JP4004529B1 - Glass top plate for heating cooker - Google Patents

Abstract

Disclosed is a glass top plate for a heating cooker having a coating layer that can easily remove dirt adhering to the surface, has excellent wear resistance and heat resistance, and has a transparent coating layer that does not impair the appearance. .
A glass top plate 1 for a cooking appliance in which a coating layer 3 is laminated on a cooking surface 21 of a substrate glass 2 made of a low expansion crystallized glass plate. The coating layer 3 is mainly composed of Zr and one or more of Bi, Sn, and In. The coating layer 3 is formed by applying a paste composed of a Zr metal resinate, one or more metal resinates of Bi, Sn, and In and an organic resin to the substrate glass 2 and baking at 500 to 900 ° C. Is done.
[Selection] Figure 1

Description

  The present invention relates to a glass top plate for a heating cooker.

  Conventionally, a glass top plate for a cooker made of a glass plate is installed on the top of a cooker such as an electromagnetic cooker or a gas cooker. An object to be heated such as a pan is installed on the glass top plate for the cooker, and the object to be heated can be cooked by a heating device inside the cooker. In particular, electromagnetic cookers tend to be increasingly demanded in recent years because of their high safety, and accordingly, the demand for glass top plates for cookers is also increasing.

As such a glass top plate for a cooker, techniques (Patent Documents 1 to 4) relating to an antifouling film have been reported in order to enhance the antifouling property.
However, since the technique described in Patent Document 1 is a film composed of a siloxane bond, the film may be peeled off in a relatively short time due to friction with a cooking utensil such as a pan or a frying pan. Further, since it is easily affected by water, film formation under an anhydrous atmosphere is necessary, and there is a problem that the working environment is limited.

  Moreover, since the technique of the said patent document 2 has low baking temperature after coating as 100-700 degreeC, when a film | membrane is formed on the glass substrate whose softening point is 900 degreeC or more, it does not contain a flux component. Therefore, there is a possibility that the reaction between the film and the substrate becomes insufficient, the adhesion strength between the film itself and the glass substrate is weak, and there is a possibility that the film easily peels due to wear of an iron pan, a stainless steel pan, or the like. In addition, when printing is performed by a screen printing method using a water-soluble zirconium compound and a zirconium oxide sol, since the viscosity of the solution is too low, it is difficult to form a uniform printed film. In addition to the possibility of flowing into a non-uniform film, there is a problem in that continuous printability is poor.

  Moreover, since the technique described in Patent Document 3 is mainly composed of a fluorine compound, the heat resistance is poor, and when the temperature exceeds 500 ° C., there is a possibility of discoloration. In addition, there is a problem that scratches are likely to occur when rubbed or polished with an abrasive detergent or metal scrubber.

  Further, the technique described in Patent Document 4 is a technique for producing a film by a sol-gel method, a spray method, or a CVD method, but there is no problem when a film is formed on a transparent glass plate. When applied to a glass plate for an electromagnetic cooker, it has a drawback of lack of continuous workability and high cost.

JP 2006-8420 A JP 2005-321108 A JP 2003-51374 A JP 2000-86297 A

  The present invention has been made in view of such conventional problems, and can easily remove dirt adhering to the surface, is excellent in wear resistance and heat resistance, is transparent and has an appearance. An object of the present invention is to provide a glass top plate for a heating cooker having a coating layer that does not deteriorate.

The present invention is a glass top plate for a cooking device in which a coating layer is laminated on a cooking surface of a substrate glass made of a low expansion crystallized glass plate,
The coating layer is formed by applying a paste composed of a Zr metal resinate, one or more of Bi, Sn, and In, and an organic resin to the substrate glass and firing at 500 to 900 ° C. ,
The total of the Zr content in the paste and the total content of one or more of Bi, Sn, and In is 1 to 10% by weight, and any one of Zr content and Bi, Sn, or In The ratio to the total content (Zr: Bi + Sn + In) is 99.9: 0.1 to 40:60, which is in the glass top plate for a heating cooker (Claim 1).

