JP4513523B2 - Cooking equipment - Google Patents

Description

The present invention relates to a cooking device using a heat and antifouling substrate having water and oil repellency excellent in heat resistance and wear resistance.

Conventionally, a glass having an antifouling thin film of an organic fluorine compound having a siloxane bond (hereinafter referred to as a fluorine-based chemical adsorption monomolecular film) formed on the surface is known as a glass having a water / oil repellent coating (for example, Patent Document 1). Similarly, a substrate in which a fluorine-based chemical adsorption monomolecular film is formed on the surface of a base material subjected to ceramic coating, enamel treatment or hard alumite treatment is known as a substrate having a water / oil repellent coating (for example, Patent Document 2). On the other hand, in order to improve heat resistance and water / oil repellency, a glass substrate having an alumina thin film formed on the surface of the glass and a fluorine-based chemical adsorption monomolecular film formed on the surface of the alumina thin film is used. A cooker is known (see, for example, Patent Document 3). In the same way, a metal oxide thin film such as silica is used as a material other than alumina, and this metal oxide thin film is interposed as an intermediate material to provide a fluorine-based chemisorption monomolecular film having a siloxane bond as the top surface. There is also a glass substrate formed in the above and a cooker using this.
Japanese Patent No. 2577204 Japanese Patent No. 2921197 Japanese Patent No. 3064808

  However, the structure in which a conventional fluorine-based chemical adsorption monomolecular film is directly formed on a glass or enameled base material has the advantage of having water and oil repellency, but regarding its heat resistance, the material composition of the substrate on which it is formed It is compatible with. For this reason, this conventional configuration has an unclear compatibility with the substrate material composition, and there is a problem that heat resistance of 200 ° C. or more cannot be secured depending on the base material material. For this reason, an antifouling substrate in which a fluorine-based chemical adsorption monomolecular film is simply formed on a glass, ceramic coating, enameled or hard anodized base material should be used in a relatively mild environment of 200 ° C or lower. I had to. This is because the silane surfactant containing an organic fluorine compound, which is the raw material of the fluorine-based chemical adsorption monomolecular film, is compatible with the metal oxide constituting the substrate material, and simply has a hydroxyl group in the metal oxide. If so, it is caused by a property that does not chemically react to form a strong siloxane bond. Therefore, depending on the type of metal oxide, a strong siloxane bond is generated, or a siloxane bond having a slightly weak bond is generated.

  In order to solve this problem and to use it at a temperature of 200 ° C. or higher, a metal oxide thin film such as alumina is interposed, and a chemisorption monomolecular film is formed thereon to improve adhesion. However, this technique of interposing the metal oxide thin film firmly fixes the metal oxide thin film to the base material in order to ensure the wear resistance of the fluorine-based chemical adsorption monomolecular film formed thereon. For this reason, the metal oxide thin film was formed on the substrate using a complicated manufacturing method and strict quality control. In this way, the conventional technology is unclear with the material composition of the substrate, and in order to improve heat resistance and ensure wear resistance, it is strictly strict with complicated manufacturing methods such as interposing a thin film such as alumina. There has been a problem that it is necessary to form a chemisorbed monomolecular film after processing a substrate with proper quality control to expose many hydroxyl groups on its surface.

  In view of the above-described conventional problems, the problem to be solved by the present invention is a heat-resistant and antifouling substrate that has water and oil repellency excellent in heat resistance and wear resistance and that can be easily manufactured, and heating using the same. It is to provide cooking equipment.

In order to solve the above-described problems, a cooking device according to the present invention includes a heat-resistant and antifouling substrate, a case that is disposed below the heat-resistant and antifouling substrate, and holds and fixes the heat-resistant and antifouling substrate, the case, and the case A cooking and heating component housed in an internal space provided between the heat-resistant and antifouling substrate, and the heat-resistant and antifouling substrate is composed of 100 to 50 wt% silicon, an alkali metal and an alkaline earth metal Silicic acid-based oxide having an elemental composition not exceeding 100 wt% in total, containing an alkali content of 30 wt% or less, 1 to 25 wt% aluminum, 1 to 18 wt% zirconium, and 1 to 19 wt% titanium An antifouling thin film of an organic fluorine compound having a siloxane bond on one side is formed, and a refractory metal containing any one of platinum, gold and panadium and bismuth oxide is formed on the other side. In which the film is formed.

  The heat-resistant substrate of the present invention is an organic fluorine compound having a siloxane bond in which a hydroxyl group present on the surface of a silicate-based oxide and a silane group contained in the organic fluorine compound sufficiently react to obtain a strong siloxane bond. Thus, a water- and oil-repellent heat-resistant and antifouling substrate excellent in heat resistance and abrasion resistance can be easily obtained.

  INDUSTRIAL APPLICABILITY According to the present invention, a heat-resistant and antifouling substrate of a fluorine-based chemical adsorption monomolecular film having a siloxane bond having both water and oil repellency, heat resistance and abrasion resistance can be easily obtained. In addition, by applying this heat-resistant and antifouling substrate to a cooking device, even if the food is stuck, it can be easily peeled off by simple cleaning, and the beauty and cleanliness can be maintained over a long period of time.

A cooking device according to a first aspect of the present invention includes a heat-resistant and antifouling substrate, a housing disposed below the heat and antifouling substrate, and holding and fixing the heat and antifouling substrate, and the housing and the heat and antifouling substrate. A cooking / heating component housed in an internal space provided therebetween, wherein the heat-resistant and antifouling substrate comprises 100 to 50 wt% of silicon, an alkali content of 30 wt% or less made of alkali metal and alkaline earth metal And 1-25 wt% aluminum, 1-18 wt% zirconium, 1-19 wt% titanium, and a silicic acid-based oxide having an elemental composition not exceeding 100 wt% in total. .

  A silane-based surfactant containing an organic fluorine compound, when brought into contact with a metal oxide, chemically reacts with a hydroxyl group present on the surface thereof to form a siloxane bond, and the surface of the metal oxide is water- and oil-repellent and antifouling. It has the property of imparting a thin film. When a silicate-based oxide in which an appropriate amount of silicon oxide or alkali-based oxide and aluminum, zirconium, or titanium are mixed is used as the metal oxide, the hydroxyl group present on the surface and the silane group contained in the organic fluorine compound However, it reacts sufficiently and a strong siloxane bond is obtained. For this reason, when an antifouling thin film of an organic fluorine compound having a siloxane bond is formed on the surface of a heat resistant substrate having this composition, a water and oil repellent heat and antifouling substrate having excellent heat resistance and abrasion resistance can be obtained. Obtained by manufacturing method and quality control.

The heat-resistant and antifouling substrate has a fired film mainly composed of a heat-resistant metal formed on the lower surface thereof.

The fired film has a colored metal color because the heat-resistant metal is the main component. Therefore, using transparent glass as the heat-resistant substrate, the metal color of the fired coating makes it difficult to see the cooking residue attached to the surface of the transparent antifouling thin film, and the beauty and cleanliness can be maintained over a long period of time. In addition, the fired film is hydrophilic, and even if an extremely thin organic fluorine compound film constituting the antifouling thin film is wound around, the fired film becomes hydrophilic due to the hydrophilic effect of the heat-resistant metal as the main component. Since the fired film has hydrophilicity, it is difficult to form polka dots, and the moisture adhering to the surface does not easily fall, and the moisture hardly falls to the cooking and heating component arranged at the lower position. For this reason, even if the cooking device is used in a hot and humid environment such as a commercial kitchen for a long period of time, the condensation moisture falling from the heat-resistant and antifouling substrate is reduced, and the cooking and heating parts that heat the cooking pan are moisture-proof. We can cope with measures.

