JP2002255584A - Glass flux, coloring composition, and decorative glass substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coloring composition which contains no lead, restricts generation of crack, and is excellent in acid resistance and alkali resistance, and also provide a decorative glass substrate. SOLUTION: The glass flux is characterized in that it is composed of SiO2 of 56-69% (interms of wt.%, and so forth), Al2 O3 of 0-3.5%, B2 O3 of 23-32%, Li2 O of 0.1-3%, Na2 O of 1-5%, K2 O of 0-4%, TiO2 of 0-5%, and ZrO2 of 1-5%. The coloring composition consists of the glass flux and coloring pigments. The decorative glass substrate 3 is obtained by coating the coloring composition on a low expansive crystallized glass substrate as a low expansive substrate, and after that, by forming a pattern 1 by firing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass flux and a coloring composition for forming a pattern on a low expansion glass substrate, and a decorative glass substrate obtained by forming a pattern on the low expansion glass substrate.

[0002]

2. Description of the Related Art In recent years, the demand for an electric cooker in which a heating element such as a halogen heater is attached to the lower portion of a top plate and an electromagnetic cooker in which heat is generated by an electromagnetic induction action using an induction coil has been particularly increased due to its safety. ing. As these top plates themselves, low expansion crystallized glass substrates having various colors such as transparent, black, and white are used, and various patterns are formed.

In forming a pattern on the surface of these low expansion crystallized glass substrates, for example, Japanese Patent Publication No. 5-40
As disclosed in Japanese Patent No. 707, a mixture of a leaded low-crystal glass flux, a coloring pigment, and an additive is pasted together with an organic binder in order to match the thermal expansion of the substrate and the pattern. And paste the paste
The pattern is formed by printing on a low expansion crystallized glass substrate by screen printing or the like and firing it. The formed pattern matches the coefficient of thermal expansion of the glass with the expansion of the crystallized glass substrate, thereby preventing the occurrence of surface cracks.

However, it is desirable that a low expansion glass substrate used as a cooker does not contain lead because there is a concern about the effect on the human body. Here, among the components constituting the glass flux, substances that are likely to have an effect on the human body include As, Pb, Cd and B
a, Sb, Zn, F and the like can be considered. Pb,
Since Ba and Zn are important components for maintaining the properties as a glass flux, it has conventionally been difficult to reduce them to zero.

On the other hand, a glass flux containing no lead (Pb) is disclosed in JP-A-9-227152. Since Ba and F may be added to the glass flux, there is a concern that the glass flux may affect the human body in the future. Therefore, by adjusting the minor component system of Zr, Li, Na, K, and Ti without using Pb, Ba, Zn, F, As, Cd, and Sb, there is no crack, antifouling property, acid resistance, and resistance to acid. It is desired to develop a glass flux excellent in alkali.

[0006]

SUMMARY OF THE INVENTION In view of the above problems, the present invention does not contain lead, suppresses the occurrence of cracks, and has an antifouling property.
An object of the present invention is to provide a glass flux excellent in acid resistance and alkali resistance, a coloring composition using the same, and a decorative glass substrate.

[0007]

According to the first aspect of the present invention, an SiO ₂ 56
To 69 _{wt%, Al} 2 O 3 _{0~3.5 wt%, B} 2 O
₃ 23 to 32% by weight, Li ₂ O 0.1 to 3% by weight,
Na ₂ O 1 to 5% by weight, K ₂ O 0 to 4% by weight, Ti
A glass flux comprising 0 to 5% by weight of O ₂ and 1 to 5% by weight of ZrO ₂ .

Since the glass flux of the present invention has the above composition, it does not contain lead, is safe, suppresses cracks, and has excellent antifouling properties, acid resistance and alkali resistance. Next, each component will be described.

(SiO ₂ ) SiO in glass flux
The content of ₂ is 56 to 69% by weight. If the content is less than 56% by weight, the coefficient of thermal expansion becomes large, the difference in thermal expansion from the substrate becomes large, and cracking or peeling may occur. If it exceeds 69% by weight, the viscous flow of the glass increases, the painted surface becomes rough, and the antifouling property deteriorates. The preferred content of SiO ₂ is 58 to 68% by weight.