  The coating layer of the glass top plate for a heating cooker of the present invention contains Zr as an essential component. Since Zr has the property of improving dirt removal properties, the glass top plate for a heating cooker can easily remove dirt attached to the surface when used in the coating layer. An excellent effect can be obtained.

  The coating layer contains one or more of Bi, Sn, and In as an essential component. The Bi, Sn, and In have an effect of improving the adhesion strength when the Zr component is adhered to the substrate glass. Therefore, when one or more of these are contained in the coating layer, the adhesive strength of the coating layer is improved, and the glass top plate for a heating cooker can have excellent wear strength and heat resistance. Moreover, since a coating layer becomes transparent and does not impair an external appearance, the glass top plate for heating cookers becomes the thing excellent in the designability.

  Thereby, on the cooking surface of the substrate glass, the dirt adhering to the surface can be easily removed by laminating a coating layer mainly composed of Zr and one or more of Bi, Sn, and In. It is possible to obtain a glass top plate for a heating cooker that has a coating layer that is excellent in wear resistance and heat resistance, is transparent, and does not impair the appearance. In addition, the said cooking surface is a surface which puts a pan etc. when using a heating cooker.

As described above, the glass top plate for a heating cooker according to the present invention is formed by laminating a coating layer mainly composed of Zr and one or more of Bi, Sn, and In on the cooking surface of the substrate glass.
In the said coating layer, the stain | pollution | contamination adhering to the glass top plate surface for heating cookers can be easily removed by containing Zr.

  On the other hand, when the coating layer does not contain any of Bi, Sn, or In and is composed only of Zr resinate, the formed coating layer does not contain a flux, and thus has very weak adhesion. It will be in close contact with the substrate glass by force. Therefore, although the stain removability can be sufficiently exhibited, there are problems that it is easily scraped off with a metal scrubber, a non-woven sponge with an abrasive, or the like, and that it is damaged.

As described above, the coating layer containing Zr and any one of Bi, Sn, and In as an essential component can be formed as follows.
That is, the coating layer of the glass top plate for a heating cooker according to the present invention is obtained by applying a paste made of Zr metal resinate, one or more metal resinates of Bi, Sn, and In and an organic resin to the substrate glass. , it is formed by firing at 500 to 900 ° C..

  In this case, in order to form a paste, for example, a coating method having excellent film formability such as a screen printing method can be performed. Therefore, it is not necessary to perform a sol-gel method, a spray method, a CVD method, or the like, which lacks continuous productivity and may increase costs, and a glass top plate for a heating cooker can be created by a simple method.

The metal resinate is a dilute solution of an organometallic compound and is a liquid having good dispersibility. Therefore, a uniform film can be formed when the coating layer is formed.
Examples of the organic resin include acrylic resins, amide resins, alkyd resins, and cellulose resins.

  Moreover, when the said calcination temperature is less than 500 degreeC, there exists a possibility that a uniform film | membrane with sufficient adhesive force cannot be formed. On the other hand, in the case where the firing temperature exceeds 900 ° C., there is a possibility that the substrate glass becomes cloudy when the substrate glass having β-quartz as a main crystal described later is used.

The total of the Zr content in the paste and the total content of one or more of Bi, Sn, and In is 1 to 10% by weight, and any of Zr content and Bi, Sn, or In The ratio (Zr: Bi + Sn + In) to one or more total contents is 99.9: 0.1 to 40:60 .

When the sum of the Zr content in the paste and the total content of one or more of Bi, Sn, and In is less than 1% by weight, the density is low, so that repellency occurs immediately after printing. Phenomenon tends to occur, and many craters (portions where no coating layer is present) may occur after firing. On the other hand, when the above sum exceeds 10% by weight, the film thickness (coating amount) of the coating layer is increased and the characteristics of the coating layer are maintained, but the transparency is partially lost or the iris color is reduced. There is a risk that the design will be reduced.
Thereby, the total of the Zr content in the paste and the total content of one or more of Bi, Sn, and In is more preferably 2 to 5% by weight.

