 8t as necessary) 203, 'V2O5, MoO3, 8n
Coo, NiO, Mll (J, C
uO, Fe2O3.

One type of colorant 1 such as Or 703 should be added preferably at least 10%w, or other subcomponents without losing the characteristics of the opalescent white color of the present invention. I can do it.

As mentioned above, the milky white frit of the present invention has essential components 7i02, ZrO, T+, 0, B2O.
3, tlF).

Because it contains the fluorine component P2O5 in a reliable predetermined ratio, it has chemical resistance, hot water injection resistance, impact resistance,
%L whiteness is provided.

EXAMPLE Various raw materials were blended and mixed to correspond to the compositions of samples 1 to 15 in Table 1, which were within the composition range of 711-y) of the present invention, and heated in a bath at 1200-1300°C. A frit was obtained by melting and then rapidly cooling.

In the same manner, a frit having the composition of the comparative example shown in the same table was obtained.

This j′1. 7 pieces are heat treated at 520 to 630°C for 5 to 20 minutes. This heat-treated 7 liter was placed on a 7 louis of 200 mesh (sieve mesh opening 74μ) with 10~209
Dry pulverization was carried out to the extent that 6.6% remained. Sprinkle the above 7 liters on a clean iron plate that has been sprayed with a lower glaze and fired at 950°C while it is still red hot, and heat it in a furnace at 950°C for 50 minutes.
Each of the test pieces obtained by firing for 0 to 90 seconds was subjected to the following performance test and the performance was compared. That is, as performance tests, the following whiteness heat impact resistance test, 10i4 acid test, 3 alkali resistance test, and 1iIit hydrothermal test were conducted.

1. Whiteness (W (Lab)) The whiteness was measured using 0DE-80H-I manufactured by Suga Shimasu Kiami)
Using a mold, measure the diffuse reflectance, a, and b values, and substitute them into Hunter's whiteness formula to calculate the whiteness (W(Lab))
get. Measured values are shown as the average value of 5 samples.

2. Hold the hot bomb test piece in a 150°C container for 20 minutes, then take it out and immediately put it into water at room temperature (18-20'C). 1. Red ink bleeds through. After checking the condition of the crack 1t using the method, repeat this operation.

Perform the above heating and cooling cycle /1/'i-5 times, those with no cracks are good, those with cracks only at the edges are fair.
Items with full surface cracks are indicated as defective.

3. Acid resistance test using a test shield conforming to the international standard l5o-2733
Add 400 ml of ice-water solution in a citric tube to 24 ml at boiling temperature.
After holding for a period of time, the decrease 1 of the wandering lips is determined per unit test surface area, and the average value of the three samples is taken, f/, /yy
? / day.

4. Hot water resistance test using a test device that complies with international standard l5o-2733,
Add 400 mβ of ion-exchanged pure water [1, 4 in boiling state]
After holding for 8 hours, the weight loss of the 3-hill wavy layer was determined per unit test surface area, the average value of the 3 samples was taken, and f/n
Indicated by //day.

5. Alkali resistance test 6 using a test device in accordance with International Standard 180-2734
Add 320 ml of sodium birophosphate aqueous solution and
After being kept in constant temperature water at 0°C for 24 hours, the weight loss of the floating layer was determined per unit test surface area.
The average value of three samples is taken and expressed as f/nr'/day.

The results of the above performance tests are shown in Table 1.

From Table 1, it is clear that Comparative Sample A-1, which contains more than 15% of ZrO2, has a lower tolerance than Samples 1 to 15. Also, the comparison sample Dvi containing more than 25% of l'i02
iit Poor water retention. Furthermore, compared to comparative samples E, FI, and Samples 1 to 15 containing more than 30% of B2O3, cocoon hydrothermal properties and alkalinity are remarkable.

Thus, sample winds 1 to 15 according to the present invention have acid resistance and alkali resistance, and 1lii' has hydrothermal resistance according to Table 1.