[0010] (Al ₂ O ₃ ) Al in the glass flux
The content of ₂ O ₃ is 0 to 3.5% by weight. If it exceeds 3.5% by weight, the viscous flow of the glass increases,
The painted surface becomes rough and the antifouling property deteriorates. The preferred content of Al ₂ O ₃ is 1 to 3% by weight.

[0011] _{(B 2 O 3) B 2} O in the glass flux
The content of ₃ is 23 to 32% by weight. If the content is less than 23% by weight, the thermal expansion coefficient of the glass may increase, and the acid resistance may deteriorate. If it exceeds 32% by weight, the alkali resistance may deteriorate. Preferred B ₂
The content of O ₃ is 25 to 28% by weight.

[0012] _{(Li 2} O) _Li 2 in the glass flux
The content of O is 0.1 to 3% by weight. 0.1% by weight
If it is less than 1, the thermal expansion coefficient of the glass increases, and cracks and peeling are likely to occur. If it exceeds 3% by weight, the alkali resistance deteriorates. The preferred Li ₂ O content is 0.5 to 2.5% by weight.

(Na ₂ O) Na ₂ O has the effect of reducing the viscous flow of glass. Na ₂ O in glass flux
Is 1 to 5% by weight. If the amount is less than 1% by weight, the viscous flow of the glass becomes high, the painted surface becomes rough, and the antifouling property may deteriorate. If it exceeds 5% by weight, the coefficient of thermal expansion of the glass increases significantly, and the alkali resistance deteriorates. The preferred content of Na ₂ O is _{2 to} 4.5% by weight.

(K ₂ O) The content of K ₂ O in the glass flux is 0 to 4% by weight. If it exceeds 4% by weight, the viscous flow of the glass becomes high, the painted surface becomes rough, the antifouling property may be deteriorated, and the coefficient of thermal expansion becomes large. Preferred K ₂ O content is 1 to 3
% By weight.

TiO in (TiO ₂ ) glass flux
The content of ₂ is 0 to 5% by weight. If it exceeds 5% by weight, the viscous flow of the glass increases, the painted surface becomes rough, and the antifouling property deteriorates. Preferred content of TiO ₂ is 0 to 3 wt%.

(ZrO ₂ ) ZrO ₂ has a role of improving acid and alkali resistance. Zr in glass flux
The content of O ₂ is 1 to 5 wt%. If the amount is less than 1% by weight, the acid resistance may be deteriorated. If it exceeds 5% by weight, the viscous flow of the glass increases, the painted surface becomes rough, and the antifouling property deteriorates. Preferred Zr
The content of O ₂ is 1.5 to 4% by weight.

The glass flux of the present invention can be used at room temperature (20
° C) to 400 ° C with a coefficient of thermal expansion of 38 to 55 × 10 ⁻⁷ /
It is preferably K. When it is less than 38 × 10 ⁻⁷ / K, the viscous flow of the glass becomes high, and the surface may become rough. If it exceeds 55 × 10 ⁻⁷ / K, cracks may occur on the painted surface regardless of the printing thickness.

According to a second aspect of the present invention, SiO ₂
% By weight, Al ₂ O _{3 0 to} 3.5% by weight, B ₂ O ₃ 2
3 to 32 _wt%, Li 2 O _0.1~3 wt%, Na ₂
O 1-5% by weight, K ₂ O 0-4% by weight, TiO ₂
A coloring composition comprising a glass flux comprising 0 to 5% by weight and 1 to 5% by weight of ZrO ₂ and a coloring pigment.

The coloring composition of the present invention is prepared by adding a coloring pigment to the above glass flux. For this reason, it is safe without lead, suppresses cracking, and is excellent in antifouling properties, acid resistance and alkali resistance.