Further, when the sum of the Zr content and the total content of any one or more of Bi, Sn, and In (Bi + Sn + In) is 100 wt%, the stain removability deteriorates when Bi + Sn + In exceeds 60 wt%. There is a fear. On the other hand, when Bi + Sn + In is less than 0.1 wt%, the wear strength may be reduced.
Thereby, (Zr: Bi + Sn + In) is more preferably 99.9: 0.1 to 60:40.

In addition, the paste further includes one or more of Au, Pt, Pd, Rh, Mn, Ni, Fe, Cr, Ca, Si, Ba, Sr, Mg, Ag, and Ti in a total of 5 wt%. You may contain below (Claim 2 ).
When these contain more than 5 wt% in total, there exists a possibility that the stain | pollution | contamination removability of the said coating layer may deteriorate.

Moreover, it is preferable that the said coating layer is formed in the cooking surface whole surface or a part (Claim 3 ).
In this case, it is possible to easily cope with application by screen printing or the like.

Further, the substrate glass is preferably linear thermal expansion coefficient of ^{-10~80 × 10 -7 / ℃ (30~500} ℃) ( claim 4).
When the linear thermal expansion coefficient of the substrate glass is out of the range of −10 to 80 × 10 ⁻⁷ / ° C. (30 to 500 ° C.), there is a problem that it is not suitable as the substrate glass used for the glass top plate for cooking. is there.

The substrate glass preferably contains β-quartz solid solution and β-spodumene as the main crystal (Claim 7 ).
The transparent low expansion crystallized glass plate having the β-quartz solid solution or β-spodumene as a main crystal is particularly suitable as a substrate glass for a glass top plate for a heating cooker.

Moreover, it is preferable that the decoration layer which consists of a glass composition and an inorganic pigment is formed in the upper surface of the said coating layer or between a coating layer and board | substrate glass (Claim 6 ).
In this case, the design property can be improved without reducing the original strength of the substrate glass.
In addition, the glass composition is more preferably a lead-free glass composition in consideration of recyclability and the like.

  In addition, when a decorative layer is formed on the upper surface of the coating layer, the effect of suppressing the wear of the coating layer can be obtained, and therefore the wear resistance of the glass top plate for a heating cooker can be further improved. it can.

As said glass composition, it is preferable that a softening point is 650 degrees C or less. Moreover, it is more preferable to use a lead-free glass composition that contains SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , and Li ₂ O as essential components and crystallizes by heat treatment at 700 to 900 ° C.

Examples of the inorganic pigment include a white inorganic pigment, a black inorganic pigment, a gray inorganic pigment, a yellow inorganic pigment, a brown inorganic pigment, a green inorganic pigment, a blue inorganic pigment, and a pink inorganic pigment.
Specifically, as the white inorganic pigment, for _{example, TiO 2, ZrO 2, ZrSiO} 4, Al 2 O 3, 3Al 2 O 3 -2SiO 2, Li 2 O · Al 2 O 3 · 8SiO 2, Al 2 TiO _5, and the like.

Examples of the black inorganic pigment include Cr-Fe-based oxides, Co-Mn-Cr-Fe-based oxides, Co-Ni-Cr-Fe-based oxides, and Co-Ni-Cr-Fe-Mn-based materials. An oxide etc. are mentioned.
Examples of the gray inorganic pigment include Sn-Sb-based oxides and Sn-Sb-V-based oxides.

Examples of the yellow inorganic pigment include Sn-V oxides, Zr-V oxides, Zr-Si-Pr oxides, Ti-Cr-Sb oxides, and the like.
Examples of the brown inorganic pigment include Zn-Al-Cr-Fe-based oxides and Zn-Mn-Al-Cr-Fe-based oxides.