The refractory metal contained in the fired film is at least platinum, gold, or palladium. When the refractory metal is such a metal, the surface is more difficult to form polka dots, and the moisture adhering to the surface is less likely to fall, and the moisture is less likely to fall to the cooking and heating component disposed at the lower position. For this reason, the cooking and heating component can cope with a simpler moisture-proof measure.

In addition, a heat-resistant and antifouling substrate, a casing that is disposed below the heat-resistant and antifouling substrate, and holds and fixes it, and a cooking and heating component that is housed in an internal space provided between the casing and the heat and antifouling substrate The heat-resistant and antifouling substrate is formed with a baked film containing bismuth oxide and a heat-resistant material formed on the lower surface thereof.

  Bismuth oxide has the property that when it is melted by firing, it expands in volume to form a porous hydrophilic colored film, and the porous film is segregated and scattered. Therefore, when the colored bismuth oxide is mixed, a beautiful fired film can be formed by a synergistic effect with the heat-resistant material. Therefore, even if transparent glass is used as the heat-resistant substrate for forming the antifouling thin film, the colored fired coating existing on the back side makes it difficult to see the cooking residue adhering to the surface of the transparent antifouling thin film. A beautiful and clean feeling can be maintained. In addition, the extremely thin organic fluorine compound constituting the antifouling thin film wraps around inside the porous fired coating film even if it goes around. Therefore, it becomes difficult to form polka dots and the moisture adhering to the surface does not easily fall, and the moisture does not easily fall on the cooking and heating component arranged at the lower position. Furthermore, this porous hydrophilic fired coating reduces interference with the bonding between the housing and the heat-resistant and antifouling substrate. Therefore, the housing can be easily and satisfactorily bonded to the heat-resistant and antifouling substrate.

Further, in the first aspect, the organosilicone film is formed on the lower surface of the sintered film Tei
The When using a heat-resistant substrate with an organosilicone film formed on the lower surface of the fired film, a vapor-phase evaporation fired film of organosilicone resin naturally forms on the back side of the organosilicone film. Is done. In the present invention, since the antifouling thin film is formed on the surface of the vapor-phase evaporation fired film, there is an advantage that the heat resistance is improved. In addition, since the organic silicone film is hydrophilic, the extremely thin organic fluorine compound constituting the antifouling thin film wraps around the porous organic silicone film even if it goes around. Therefore, it becomes difficult to form polka dots and the moisture adhering to the surface does not easily fall, and the moisture does not easily fall on the cooking and heating component arranged at the lower position. Furthermore, this porous fired coating reduces interference with the bonding between the housing and the heat-resistant and antifouling substrate. Therefore, the housing is simple and can be bonded to the heat-resistant and antifouling substrate very well.

  The cooking device according to the second invention is a fired film containing 1 to 30 wt% of bismuth oxide used in the first invention. A fired coating containing 1 to 30 wt% of bismuth oxide provides a porous fired coating that reduces interference with the housing and the heat-resistant and antifouling substrate. Bond well.

Cooking appliances of the third invention, heat antifouling substrate used in the first or second aspect is one that is joined to the housing using an organic silicone adhesive. The organic silicone adhesive is an adhesive excellent in heat resistance, and has an affinity with a heat-resistant and antifouling substrate, so that it becomes familiar and can easily maintain an excellent bonding force for a long period of time.

An object of the present invention, since it achieved by the embodiment of the essential part of the invention, hereinafter, the embodiments will be described in detail with reference to the drawings. The present invention is not limited to the present embodiment. Further, in the description of the present embodiment, the same reference numerals are given to the portions having the same configuration and effects.

(Embodiment 1)
Fig.1 (a) is a block diagram of the heat-resistant antifouling board | substrate in Embodiment 1 of this invention. The heat-resistant and antifouling substrate 1 of the present embodiment includes a heat-resistant substrate 3 having a silicate oxide 2 on its surface and an antifouling thin film 4 of an organic fluorine compound having at least a siloxane bond formed on the surface of the silicate oxide 2. It consists of and. On the other hand, the silicic acid-based oxide 2 has an elemental composition of 50 wt% to 100% of silicon and a total amount of alkalis composed of alkali metal and alkaline earth metal of 30 wt% or less.

  A silane-based surfactant containing an organic fluorine compound, when brought into contact with a metal oxide, chemically reacts with a hydroxyl group present on the surface thereof to form a siloxane bond, and the surface of the metal oxide is water- and oil-repellent and antifouling. It has the property of imparting a thin film. Therefore, any material as a metal oxide has many hydroxyl groups on its surface and chemically reacts with a silane-based surfactant containing an organic fluorine compound to form a strong siloxane bond. Selection was made as to whether it had excellent heat resistance and maintained for a long time. In this material selection, the lump obtained by molding and sintering the powder was first polished to obtain a metal oxide plate. Next, heptadecafluorodecyltrichlorosilane was prepared as a raw material for an organic fluorine compound having a siloxane bond, and an organic solution diluted with hexamethylsiloxane was prepared. Then, the metal oxide plate is immersed in this organic solution under a nitrogen atmosphere, and then left in the air, whereby an antifouling thin film made of an organic fluorine compound having a siloxane bond is formed on the surface of the metal oxide. Obtained. The water repellency and heat resistance of the antifouling thin film were evaluated when the metal oxide plate having the antifouling thin film was left in an electric furnace at 300 ° C. for a predetermined time. As a result, the heat resistance of the metal oxide forming the antifouling thin film is improved when silicic acid is used, and the heat resistance is lowered when the oxide of alkali metal or alkaline earth metal is used. It was found that the effect on heat resistance was somewhat small.

Then, the composition optimization examination of the silicic acid system oxide which can maintain the outstanding heat resistance regarding water repellency for a long time was performed to the antifouling thin film 4 of the organic fluorine compound having a siloxane bond. The manufacturing method of the heat-resistant antifouling substrate 1 will be described. First, the heat-resistant substrate 3 made of the silicate-based oxide 2 was prototyped. This heat-resistant substrate 3 is made by using a powder obtained by mixing silicic acid, an oxide of an alkali metal and an alkaline earth metal, boric acid, iron oxide, manganese oxide, and cobalt oxide in an arbitrary ratio, and molding and sintering the mixed powder. This is a product obtained by polishing the lump to obtain a silicate oxide 2 having a different composition. After the heat-resistant substrate 3 is cleaned to remove the dirt adhering to the surface, heptadecafluorodecyltrichlorosilane is prepared as a raw material for an organic fluorine compound having a siloxane bond, and diluted with hexamethylsiloxane. Was formulated. Then, the heat-resistant antifouling substrate 1 on which the antifouling thin film 4 of at least an organic fluorine compound having a siloxane bond is formed by immersing the heat-resistant substrate 3 in this organic solution under a nitrogen atmosphere and then leaving it in the air. Obtained. The heat-resistant and antifouling substrate 1 is a water-repellent material having a water contact angle (measured at room temperature) of 110 to 115 ° immediately after film formation.