It exhibits excellent thermal shock resistance and opalescent properties, and completely overcomes the deficiencies of conventional opalescent 7 liters of this type. Therefore, the 711 of the present invention Cast enameled bathtubs, cast hollow sinks, etc. 1d are used under harsh usage conditions, such as mildly acidic detergents, strongly alkaline baths, etc., and milky white. Because of its extremely excellent properties, it is sufficient to use approximately 1/2 the amount of conventional glaze or antimony thread frit, and thus the amount of glaze used can be greatly reduced. The reduction in heat resistance leads to a further improvement in heat-resistant cushioning properties.Therefore, the seven points of the present invention eliminate the troublesome process of using different glazes depending on the part of the product, for example, the upper part and the inner part of the sink. If you use this method, you don't need it at all, and you can make the product with just one type of 7 liters.
It can also be applied to other parts of the world, greatly streamlining the manufacturing process.

Patent Applicant Nippon Friwoto Co., Ltd. Nippon Insulators Co., Ltd. Agent Tadao Usami Procedural Amendment July 5, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1 Case Description 1981 Patent Application No. 091726 2 Title of Invention Dry type Milk white for castings 71), 1-3 Relationship with the case of the person making the amendment Patent applicant address 36-1-50 Asahi-cho, Handa City, Aichi Prefecture
Number of inventions increased by amendment 7, Column 8 of "Detailed explanation of the invention" in the specification to be amended Contents of amendment Attachment notice υ 8, 1 part of the amendment 1, 13th F: J: Second line 1~ Line 48 “Table 1 1τ distortion is...1.
And G-nii, 1 sample insect 1~! 1IT compared to b15 by 1-1
It is clear that Fl water quality is inferior, and Z r02 1
Comparative sample L containing more than 5% lri sample sample-1~!
15 compared to 1. It is clear that the acid resistance is inferior by 7.

In addition, the comparison sample containing 12% or less of TlO2 was
- Opalescence and thermal shock resistance are inferior to Nχ15, 255
Comparative samples F and (2), which contain more than all of them, are inferior in hot water resistance compared to samples 1 to 1 and 15. Comparative samples E and F, which contain 5% or less of B2O3 in their history, are more flammable and less opalescent than samples 1 to 15, and comparative sample M, which contains more than 30% of B2O3
The hot water resistance and mn Alreca 1.1 j% are significantly inferior to cj comparison samples No. 1 to No. 15. ” he corrected.

2. Page 12, “Table 1 J is corrected to the attached table.

Tagami

Claims (1)

[Claims] 1.8i02 and 2.0 to 15.0% by weight of ZrO
2 and 12.0 to 25.0 heavy electric% of TiO2, the total amount is 50.0 to 85.0% by weight, and B2O3 is 5.0 to 30% by weight.
．． 0% by weight, and a first component group consisting of 50 to 30.0% by weight (herein, B is a metal), and an oxide containing F, elemental component A, and P2O5 A milky white frit for dry casting 2 whose main component is a second component group consisting of ,
Opalescent white 7lit3 according to claim 1, wherein P2O5 is 0.5 to 10 parts by weight, and the second component group is Al203, ZnO, M
gOs and/or CaO, BaU and/or 8r
Milky white 7 lit according to claims 1 and 2 including Oi 4, At 2U3 'ti 5.9 contained in the second component group for the first component group + oo ton i part Parts by weight or less, Zn0 (g) below 100 parts, negative side and/or OaO below 50 parts by weight, BaO and/or SrO
is 10.0 parts by weight, and contains KatsuznO, Leg O, and Ca.
Milk white 7 according to claim 3, in which the IC has a total t of O, Sr, and BaO in the range of 5.0 to 250 parts by weight.
List 5, Claims 1, 2, and 3, wherein the second component group I is in the range of 5.0 to 30.0 parts by weight with respect to 100 parts by weight of the first component group. Opalescent frit 6 as described in Items 1 and 4, Opalescent auxiliary agent 1 An improver for improving surface tension @ alignment, etc., and subcomponents such as a darkening agent.Claims 1 and 2
7 milky whites as described in Section 3, Section 3, Section 4 and Section 5.