Examples of the green inorganic pigment include Ca—Cr—Si oxides, Cr—Al oxides, Co—Zn—Al—Cr oxides, and Zr—Si—Pr—V oxides. It is done.
Examples of the blue powder include Co—Al—Zn-based oxides, Co—Al-based oxides, and Zr—Si-based oxides.
Examples of the pink inorganic pigment include, for example, Mn—Al oxide, Ca—Sn—Si—.
Examples thereof include Cr-based oxides, Sn—Cr-based oxides, and Zr—Si—Fe-based oxides.

Moreover, it is preferable that the said decoration layer is formed so that it may become arbitrary patterns (Claim 9).
Examples of the arbitrary pattern include a dot shape, a line shape, and a solid having a certain area.

When the decoration layer is formed on the upper surface of the coating layer, the decoration layer is preferably a pattern having a small area so that the effect of removing dirt of the coating layer can be sufficiently exhibited.
On the other hand, when the decoration layer is formed between the coating layer and the substrate glass, the effect of removing the dirt of the coating layer is not reduced, and the shape of the decoration layer is not limited.

  Moreover, the decoration layer which consists of a glass composition and an inorganic pigment may also be formed in the surface on the opposite side to a cooking surface by a well-known method. In this case, the design of the top plate for a cooker provided with a coating layer having a stain removing effect can be improved by the decorative layer formed on the side opposite to the cooking surface.

Example 1
In this example, an example of the glass top plate for a heating cooker according to the present invention will be described with reference to FIG.
The glass top plate 1 for a heating cooker of this example is formed by laminating a coating layer 3 on a cooking surface 21 of a substrate glass 2 made of a low expansion crystallized glass plate. The coating layer 3 is mainly composed of Zr and one or more of Bi, Sn, and In.

  As the substrate glass 2, there are two kinds of transparent low expansion crystallized glass (Neoceram N-0) having β quartz as a main crystal and white opaque crystallized glass (Neoceram N-11) having β-spodumene as a main crystal. Using.

  The coating layer 3 is a paste made of a metal resinate and an organic resin. The paste is printed (applied) onto the cooking surface 21 of the substrate glass 2 using a stainless steel 350 mesh screen and baked at 800 ° C. Was formed.

As the paste, a Zr-Bi paste using a metal resinate of Zr and Bi and adjusted so that the Zr content concentration in the paste was 4.95 wt% and the Bi content concentration was 0.05 wt% was used.
As the Zr metal resinate, a commercially available Zr resinate (concentration 10%) was used.
As the Bi metal resinate, a commercially available Bi resinate (concentration 25%) was used.

As the organic resin, one obtained by dissolving ethyl cellulose in an organic solvent (butyl cellosolve) to a concentration of 3% was used.
A glass top plate 1 for a heating cooker using Neoceram N-0 as the substrate glass 2 is referred to as a sample E1, and a glass top plate 1 for a heating cooker using Neoceram N-11 as the substrate glass 2 is referred to as a sample E2.

(Example 2)
This example is an example in which the Zr content and the Bi content in the Zr-Bi paste of Example 1 are changed.
Specifically, using the same metal resinate and organic resin as in Example 1, a Zr—Bi paste of Zr: 2.5 wt% and Bi: 2.5 wt% was prepared. Others are the same as in the first embodiment.
A glass top plate for a heating cooker using Neoceram N-0 as the substrate glass is designated as sample E3, and a glass top plate for a heating cooker using Neoceram N-11 as the substrate glass is designated as sample E4.

(Example 3)
This example is an example in which the Zr content and the Bi content in the Zr-Bi paste of Example 1 are changed.
Specifically, using the same metal resinate and organic resin as in Example 1, a Zr—Bi paste of Zr: 3 wt% and Bi: 2 wt% was prepared. Others are the same as in the first embodiment.
A glass top plate for a heating cooker using Neoceram N-0 as the substrate glass is designated as sample E5, and a glass top plate for a heating cooker using Neoceram N-11 as the substrate glass is designated as sample E6.