  For the heat resistance, the water repellency when the heat-resistant and antifouling substrate 1 is left for a predetermined time in an atmosphere of 300 ° C. is expressed by the contact angle of water. This value is a measured value at room temperature, and is a measurement result of taking out the heat-resistant and antifouling substrate 1 from a 300 ° C. furnace after cooling for a predetermined time, cooling it to room temperature, and dropping water droplets on the surface. The relationship between the chemical composition of the silicic acid-based oxide 2 used in the study and the heat resistance is shown in FIGS. 1 (b) and 1 (c). FIG. 1B shows the relationship between the silicon content in the silicate-based oxide and the contact angle (water, room temperature value) when left at 300 ° C. for a predetermined time. FIG. 1 (c) shows the content of the total amount of alkalis consisting of alkali metal and alkaline earth metal in the silicic acid-based oxide and the contact angle (water, measured at room temperature) when left at 300 ° C. for a predetermined time. It is a relationship. The content of each element in the silicic acid-based oxide is a result obtained by analyzing the composition with an X-ray microanalyzer, and is expressed by a metal element for simplicity of explanation. It has become. Silicic oxides contain oxides of boron, iron, manganese, and cobalt in addition to silicic acid and alkali oxides.

  From the result of FIG. 1 (b), the contact angle after endurance changes when the silicon content reaches 50 wt%, and when it is 50 to 100 wt%, the contact angle is large and the water repellency is maintained for a long time. Although it has heat resistance, it can be seen that if it is less than 50 wt%, the contact angle is small and the water repellency is immediately reduced, and there is no heat resistance. This is probably because the higher the silicon content, the more silicic acid having more hydroxyl groups, so that the hydroxyl groups and the silane groups contained in the organic fluorine compound react sufficiently to obtain a strong siloxane bond. It is. On the other hand, it seems that the smaller the silicon content, the less the hydroxyl group content, making it impossible to obtain a strong siloxane bond.

  Further, from the result of FIG. 1 (c), the contact angle after endurance changes when the total content of alkali content is 30 wt%, and when it is 30 wt% or less, the contact angle is large and the water repellency is maintained for a long time. Although it has excellent heat resistance, when it exceeds 30 wt%, it can be seen that the contact angle is small and the water repellency is immediately reduced, resulting in no heat resistance. This is because the higher the total alkali content, the more silicic acid-based oxides are more alkaline, so the silane-based surfactant containing the organic fluorine compound that is the raw material for the fluorine-based chemical adsorption monomolecular film is decomposed, This is probably because siloxane bonds cannot be obtained. On the contrary, it is considered that the lower the content of the total alkali content, the more easily the silicate-based oxide is neutral, so that a stronger siloxane bond can be obtained.

  FIG. 2 is a characteristic diagram in which a wet cloth having a weight of about 2 kg is placed on the surface of the heat-resistant and antifouling substrate 1, and the wear resistance is evaluated by performing reciprocating movements a predetermined number of times in 60 cycles per minute. is there. FIG. 2A shows the relationship between the silicon content in the silicate-based oxide and the contact angle (water, room temperature value) when the reciprocating motion is performed a predetermined number of times. FIG. 2 (b) shows the total content of alkali components consisting of alkali metals and alkaline earth metals in silicic acid-based oxides, and contact angles when reciprocating a predetermined number of times (water, room temperature measured values). It is a relationship. The content of each element in the silicic acid-based oxide is a result obtained by analyzing the composition with an X-ray microanalyzer as described above, and is expressed by a metal element for the sake of simplicity. These elements are oxides. Silicic oxides contain oxides of boron, iron, manganese, and cobalt in addition to silicic acid and alkali oxides.

  From the result of FIG. 2 (a), the contact angle after endurance changes when the silicon content reaches 50 wt%, and when it is 50 to 100 wt%, the contact angle is large and the water repellency is maintained for a long time. Although it has abrasion resistance, it can be seen that when it is less than 50 wt%, the contact angle is small and the water repellency is immediately reduced, and there is no abrasion resistance. Further, from the result of FIG. 2B, the contact angle after the durability changes with the total alkali content of 30 wt% as a boundary, and when it is 30 wt% or less, the contact angle is large and the water repellency is maintained for a long time. However, when it exceeds 30 wt%, the contact angle is small and the water repellency is immediately reduced, and it is understood that there is no wear resistance.

  Examples of detailed results of the present invention performed using various materials are shown in Table 1. The effect was determined by the above-mentioned 300 ° C. heat resistance test and abrasion resistance test, and the contact angle (water, room temperature measured value) at that time. In the present invention, an antifouling thin film of an organic fluorine compound having a siloxane bond is directly formed on a glass heat-resistant substrate made of a silicate-based oxide having a silicon content of 50 to 100 wt% and a total alkali content of 30 wt or less. It is a heat-resistant and antifouling substrate. The comparative example is a heat and antifouling antifouling film in which an antifouling thin film of an organic fluorine compound having a siloxane bond is directly formed on a glass heat resistant substrate made of silicic oxide with a total amount of alkali of less than 50 wt% silicon. It is a substrate. In the conventional example, a thin film made of sol-gel of silicic acid or alumina is formed on a glass heat-resistant substrate made of silicic acid-based oxide with an optional alkali content of 30 wt% or less, and a siloxane bond is formed on this thin film. It is a heat-resistant and antifouling substrate on which an antifouling thin film of an organic fluorine compound containing

  The product of the present invention has a large contact angle and excellent durability even when subjected to a 300 ° C. heat resistance test and an abrasion resistance test, and it is also possible to apply the antifouling thin film directly to the heat resistant substrate. There was an advantage that can be easily obtained. On the other hand, when the 300 ° C. heat resistance test and the abrasion resistance test were performed, the comparative example had a problem that the contact angle was small and the durability was inferior. In the conventional example, when a 300 ° C. heat resistance test and an abrasion resistance test are performed, the contact angle is large and the durability is good, but a thin film made of sol-gel of silicic acid or alumina is formed on a heat-resistant substrate. However, it was necessary to process substrates with complicated manufacturing methods and strict quality control.

  The effect of the present invention was evaluated by water repellency, but even if it was oil repellant, the same effect was obtained, and even if a mixed solution of sugar, soy sauce and mirin was baked many times, it could be easily peeled off. In addition, the effect is determined using a glass substrate mainly composed of a silicate-based oxide as a heat-resistant substrate, but a soot substrate formed with a silicate-based oxide glass of this composition on the surface, or this composition The same effect can be obtained by using a glass substrate or ceramic in which any of the above silicate oxide glasses is used and the printed fired film is partially formed. Therefore, it can be applied to cooking containers such as pots and cups, cooking dishes and cooking plates on which these are placed. Furthermore, the content of each element in the silicate-based oxide is a result obtained by composition analysis with an X-ray microanalyzer, and is expressed by a metal element for the sake of simplicity of explanation. It is a thing. The results, examples, and composition analysis methods are the same in various embodiments described below.

  Further, when the chemical composition of the silicic acid-based oxide 2 examined is examined in more detail, the contact angle is further increased and the water repellency is maintained for a long time, particularly when the total alkali content is 13 wt% or less. It can be seen that it has even better heat resistance and wear resistance. The reason for this is that if the total alkali content is 13 wt% or less, the silicate oxide is neutral, so that a stronger siloxane bond can be obtained, and the alkaline component that elutes under high temperature or humidification. This is presumably because the siloxane bond that binds the antifouling thin film 4 is prevented from being deteriorated to form a strong bond. Further, when these materials are used, there is an effect that even if sticking of the cooked food occurs, it can be easily peeled off by simple cleaning.