Examples of the coloring pigment used in the coloring composition of the present invention include black (Cr-Fe, Co-Mn-Cr).
-Fe, Co-Ni-Cr-Fe, Co-Ni-Cr-
Fe-Mn), gray (Sn-Sb, Sn-Sb-V)
Etc.), yellow (Sn-V, Zr-V, Zr-Si-Pr, T
i-Cr-Sb, Zr-Si-Cd-S, CdS, etc.),
Tea (Zn-Al-Cr-Fe, Zn-Mn-Al-Cr
-Fe etc.), green (Ca-Cr-Si, Cr-Al, Co
-Zn-Al-Cr, Zr-Si-Pr-V), blue (Co-Al-Zn, Co-Al, Co-Si, Zr-
Si-V, etc.), pink (Mn-Al, Ca-Sn-Si)
-Cr, Sn-Cr, Zr-Si-Fe, etc.), red (Zr
-Si-Cd-Se-S, Cd-Se-S, etc.)
These can be mixed in any proportion so as to obtain a desired color.

According to a third aspect of the present invention, the glass flux is 50 to 100% by weight, and the color pigment is 0% by weight.
Preferably, it is about 50% by weight. When the glass flux is less than 50% by weight or the color pigment is 50% by weight
If it exceeds, the painted surface may be rough and the antifouling property may be deteriorated.

It is preferable that the coloring composition further contains TiO ₂ as an additive. This TiO ₂ is added to the coloring composition separately from that contained in the glass flux. This eliminates the sense of transparency of the pattern and allows the pattern to be clearly recognized.

[0023] As in the invention of claim 5, the content of the additive is preferably 0 to 20 parts by weight based on 100 parts by weight of the total weight of the glass flux and the coloring pigment. If the amount of TiO ₂ as an additive exceeds 20 parts by weight, the surface may be rough and the gloss of the painted surface may be lost.

According to a sixth aspect of the present invention, the surface of the low expansion glass substrate is formed by adding 56 to 69% by weight of SiO ₂ and Al ₂ O _{30 to}
3.5 _{wt%, B} 2 O 3 _23~32 wt%, _Li 2 O
0.1-3 _wt%, Na 2 O _{1~5 wt%, K} 2 O
0-4 wt%, _TiO 2 0 to 5 wt%, and ZrO
The coloring composition with a picture having a glass flux consisting of ₂ to 5% by weight and a coloring pigment, and fired, a decorative glass substrate, characterized in that by forming a pattern.

The decorative glass substrate of the present invention is obtained by forming a pattern made of the coloring composition and firing the pattern. For this reason, it is safe without lead, suppresses cracking, and is excellent in antifouling properties, acid resistance and alkali resistance.

In performing the painting, an acrylic vehicle or the like is added to the coloring composition to form a paste, which is applied by a method such as screen printing, roll coating printing, brush coating, bar coating printing, or the like. The thickness of the pattern when applied once is preferably 3 to 20 μm. If it is less than 3 μm, the concealability of the pattern will be poor, and the pattern may not be clear, and if it is more than 20 μm, the pattern may be cracked. The application of the coloring composition may be performed once or twice or more, but the total thickness is preferably not more than 20 μm.

Examples of the low expansion glass substrate include low expansion crystallized glass and quartz glass. The low expansion glass substrate preferably has a coefficient of thermal expansion of -5 to 60 × 10 ⁻⁷ / K. Thereby, the low expansion glass substrate is excellent in heat resistance and thermal shock resistance. If it is less than −5 × 10 ⁻⁷ / K, it may be peeled off without matching the expansion of the glass flux in the coloring composition, and if it exceeds 60 × 10 ⁻⁷ / K, it may be broken by thermal shock. There is a possibility that.

In manufacturing the decorative glass substrate, an organic binder is added to the coloring composition to form a paste, which is printed on a low expansion glass substrate and fired.
The firing temperature is preferably from 750 to 850 ° C.

According to a seventh aspect of the present invention, the glass flux is 50 to 100% by weight, and the color pigment is 0% by weight.
Preferably, it is about 50% by weight. Thereby, the antifouling property of the painted surface is improved. Like the invention of claim 8,
The coloring composition further includes TiO2 as an additive.
Is preferably contained. Thereby, the pattern can be clearly recognized. Like the invention of claim 9,
The content of the additive is preferably 0 to 20 parts by weight based on 100 parts by weight of the total weight of the glass flux and the coloring pigment. Thereby, the concealing property is enhanced, and the pattern becomes clear without being transparent.