(Example 4)
In this example, as shown in FIG. 2, a decorative layer 4 is formed between the substrate glass 2 and the coating layer 3 of Example 3.
Specifically, using a paste made of a lead-free glass composition, an inorganic pigment, and an organic resin, a dot having a diameter of 0.65 mm and a pitch of 1 mm is used on the cooking surface 21 of the substrate glass 2 and a stainless steel # 350 mesh is used. Then, the decorative layer 4 was formed by coating by screen printing and baking at 800 ° C.

As the lead-free glass composition, a lead-free glass composition having a softening point of 650 ° C. or less, containing SiO ₂ : 63 wt%, Al ₂ O ₃ : 12 wt%, B ₂ O ₃ : 20 wt%, and Li ₂ O: 5 wt%. As the inorganic pigment, a Co—Ni—Cr—Fe black pigment was used, and a commercially available acrylic resin was used as the organic resin.

Thereafter, the coating layer 3 was formed in the same manner as in Example 3.
A glass top plate for a heating cooker using Neoceram N-0 as the substrate glass 2 is designated as sample E7, and a glass top plate for a heating cooker using Neoceram N-11 as the substrate glass 2 is designated as sample E8.

(Comparative Example 1)
In this example, the Zr-Bi paste in Example 1 is changed to a Bi paste.
Bi: 5 wt% Bi paste was prepared using the same metal resinate and organic resin as in Example 1. Others are the same as in the first embodiment.
A sample using Neoceram N-0 as the substrate glass is referred to as Sample C1, and a sample using Neoceram N-11 as the substrate glass is referred to as Sample C2.

(Comparative Example 2)
In this example, the Zr-Bi paste in Example 1 is changed to a Zr paste.
Using the same metal resinate and organic resin as in Example 1, a Zr: 5 wt% Zr paste was prepared. Others are the same as in the first embodiment.
A sample using Neoceram N-0 as the substrate glass is referred to as Sample C3, and a sample using Neoceram N-11 as the substrate glass is referred to as Sample C4.

<Evaluation>
Next, it becomes dirty about the glass top plate (sample E1-sample E8, sample C1-sample C4) for heating cookers produced in Examples 1-4 and Comparative Examples 1 and 2, neo-serum N-0, and neo-serum N-11. Removability, peelability, and heat resistance were evaluated.
The stain removal property was evaluated by conducting a burn wiping test and a sustainability test.

The above scorching wiping test is performed by dropping 10 drops of a solution adjusted to sugar: soy sauce = 1: 1 onto the cooking surface of a glass top plate for a heating cooker, and then being made of stainless steel so that the solution is completely covered. The pan was placed and steamed at 200 ° C. for 30 minutes using an electromagnetic cooker to prepare a burn.
After the prepared burn was sufficiently cooled, it was rubbed with a wet cloth for a maximum of 30 times to test whether the burn on the Zr or Zr-Bi film could be extracted.
The results are shown in Table 1. An evaluation result of ◯ is accepted, and an evaluation result of x is rejected.

(Burn wiping test evaluation criteria)
○: Burn could be removed in 30 times or less ×: Burn could not be removed in 30 times

In the sustainability test, the burnt wiping test was repeated up to 30 times for those that passed in the burn wiping test, and the sustainability was evaluated.
The results are shown in Table 1. As for the soil removability, the evaluation of the sustainability test is “good” and the “x” is rejected.
(Sustainability test evaluation criteria)
○: Even after repeated 30 times, the burn wiping test passed. ×: Repeated less than 30 times, and the burn wiping test failed.

Next, the above peelability was observed by visually observing the coating film after 5 g of abrasive detergent was dropped on the cooking surface of the glass top plate for a cooker and rubbed 1000 times with a metal scrubber. The peelability was evaluated.
The results are shown in Table 1. An evaluation result of ◯ is accepted, and an evaluation result of x is rejected.