(Embodiment 2)
In the second embodiment, the chemical composition of the silicic acid-based oxide 2 studied in the first embodiment is examined in more detail, and in particular, the heat resistance and resistance to resistance are compared with other transition metal oxides. This study examines the optimum content of aluminum oxide, which has a large effect on wear. The silicic acid-based oxide used in the study is based on a composite oxide of 50 wt% silicon and 30 wt% alkali. As the composition of the aluminum oxide changes, boron oxide, iron, manganese and cobalt The composition is adjusted by changing the composition of the oxide.

  FIG. 3 shows the relationship between the aluminum content in the silicate-based oxide and the contact angle (water, room temperature value) when left at 300 ° C. for a predetermined time. In FIG. 3, it can be seen that when the aluminum content is 1 to 25 wt%, the contact angle is further increased, the water repellency is maintained for a long time, and the heat resistance is further improved.

The reason seems to be as follows. The first point is that aluminum oxide has many hydroxyl groups, and the greater the amount, the greater the number of siloxane bonds that bind the antifouling thin film and the stronger the bond. On the contrary, the smaller the amount of aluminum oxide, the smaller the amount of hydroxyl groups, so that only a few siloxane bonds that bind the antifouling thin film are formed, resulting in weak bonds. Secondly, since aluminum oxide has a thermal expansion is greater with respect to silicate increases the thermal expansion of the heat-resistant substrate as the amount is large, the peeling due to thermal expansion of the siloxane bond that is bound antifouling film Being bigger and weaker. On the contrary, if the amount of aluminum oxide is small, the thermal expansion of the heat-resistant substrate is reduced, and the siloxane bond that binds the antifouling thin film is prevented from peeling due to thermal expansion to form a strong bond. Third, because the aluminum component content is optimized, the strong bonding phenomenon caused by hydroxyl groups and the peeling phenomenon caused by thermal expansion are balanced to form a strong bond. Further, when these materials are used, there is an effect that even if sticking of the cooked food occurs, it can be easily peeled off by simple cleaning.

(Embodiment 3)
In the third embodiment, the chemical composition of the silicate-based oxide 2 studied in the first or second embodiment described above is examined in more detail. In particular, the heat resistance is higher than that of other transition metal oxides. The optimum content of zirconium oxide, which has a slightly large effect on the content, was investigated. The silicic acid-based oxide used in the study is based on a composite oxide of 50 wt% silicon and 30 wt% alkali. As the composition of zirconium oxide changes, boron oxide, iron, manganese and cobalt The composition is adjusted by changing the composition of the oxide.

  FIG. 4 shows the relationship between the zirconium content in the silicate-based oxide and the contact angle (water, room temperature value) when left at 300 ° C. for a predetermined time. In FIG. 4, it can be seen that when the zirconium content is 1 to 18 wt%, the contact angle is further increased, the water repellency is maintained for a long time and the heat resistance is further improved.

The reason seems to be as follows. The first point is that zirconium oxide has many hydroxyl groups because it easily recrystallizes, and the larger the amount, the more siloxane bonds that bind the antifouling thin film are produced and become stronger bonds. Being. On the contrary, the smaller the amount of zirconium oxide, the smaller the amount of hydroxyl groups, so that only a few siloxane bonds that bind the antifouling thin film are formed, resulting in weak bonds. Secondly, since the zirconium oxide thermal expansion is greater with respect to silicate increases the thermal expansion of the heat-resistant substrate as the amount is large, the peeling due to thermal expansion of the siloxane bond that is bound antifouling film Being bigger and weaker. Conversely, if the amount of zirconium oxide is small, the thermal expansion of the heat-resistant substrate is reduced, and peeling due to thermal expansion of the siloxane bond to which the antifouling thin film is bonded is prevented to form a strong bond. Thirdly, since the zirconium component content is optimized, the strong bonding phenomenon caused by hydroxyl groups and the peeling phenomenon caused by thermal expansion are balanced to form a strong bond. In addition, when these materials are used, the effect of being able to be easily peeled off by simple cleaning and the effect of being excellent in wear resistance even when sticking of the cooked food occurs.

  Moreover, even if it examined with the composition which further contained 1-25 wt% aluminum as an oxide like the above-mentioned Embodiment 2, the same effect produced.

(Embodiment 4)
In the fourth embodiment, the chemical composition of the silicate-based oxide 2 studied in the first, second, or third embodiment described above is examined in more detail, and in particular, compared with other transition metal oxides. This study examines the optimum content of titanium oxide, which has a slight effect on heat resistance. The silicic oxide used in the study is based on a composite oxide of 50 wt% silicon and 30 wt% alkali. Boron oxide, iron, manganese, and cobalt accompanying titanium oxide composition changes. The composition was adjusted by changing the composition of the oxide.

  FIG. 5 shows the relationship between the titanium content in this silicic acid-based oxide and the contact angle (water, room temperature value) when left at 300 ° C. for a predetermined time. In FIG. 5, it can be seen that when the titanium content is 1 to 19 wt%, the contact angle is further increased, the water repellency is maintained for a long time, and the heat resistance is further improved.

The reason seems to be as follows. The first point is that titanium oxide easily recrystallizes and therefore has many hydroxyl groups. The larger the amount of titanium oxide, the more siloxane bonds that bind the antifouling thin film are produced and the stronger the bond. It has become. Conversely, the smaller the amount of titanium oxide, the smaller the amount of hydroxyl groups, so that only a few siloxane bonds that bind the antifouling thin film are formed, resulting in weak bonds. Secondly, because titanium oxide has a thermal expansion is greater with respect to silicate increases the thermal expansion of the heat-resistant substrate as the amount is large, the peeling due to thermal expansion of the siloxane bond that is bound antifouling film Being bigger and weaker. Conversely, if the amount is small, the thermal expansion of the heat-resistant substrate is reduced, and the siloxane bond that binds the antifouling thin film is prevented from being peeled off due to the thermal expansion to form a strong bond. Third, because the titanium component content is optimized, the strong bonding phenomenon caused by hydroxyl groups and the peeling phenomenon caused by thermal expansion are balanced to form a strong bond. In addition, when these materials are used, the effect of being able to be easily peeled off by simple cleaning and the effect of being excellent in wear resistance even when sticking of the cooked food occurs.

  Further, a composition further containing 1 to 25 wt% of aluminum as an oxide as in the second embodiment, and further including 1 to 18 wt% of titanium as an oxide as in the third embodiment. A composition that further contains both 1 to 25 wt% aluminum and 1 to 18 wt% titanium as oxides as in Embodiments 2 and 3 described above, and similar effects can be obtained even if studied. occured.

(Embodiment 5)
In the fifth embodiment, the surface roughness of the silicate-based oxide 2 studied in the first to fourth embodiments is examined in detail. The silicic acid-based oxide used in the study is an oxide of 50 wt% silicon and 13 wt% alkali. In addition to 10 wt% of zirconium and titanium oxide, aluminum, boron, and iron mixed in approximately equal amounts. And manganese and cobalt oxides.