[0030] As in the tenth aspect of the present invention, the decorative glass substrate is preferably a top plate of a cooker. Because the top pyrate of the cooker is exposed to high temperatures,
Heat resistance and thermal shock resistance are required, and further, acid resistance, alkali resistance and antifouling properties are required. Under such severe conditions, the decorative glass substrate of the present invention can exhibit satisfactory performance. Examples of the cooking device include an electromagnetic cooking device, an electric cooking device, and a gas cooking device.

Preferably, the decorative glass substrate is a heater panel. Since the heater panel is installed near the heater, it is exposed to high temperatures. For this reason, thermal shock resistance and heat resistance are required. According to the decorative glass substrate of the present invention, these requirements can be satisfied.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 Embodiments 1 to 7 and Comparative Examples 1 to 7 of the present invention are described.
3 will be described. A glass flux having a composition shown in Table 1 was prepared. The following physical properties were measured for each glass flux.

(Coefficient of thermal expansion) Measured by a thermal dilatometer by a compression load method. (Gloss) Observation was made by visual observation, and the case where there was gloss was judged as ○, and the case where there was no gloss was judged as ×. (Presence / absence of cracks) Observed by a scanning electron microscope, it was judged that there was no crack, and that the spot was found as x.

(Acid Resistance) Commercially available acidic beverages (for example,
The sample was immersed in lemon water (pH = 2-3), and the surface change was visually observed. The case where the surface did not change was judged as ○, and the case where the surface changed was judged as ×. (Alkali resistance) It was immersed in a commercially available alkaline detergent (for example, undiluted solution of detergent for kitchen oil stain pH = 9 to 12) at room temperature for 24 hours, and the change of the surface was visually observed. The case where the surface did not change was judged as ○, and the case where the surface changed was judged as ×.

(Thermal Shock Resistance) After quenching in water at ΔT = 600 ° C., the specimen was visually observed. The above measurement results are shown in Table 1.

[0036]

[Table 1]

As is known from the table, SiO 2₂ 56
~ 69% by weight, Al₂O₃ 0-3.5% by weight, B₂O
₃ 23-32% by weight, Li₂O 0.1-3% by weight,
Na ₂O 1-5% by weight, K₂O 0-4% by weight, Ti
O₂ 0-5% by weight, and ZrO₂ From 1 to 5% by weight
Glass flux having different composition (Experimental Examples 1 to 7)
Has a coefficient of thermal expansion of 45.1 to 47.9 × 10^-7/ K
There is good gloss, no cracks, acid and alkali resistant
Resilience and thermal shock resistance were excellent.

On the other hand, in Comparative Example 1, SiO ₂ is larger than the above numerical range, and Na ₂ O and ZrO ₂ are smaller. In this case, the coefficient of thermal expansion was small, there was no luster, and the surface was rough. In Comparative Example 2, SiO ₂ is smaller than the above numerical range, and Al ₂ O ₃ and Na ₂ O are larger. In this case, the thermal expansion coefficient was large, cracks occurred, and the acid resistance was poor. Comparative Example 3 was composed of Al ₂ O ₃ and B ₂ O
₃ is larger than the above numerical range, and ZrO ₂ is smaller. In this case, the coefficient of thermal expansion was small and the gloss was poor.
Also, the alkali resistance was poor.

Embodiment 2 90% by weight of the glass flux of Example 6 of Embodiment 1
5 parts by weight of TiO ₂ as an additive and three parts by weight of 85 parts by weight of an acrylic vehicle with respect to 100 parts by weight of the total weight of 10% by weight of a black coloring pigment (Co-Mn-Cr-Fe). The mixture was mixed with a roller mill to obtain a coloring composition.
As shown in FIGS. 1 and 2, this colored composition was applied to a low expansion crystallized glass substrate 2 by screen printing to a thickness of 10 μm.
m was applied once and baked at 800 ° C. to obtain a decorative glass substrate 3. The color tone, coefficient of thermal expansion, gloss, presence or absence of cracks, acid resistance, alkali resistance and thermal shock resistance of the obtained decorative glass substrate pattern
The measurement was performed in the same manner as in the first embodiment. Table 2 shows the measurement results.

[0040]

[Table 2]

From the above measurement results, it was confirmed that the properties of the glass flux did not change even when the coloring pigment and TiO ₂ as an additive were added.