(Peelability evaluation criteria)
○: No peeling of coating film is confirmed ×: No peeling of coating film is confirmed

Then, the heat resistance was evaluated about the sample E1-sample E8 which passed by the said burning wiping property, sustainability, and peelability. After heating, the heat resistance was evaluated from the surface state, burn-off property, and durability.
First, the surface state after heating at 600 ° C. for 20 hours was visually confirmed to evaluate heat resistance. The results are shown in Table 1. An evaluation result of ◯ is accepted, and an evaluation result of x is rejected.
(Surface condition evaluation criteria)
○: No white turbidity, dullness, etc., and no difference from the initial state ×: White turbidity, dullness, etc. confirmed

Then, the above-mentioned burning wiping test and sustainability test were similarly performed about the sample after this heating.
The results are shown in Table 1. The heat resistance is determined to be acceptable when the evaluation results of the surface state, scorching wiping property, and sustainability are all ◯.

  As is known from Table 1, Samples E1 to E8, which are examples of the present invention, were all good in scoring, continuity, peelability, and heat resistance. For this reason, it is possible to easily remove the dirt adhering to the surface, and the glass top plate for a heating cooker having a coating layer that is excellent in wear resistance and heat resistance, has a transparent and does not impair the appearance, and is easy to use. It was possible to make it by the method.

Further, as can be seen from Table 1, the sample C1 and the sample C2, which are comparative examples of the present invention, did not contain dirt, and therefore did not have dirt removal property and failed to burn.
Moreover, since the sample C3 and sample C4 which are comparative examples of this invention do not contain Bi, the coating layer did not have adhesive strength, the wear strength was low, and the peelability was unacceptable.

  In Examples 1 to 4, a glass top plate for a heating cooker having a coating layer mainly composed of Zr and Bi was produced. Similar results were obtained using Sn and In instead of Bi. Can be obtained.

Explanatory drawing which shows the glass top plate for heating cookers in Example 1. FIG. Explanatory drawing which shows the glass top plate for heating cookers in Example 4. FIG.

Explanation of symbols

1 Glass top plate for cooking device 2 Substrate glass 21 Cooking surface 3 Coating layer

Claims (7)

A glass top plate for a cooker, in which a coating layer is laminated on a cooking surface of a substrate glass made of a low expansion crystallized glass plate,
The coating layer is formed by applying a paste composed of a Zr metal resinate, one or more of Bi, Sn, and In, and an organic resin to the substrate glass and firing at 500 to 900 ° C. ,
The total of the Zr content in the paste and the total content of one or more of Bi, Sn, and In is 1 to 10% by weight, and any one of Zr content and Bi, Sn, or In A glass top plate for a heating cooker characterized in that the ratio (Zr: Bi + Sn + In) to the total content is 99.9: 0.1 to 40:60 . 2. The paste according to claim 1, further comprising at least one of Au, Pt, Pd, Rh, Mn, Ni, Fe, Cr, Ca, Si, Ba, Sr, Mg, Ag, and Ti. A glass top plate for a heating cooker characterized by containing a total of 5 wt% or less. The glass top plate for a heating cooker according to claim 1 or 2, wherein the coating layer is formed on the entire cooking surface or a part thereof. 4. The substrate glass according to claim 1, wherein the substrate glass has a linear thermal expansion coefficient of −10 to 80 × 10. ^-7 A glass top plate for a heating cooker characterized by being / ° C (30 to 500 ° C). The glass top plate for a heating cooker according to any one of claims 1 to 4, wherein the substrate glass has a β-quartz solid solution and β-spodumene as a main crystal. The heating according to any one of claims 1 to 5, wherein a decoration layer comprising a glass composition and an inorganic pigment is formed on the upper surface of the coating layer or between the coating layer and the substrate glass. Glass top plate for cooker. The glass top plate for a heating cooker according to claim 6, wherein the decorative layer is formed in an arbitrary pattern.

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