  FIG. 6 shows the relationship between the ten-point surface roughness of the silicate-based oxide and the contact angle (water, room temperature value) when left at 300 ° C. for a predetermined time. The ten-point surface roughness is a value obtained by the following method. First, a reference length of 2 mm was extracted from the measured roughness curve in the direction of the average line. And in the roughness curve of this extracted part, from the average line, the absolute value of the altitude of the highest peak from the highest peak to the fifth peak among the many peaks and valleys measured in the direction of the vertical magnification, and the lowest valley The absolute value of the elevation of the bottom valley up to the fifth was obtained. Finally, the sum of the average value of the absolute value of the peak summit from the highest to the fifth mentioned above and the average value of the absolute value of the valley bottom elevation from the lowest to the fifth mentioned above is obtained and expressed as ten-point surface roughness. . Moreover, since the average line was wavy in the measured roughness curve, when a concave or convex was observed, the measurement was repeated until a flat line with no irregularities observed was obtained. This is to prevent a false value that is significantly different from the true value from being calculated due to unevenness caused by the undulation. In the measured roughness curve, the average line is a flat line where no irregularities are observed, but when the flat line is inclined upward or downward, the inclined flat line is treated as an average line, and this flat line The absolute value of the summit elevation and the absolute value of the valley bottom elevation were obtained, and the 10-point surface roughness was calculated.

  In FIG. 6, it can be seen that when the ten-point surface roughness is 0.01 to 0.5 μm, the contact angle increases, the water repellency is maintained for a long time, and the heat resistance is further improved. The reason seems to be as follows. The reason seems to be as follows. The first point is that the larger the 10-point surface roughness, the larger the surface area of the silicate oxide, the greater the number of hydroxyl groups, and the greater the number of siloxane bonds that bind the antifouling thin film. It must be a simple bond. Conversely, the smaller the 10-point surface roughness, the smaller the surface area of the silicic acid-based oxide, and the smaller the number of hydroxyl groups, the fewer siloxane bonds that bind the antifouling thin film. It must be a weak bond. The second point is that the larger the 10-point surface roughness value, the larger the surface area, so the thermal expansion of the heat-resistant substrate is increased, and the siloxane bond bonding the antifouling thin film is exfoliated due to thermal expansion, making it a weak bond. Yes. Conversely, the smaller the 10-point surface roughness value, the smaller the surface area, so the thermal expansion of the heat-resistant substrate is reduced, and the siloxane bond that binds the antifouling thin film is prevented from peeling off due to the thermal expansion to form a strong bond. Yes. The third point is that the ten-point surface roughness value is optimized, so that the strong bonding phenomenon due to hydroxyl groups and the peeling phenomenon due to thermal expansion are balanced to form a strong bond. Further, when this ten-point surface roughness was used, the effect of being able to be easily peeled off by simple cleaning even if the food was stuck, and the effect of being excellent in wear resistance were also produced.

(Embodiment 6)
In the sixth embodiment, the physical properties of the heat-resistant substrate 3 on the surface of which the silicate-based oxide 2 studied in any of the first to fifth embodiments was examined.

  Crystallized glass has many hydroxyl groups because it is mixed in an amount of about 9 to 4 wt% as an oxide obtained by crystallizing a zirconium component or a titanium component, and has a thermal expansion coefficient of 1 × 10 −6 / ° C. and other glass. Since it is extremely small compared to the above, it will not crack strongly against rapid heating and quenching. The tempered glass is a glass in which the strength is increased by blowing the air in a state where the glass is heated close to the softening temperature to rapidly cool the surface, and thus has many hydroxyl groups. Moreover, when one place destroys, it has a property which is grind | pulverized into many strips over the whole surface. General glass is glass that is not called crystallized glass or tempered glass. Table 2 shows the results of evaluating the effects of the present invention by forming an antifouling thin film of an organic fluorine compound having a siloxane bond directly on these heat resistant substrates of glass to obtain a heat resistant antifouling substrate. The effect was determined by the aforementioned 300 ° C. heat resistance test and the aforementioned abrasion resistance test.

  When the main constituent material is crystallized glass or tempered glass, the heat-resistant substrate having a silicate oxide on the surface has a larger contact angle, water repellency for a long time, and better heat resistance. Yes. For this reason, when an antifouling thin film of an organic fluorine compound having a siloxane bond is formed on these glasses, a heat and antifouling substrate having both water and oil repellency and heat resistance can be obtained by a simple production method and quality control. In addition, when these materials are used, the effect of being able to be easily peeled off by simple cleaning and the effect of being excellent in wear resistance even when sticking of the cooked food occurs.

(Embodiment 7)
In the seventh embodiment, the material composition used for the antifouling thin film 4 of an organic fluorine compound having at least a siloxane bond, which is the first embodiment, was examined.

  When the antifouling thin film having a siloxane bond has a material composition having at least an alkyl group or a fluoroalkyl group, an antifouling thin film excellent in water repellency, oil repellency and heat resistance can be easily provided. In addition, since the antifouling thin film using this material is a monomolecular film, a transparent and heat resistant film with a film thickness of several nanometers that does not interfere with light is formed, and the color of the substrate is impaired. No antifouling thin film is formed.

The following are effective as the silane compound of the present invention.
(1) SiX4 (equivalent to n = 0)
(2) SiX3-O-SiX3 (corresponding to n = 1)
(3) Si (OC2H5) 4
(4) Si (OCH3) 3-O-Si (OCH3) 3
(5) Si (OC2H5) 3-O-Si (OCH3) 3
(6) Si (OC2H5) 3-O-Si (OC2H5) 3
(7) Si (NCO) 4
(8) Si (NCO) 3-O-Si (NCO) 3
(9) SiCl4
(10) SiCl3-O-SiCl3
(11) SiYpCl4-p
(12) CH3 (CH2) sO (CH2) tSiYqCl3-q
(13) CH3 (CH2) u-Si (CH3) 2 (CH2) v-SiYqCl3-q
(14) CF3COO (CH2) wSiYqCl3-q
However, p is an integer of 1-3, q is an integer of 0-2, r is an integer of 1-25, s is an integer of 0-12, t is an integer of 1-20, u is an integer of 0-12, v represents an integer of 1 to 20, and w represents an integer of 1 to 25. Y is hydrogen, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
(15) CH3CH2O (CH2) 15SiCl3
(16) CH3 (CH2) 2Si (CH3) 2 (CH2) 15SiCl3
(17) CH3 (CH2) 6Si (CH3) 2 (CH2) 9SiCl3
(18) CH3COO (CH2) 15SiCl3
(19) CF3 (CF2) 7- (CH2) 2-SiCl3
(20) CF3 (CF2) 5- (CH2) 2-SiCl3
(21) CF3 (CF2) 7-C6H4-SiCl3
Instead of the chlorosilane compound, an isocyanate compound in which all chlorosilyl groups are replaced with isocyanate groups, for example, (22)-(26) shown below may be used.
(22) SiYp (NCO) 4-p
(23) CH3- (CH2) rSiYp (NCO) 3-p
(24) CH3 (CH2) sO (CH2) tSiYq (NCO) q-P
(25) CH3 (CH2) u-Si (CH3) 2 (CH2) v-SiYq (NCO) 3-q
(26) CF3COO (CH2) vSiYq (NCO) 3-q
However, p, q, r, s, t, u, v, w, and X are the same as described above.