According to the first and second embodiments, the glass flux of the present invention contains Pb, Ba, Zn, F, A
Contains no harmful components such as s, Cd, and Sb, and further improves the acid resistance and alkali resistance by adding Zr.
The gloss, crack-free, acid resistance and alkali resistance equivalent to the conventional leaded glass flux could be obtained. Also,
A low-expansion crystallized glass substrate formed with a pattern using this glass flux also has the same characteristics and does not contain any harmful components. Therefore, it can be said that this decorative glass substrate is safe even if it is used for a portion that touches the human body such as a top plate of an electric cooker, an electromagnetic cooker, and a gas cooker.

[0043]

According to the present invention, there is provided a glass flux which does not contain lead, suppresses the generation of cracks, and is excellent in antifouling property, acid resistance and alkali resistance, a coloring composition using the same, and a decorative glass substrate. can do.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a decorative glass substrate according to a second embodiment.

FIG. 2 is a plan view of a decorative glass substrate according to a second embodiment.

[Explanation of symbols]

 1 ... pattern, 2 ... low expansion crystallized glass substrate, 3. . . Decorative glass substrate,

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G062 AA18 BB01 BB05 DA06 DB01 DB02 DB03 DC04 DC05 DD01 DE01 DF01 EA02 EA03 EB03 EC03 ED01 EE01 EF01 EG01 FA01 FA10 FB01 FB02 FB03 FC01 FC02 FC03 FD01 GA01 FE01 F01 FF01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM05 MM12 NN05

Claims (11)

[Claims] 1. An SiO ₂ content of 56 to 69% by weight, Al ₂ O
₃ 0 to 3.5 _{wt%, B} 2 O 3 23 through 32 wt%,
Li ₂ O 0.1 to 3% by weight, Na ₂ O 1 to 5% by weight, K ₂ O 0 to 4% by weight, TiO ₂ 0 to 5% by weight,
And glass flux, characterized in that it consists of _ZrO 2 1 to 5% by weight. _2. 56 to 69% by weight of SiO ₂ , Al ₂ O
₃ 0 to 3.5 _{wt%, B} 2 O 3 23 through 32 wt%,
Li ₂ O 0.1 to 3% by weight, Na ₂ O 1 to 5% by weight, K ₂ O 0 to 4% by weight, TiO ₂ 0 to 5% by weight,
And a glass flux comprising 1 to 5% by weight of ZrO ₂ and a coloring pigment. 3. The method according to claim 2, wherein the glass flux is 50 to 100% by weight, and the coloring pigment is 0 to 5% by weight.
A coloring composition, which is 0% by weight. 4. The coloring composition according to claim 2, wherein the coloring composition further contains TiO ₂ as an additive. 5. The coloring composition according to claim 4, wherein the content of the additive is 0 to 20 parts by weight based on 100 parts by weight of the total weight of the glass flux and the coloring pigment. object. 6. The method according to claim 6, wherein the surface of the low expansion glass substrate is SiO _2.
56 to 69 _{wt%, Al} 2 O 3 _0~3.5 wt%, B
₂ O ₃ 23 through 32 _wt%, Li 2 O 0.1 to 3 _wt%, Na 2 O 1 to _5% by weight, K 2 O 0 to 4 wt%,
TiO ₂ 0-5% by weight and ZrO ₂ 1-5% by weight
A decorative glass substrate obtained by painting and firing a coloring composition having a glass flux comprising a color pigment and a coloring pigment. 7. The method according to claim 6, wherein the glass flux is 50 to 100% by weight, and the coloring pigment is 0 to 5% by weight.
A decorative glass substrate, which is 0% by weight. 8. The decorative glass substrate according to claim 6, wherein the coloring composition further contains TiO ₂ as an additive. 9. The decorative glass substrate according to claim 8, wherein the content of the additive is 0 to 20 parts by weight based on 100 parts by weight of the total weight of the glass flux and the coloring pigment. . 10. The decorative glass substrate according to claim 6, wherein the decorative glass substrate is a top plate of a cooker. 11. The decorative glass substrate according to claim 6, wherein the decorative glass substrate is a heater panel.