Moreover, it may replace with the said silane type compound and may use the silane type compound specifically illustrated to following (27)-(33).
(27) CH3CH2O (CH2) 15Si (NCO) 3
(28) CH3 (CH2) 2Si (CH3) 2 (CH2) 15Si (NCO) 3
(29) CH3 (CH2) 6Si (CH3) 2 (CH2) 9Si (NCO) 3
(30) CH3COO (CH2) 15Si (NCO) 3
(31) CF3 (CF2) 7- (CH2) 2-Si (NCO) 3
(32) CF3 (CF2) 5- (CH2) 2-Si (NCO) 3
(33) CF3 (CF2) 7-C6H4-Si (NCO) 3
Further, as the silane-based compound, it is generally possible to use a substance represented by SiYk (OA) 4-k (Y is the same as above, A is an alkyl group, and k is 0, 1, 2, or 3). is there. Among them, CF3- (CF2) n- (R) 1-SiYq (OA) 3-q (n is an integer of 1 or more, preferably an integer of 1-22, R is an alkyl group, vinyl group, ethynyl group, aryl group. , A substituent containing silicon or an oxygen atom, l is 0 or 1, Y, A and q are the same as described above, and a more excellent antifouling film can be formed. In addition, it is not limited, CH3- (CH2) r-SiYq (OA) 3-q and CH3- (CH2) s-0- (CH2) t-SiYq (OA) 3-q, CH3 -(CH2) u-Si (CH3) 2- (CH2) v-SiYq (OA) 3-q, CF3COO- (CH2) v-SiYq (OA) 3-q (where q, r, s, t, u, v, w, Y and A are the same as above) Noh.

Furthermore, specific examples of the silane compound include (34) to (57) shown below.
(34) CH3CH2O (CH2) 15Si (OCH3) 3
(35) CF3CH2O (CH2) 15Si (OCH3) 3
(36) CH3 (CH2) 2Si (CH3) 2 (CH2) 15Si (OCH3) 3
(37) CH3 (CH2) 6Si (CH3) 2 (CH2) 9Si (OCH3) 3
(38) CH3COO (CH2) 15Si (OCH3) 3
(39) CF3 (CF2) 5 (CH2) 2Si (OCH3) 3
(40) CF3 (CF2) 7-C6H4-Si (OCH3) 3
(41) CH3CH2O (CH2) 15Si (OC2H5) 3
(42) CH3 (CH2) 2Si (CH3) 2 (CH2) 15Si (OC2H5) 3
(43) CH3 (CH2) 6Si (CH3) 2 (CH2) 9Si (OC2H5) 3
(44) CF3 (CH2) 6Si (CH3) 2 (CH2) 9Si (OC2H5) 3
(45) CH3COO (CH2) 15Si (OC2H5) 3
(46) CF3COO (CH2) 15Si (OC2H5) 3
(47) CF3COO (CH2) 15Si (OCH3) 3
(48) CF3 (CF2) 9 (CH2) 2Si (OC2H5) 3
(49) CF3 (CF2) 7 (CH2) 2Si (OC2H5) 3
(50) CF3 (CF2) 5 (CH2) 2Si (OC2H5) 3
(5l) CF3 (CF2) 7C6H4Si (OC2H5) 3
(52) CF3 (CF2) 9 (CH2) 2Si (OCH3) 3
(53) CF3 (CF2) 5 (CH2) 2Si (OCH3) 3
(54) CF3 (CF2) 7 (CH2) 2SiCH3 (OC2H5) 2
(55) CF3 (CF2) 7 (CH2) 2SiCH3 (OCH3) 2
(56) CF3 (CF2) 7 (CH2) 2Si (CH3) 2OC2H5
(57) CF3 (CF2) 7 (CH2) 2Si (CH3) 2OCH3
In addition, when the compounds (22) to (57) are used, hydrochloric acid is not generated, and there are also merit in terms of equipment maintenance and work.

  As the solvent for diluting the raw material solution containing the silane compound, a non-aqueous solvent is used in order to prevent the silane compound from reacting with water. In particular, when the non-aqueous solvent is silicone, the silane compound is solvated by the silicone, so that the non-aqueous solvent is hardly affected by water from the outside and becomes an excellent non-aqueous solvent. As the solvent, it is preferable to use a non-aqueous solvent that does not contain active hydrogen, and it is possible to use a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, or the like that does not contain water.

  In addition to petroleum-based solvents, petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, ligroin, dimethyl millicorn, phenyl silicone , Alkyl-modified silicone, polyester silicone and the like. In addition, the fluorocarbon solvents include chlorofluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well.

  Next, the process of apply | coating the solution containing a silane compound is demonstrated. When the application of the solution containing the silane compound is in an anhydrous atmosphere with a humidity of 35% or less, the silane compound does not react with water from the outside air, so that the siloxane formed by bonding these silane compounds together on the surface An antifouling thin film having a bond is formed. In addition, if a drying step for removing the solvent is provided in the subsequent step of the step of applying the solution containing the silane compound, the silane compound is concentrated in the drying step, so that an antifouling thin film having a high-density siloxane bond is formed. Thus, the heat resistance can be greatly improved. If this drying step is in an anhydrous atmosphere with a humidity of 35% or less, and further a step of washing excess unreacted silane compound as a subsequent step, an antifouling thin film having a higher density of siloxane bonds is formed. Thus, the heat resistance can be greatly improved. In addition, when these materials are used, the effect of being able to be easily peeled off by simple cleaning and the effect of being excellent in wear resistance even when sticking of the cooked food occurs.

(Embodiment 8)
The eighth embodiment is an examination of the raw material of the material used for the antifouling thin film 4 of the organic fluorine compound having at least a siloxane bond, which is the first embodiment or the seventh embodiment. The raw material used for the antifouling thin film 4 is any one of halogenated silane, alkoxysilane, isocyanate silane, and aminosilane. When these raw materials are used, a heat-resistant antifouling thin film having a siloxane bond formed by bonding these silane compounds to each other can be easily formed on the surface. In addition, when these materials are used, the effect of being able to be easily peeled off by simple cleaning and the effect of being excellent in wear resistance even when sticking of the cooked food occurs.

(Embodiment 9)
The ninth embodiment is the contents of the study on the solvent for diluting the raw material used for the antifouling thin film 4 of the organic fluorine compound having at least a siloxane bond, which is the aforementioned eighth embodiment. It has been found that when the solvent is an organic silicone, the silane compound is solvated by the organic silicone, so that it is not easily affected by water from the outside, and a heat-resistant antifouling thin film is easily formed. In addition, when these materials are used, the effect of being able to be easily peeled off by simple cleaning and the effect of being excellent in wear resistance even when sticking of the cooked food occurs.

(Embodiment 10)
The tenth embodiment is a raw material used for the antifouling thin film 4 of an organic fluorine compound having at least a siloxane bond, which is one of the above-described eighth to ninth embodiments. . It is found that halogenated silane compounds are optimal, especially chlorosilanes, and it is easy to form heat-resistant antifouling thin films in which siloxane bonds formed by bonding of chlorosilane compounds are strongly chemically bonded to heat-resistant substrates. did. In addition, when these materials are used, the effect of being able to be easily peeled off by simple cleaning and the effect of being excellent in wear resistance even when sticking of the cooked food occurs.

(Embodiment 11)
In the eleventh embodiment, the heat-resistant and antifouling substrate 1 according to any of the first to tenth embodiments is applied to a cooking device, and the configuration is shown in FIG. The cooking device includes a heat-resistant and antifouling substrate 1 made of a glass heat-resistant substrate 3 having an antifouling thin film 4 formed on the upper surface, a case 5 disposed below the heat-resistant and antifouling substrate 1 for mounting the heat-resistant and antifouling substrate 1, It has at least a cooking heating component 6 such as an electromagnetic induction heater, a gas burner, and a controller thereof housed in the internal space of the body 5.

  On the other hand, the heat-resistant and antifouling substrate 1 is preliminarily formed with a fired film 7 mainly composed of a heat-resistant metal on its lower surface, and an antifouling thin film 4 is formed on its upper surface in a subsequent process. And the housing | casing 5 and the heat-resistant antifouling board | substrate 1 are joined with the baking film 7 interposed. The cooking pan containing the ingredients and the like is placed on the antifouling thin film 4 formed on the upper surface of the heat-resistant antifouling substrate 1 and heated by the cooking heating component 6. The fired film 7 contains a small amount of bismuth oxide or glass as a binder, and the balance is at least one heat-resistant metal selected from gold, platinum, palladium, nickel, copper, and silver. The fired film 7 has a colored metal color because it is mainly composed of a heat-resistant metal. Therefore, using transparent glass as the heat-resistant substrate 3, the metal color of the fired coating 7 makes it difficult to see the cooking residue attached to the surface of the transparent antifouling thin film 4, and maintains a beautiful and clean feeling over a long period of time. it can. Note that, if necessary, in order to further improve the aesthetics, mica may be fixed to the lower side of the heat-resistant substrate 3 with an adhesive, and a fired film 7 may be further formed thereon.

  The antifouling thin film 4 is made of an organic fluorine compound liquid having a siloxane bond as a raw material, and is applied to the upper surface of the heat resistant substrate 3 to become an antifouling thin film through a drying process. The organic fluorine compound evaporated in this coating and drying process travels to the fired film 7 formed in advance on the lower surface thereof to form an extremely thin organic fluorine compound film. On the other hand, the fired film 7 has a hydrophilic property since the heat-resistant metal is a main component and is fired. Therefore, even if a very thin organic fluorine compound film that is wrapped around adheres to the surface of the fired film 7, it is still hydrophilic. It comes to have. When the fired film 7 formed on the lower surface of the heat-resistant and antifouling substrate 1 has hydrophilicity, it becomes difficult for water adhering to the surface where polka dots are difficult to be dropped to fall, which is arranged at the lower position thereof. An effect is obtained in which moisture hardly falls on the cooking heating component 6.

For this reason, even if the cooking device is used for a long time in a hot and humid environment such as a commercial kitchen, the cooking and heating component 6 for heating the cooking pan falls from the heat-resistant and antifouling substrate 1 disposed on the cooking pan. Condensation moisture is reduced, and there is no trouble caused by falling condensation moisture. Moreover, the cooking heating component 6 has an advantage that it can sufficiently cope with a simple moisture-proof measure. On the other hand, if the heat-resistant and antifouling substrate 1 has no fired coating 7, the lower surface thereof is only the glass surface used as the heat-resistant substrate 3. When an extremely thin organic fluorine compound film is attached to the lower glass surface of the heat-resistant substrate 3 and adheres thereto, it bonds and has water repellency, so that moisture adhering to the surface easily falls. Therefore, when the cooking device is used for a long time in a high-temperature and high-humidity environment, the cooking and heating component 6 needs to have a complex moisture-proof measure in consideration of the condensed moisture falling.

  The cooking and heating component 6 is a heat generation means such as an electromagnetic induction heater, a gas burner, and an electric heater, and its controller, and the heat-resistant and antifouling substrate 1 is configured according to the configuration of these heat generation means. Needless to say. For example, when the cooking / heating component 6 is an electromagnetic induction heater or an electric heater heat generating means and its controller, the heat-resistant antifouling substrate 1 is a flat plate, and when the cooking / heating component 6 is a gas burner and its controller, The antifouling substrate 1 is a flat plate having a cavity for releasing combustion exhaust gas from the gas burner. In addition, these flat plates may have a configuration in which small irregularities are formed on the surface thereof by, for example, partially forming a printed film so that the pan does not fall because the cooking pan is placed thereon.

(Embodiment 12)
In the twelfth embodiment, the result of studying the material of the refractory metal contained in the fired film according to the eleventh embodiment will be described with reference to FIG. If the refractory metal is at least either platinum, gold or palladium, the surface is more difficult to form polka dots and the water adhering to the surface is less likely to fall. Moisture did not fall easily. For this reason, the cooking and heating component 6 can cope with moisture-proof measures obtained by a simpler manufacturing method and quality control.

(Embodiment 13)
In the thirteenth embodiment, the heat-resistant and antifouling substrate 1 according to any of the first to tenth embodiments is applied to a cooking device, and the configuration thereof will be described with reference to FIG. The cooking device includes a heat-resistant and antifouling substrate 1 composed of a heat-resistant substrate 3 having an antifouling thin film 4 formed on the upper surface, a case 5 disposed below the heat-resistant and antifouling substrate 1 for mounting the heat-resistant and antifouling substrate 1, It has at least a cooking and heating component 6 such as an electromagnetic induction heater, a gas burner and its controller housed in the internal space.

  On the other hand, the heat-resistant and antifouling substrate 1 is preliminarily formed with a fired film 7 containing bismuth oxide and a heat-resistant material on its lower surface, and an antifouling thin film 4 is formed on its upper surface in a subsequent process. And the housing | casing 5 and the heat-resistant antifouling board | substrate 1 are joined with the adhesive agent 8 with the baking film 7 interposed. The cooking pan containing the ingredients and the like is placed on the antifouling thin film 4 formed on the upper surface of the heat-resistant antifouling substrate 1 and heated by the cooking heating component 6.

  Bismuth oxide has a property that when it is melted by firing, it expands in volume to form a porous hydrophilic colored film, and the porous film is segregated and scattered. Further, when bismuth oxide to be colored is used, the fired film 7 can form a beautiful colored film due to a synergistic effect with the heat-resistant material. Therefore, even if transparent glass is used as the heat-resistant substrate 3 for forming the antifouling thin film 4, the colored fired coating 7 existing on the back side of the antifouling thin film 4 makes it difficult to see cooking residues attached to the surface of the transparent antifouling thin film 4. Thus, the beauty and cleanliness can be maintained for a long time. Therefore, the baked coating 7 contains bismuth oxide, and the balance is at least one heat-resistant metal selected from gold, platinum, palladium, nickel and copper, or the balance is mica or carbon.

On the other hand, the antifouling thin film 4 is made of an organic fluorine compound liquid having a siloxane bond as a raw material, and is applied to the upper surface of the heat-resistant substrate 3 to become an antifouling thin film through a drying process. The organic fluorine compound evaporated in this coating and drying process travels to the fired film 7 containing bismuth oxide previously formed on the lower surface thereof, and an extremely thin film is formed. When bismuth oxide is melted by firing, it expands in volume and forms a porous hydrophilic film, and the porous film segregates and is scattered. For this reason, the extremely thin organic fluorine compound film that has wrapped around also penetrates into the porous fired coating 7, thereby reducing interference with the bonding between the housing 5 and the heat-resistant and antifouling substrate 1. By these things, the housing | casing 5 can be favorably joined with the heat-resistant antifouling substrate 1. Further, this porous hydrophilic fired coating 7 makes it difficult for polka dots to be formed, and makes it difficult for moisture adhering to the surface to fall, and makes it difficult for moisture to fall on the cooking heating component 6 disposed at the lower position. It was.

  On the other hand, when the heat-resistant and antifouling substrate 1 does not have the fired coating 7 having the above material composition, the extremely thin organic fluorine compound film that surrounds the substrate 5 and the heat-resistant and antifouling substrate 1 are obstructed. This makes it difficult to obtain good bonding. Further, when a very thin organic fluorine compound film is attached around the lower glass surface of the heat-resistant substrate 3, it bonds and has water repellency, so that the water adhering to the surface easily falls. Therefore, when the cooking device is used for a long time in a high-temperature and high-humidity environment, the cooking and heating component 6 needs to have a complex moisture-proof measure in consideration of the condensed moisture falling.

(Embodiment 14)
In the fourteenth embodiment, the amount of bismuth oxide to be mixed with the fired coating 7 used in the cooking device according to the thirteenth embodiment was examined. As a result, the mixing amount of bismuth oxide was optimally 1 to 30 wt%. If it is less than 1 wt%, the degree of porosity will be insufficient, and the extremely thin organic fluorine compound film that surrounds will interfere with the bonding between the housing 5 and the heat-resistant and antifouling substrate 1, and a good bonding will be achieved. This is because it becomes difficult to obtain. On the other hand, if it exceeds 30 wt%, the porous film is too large and becomes a very fragile film, a strong film cannot be obtained, and the degree of porosity is too smooth and becomes slightly smooth. This is because the film obstructs the bonding between the housing 5 and the heat-resistant and antifouling substrate 1 and makes it difficult to obtain a good bond. Accordingly, the fired film 7 contains 1 to 30 wt% of bismuth oxide, the balance being at least one heat-resistant metal selected from gold, platinum, palladium, silver, copper, nickel, or the like, or the balance being mica. And carbon. Since the heat-resistant metal has a light black color, when transparent glass is used for the heat-resistant substrate 3, it has the effect of making it difficult to see the cooking residue attached to the antifouling thin film 4. From these facts, the following study was conducted on the fired coating 7 containing 5 wt% of bismuth oxide and the balance of platinum or gold as the main component.

(Embodiment 15)
In the fifteenth embodiment, a method for carrying out the cooking device in any one of the above-described first to eleventh embodiments in more detail is examined. As a result, as shown in FIG. 8, when the heat-resistant substrate 3 having the organic silicone film 9 formed in advance on the lower surface of the fired coating 7 is used, a very thin organic silicone resin vapor-phase evaporation film can be easily formed. It was found that the antifouling thin film 4 having excellent heat resistance can be obtained by forming the antifouling thin film 4 on the upper surface thereof in a later step.

A specific production method will be described. First, the heat-resistant substrate 3 on which the fired film 7 was formed in advance was prepared, and a liquid paint of an organic silicone resin was applied to the surface of the fired film 7 and dried and fired. As a result, the organic silicone film 9 is formed on the surface of the fired film 7. At the same time, the vapor phase of the extremely thin organic silicone resin is also formed on the non-formed surface of the heat-resistant substrate 3, which is the opposite surface of the fired film 7. An evaporation film is formed. Next, the heat-resistant substrate 3 on which these films were formed was washed to remove dirt adhering to the surface. Next, heptadecafluorodecyltrichlorosilane was prepared as a raw material for an organic fluorine compound having a siloxane bond, and an organic solution diluted with hexamethylsiloxane was prepared. Then, the heat-resistant antifouling substrate on which the antifouling thin film 4 of the organic fluorine compound having at least a siloxane bond is formed by immersing the heat-resistant substrate 3 in this organic solution in a nitrogen atmosphere and then leaving it in the air. 1 was obtained. After that, the cooking device is assembled with this substrate.

  When the heat-resistant substrate 3 on which the organic silicone film 9 is previously formed on the lower surface of the fired film 7 is used, a vapor-phase evaporation film of an organic silicone resin is formed, and the antifouling thin film 4 is formed on this film. As a result, the organic silicone film 13 is hydrophilic, so that the housing 5 and the heat-resistant and antifouling substrate 1 can be bonded to each other with the adhesive 8. In addition, since the organic silicone film 9 is hydrophilic, the extremely thin organic fluorine compound constituting the antifouling thin film wraps around the porous organic silicone film 9 even if it goes around. Therefore, there is an advantage that polka dots are difficult to be formed, and moisture adhering to the surface does not easily fall, and moisture hardly falls on the cooking heating component 6 disposed at the lower position.

(Embodiment 16)
In the sixteenth embodiment, the material of the adhesive 8 that joins the housing 5 and the heat-resistant antifouling substrate 1 in FIGS. 7 and 8 is examined. As a result, it was found that an organic silicone resin is optimal. This is because the organic silicone resin used as the adhesive 8 is heat resistant, the organic fluorine compound film formed on the upper surface of the heat-resistant antifouling substrate 1 or its modified film, or the fired film 7 formed on the lower surface thereof. Furthermore, the affinity with the organic silicone film 9 is good, so that the familiarity is good and an excellent bonding force can be maintained for a long time. In addition, the heat-resistant antifouling substrate 1 is bonded to the housing 5 at the end of the upper surface or the lower surface, and a jig or the like is provided on the housing 5 so that the bonding is good.

(Embodiment 17)
In the seventeenth embodiment, the heat-resistant and antifouling substrate 1 in any of the first to tenth embodiments described above is applied to a cooking device having another configuration, and the configuration is shown in FIG. The cooking device includes a heat-resistant and antifouling substrate 1 made of a transparent glass heat-resistant substrate 2 on which an antifouling thin film 4 is formed, a cooking chamber 10 in which the heat-resistant and antifouling substrate 1 is arranged on the side surface, and the interior of the cooking chamber 10. Or at least it has the cooking heating component 11 arrange | positioned in the outer surface, and the housing | casing 12 which accommodates the cooking chamber 10 and the cooking heating component 11, and the heat-resistant antifouling board | substrate 1 has the antifouling thin film 4 on the inner surface of the cooking chamber 10. The tin thin film 13 is formed on the outer surface side of the cooking chamber 10 on the side.

  The tin thin film 13 has an effect of reflecting infrared rays generated during cooking. Therefore, when transparent or translucent glass is used as the heat-resistant substrate 3 and the tin thin film 13 is formed on the outer surface side of the cooking chamber 10, infrared rays generated from the cooked food are reflected by the tin thin film 13 and are irradiated again on the cooked food. The effect that cooking time is shortened arises. In addition, the antifouling thin film 4 formed on the inner surface side of the cooking chamber 10 can easily wipe off cooking residues adhering to the surface, so that the beauty and cleanliness can be maintained over a long period of time.

  As described above, the heat-resistant and antifouling substrate of the present invention and the cooking device using the same are easy even if the food is stuck due to its excellent water and oil repellency, heat resistance and wear resistance. It can be easily peeled off by cleaning and maintain its beauty and cleanliness over a long period of time, so it can be applied to IH cooking appliances, hot plates, grill pans, frying pans, microwave ovens, electric ovens, etc.

(A) Configuration diagram of the heat-resistant and antifouling substrate in Embodiment 1 of the present invention (b) Characteristic diagram showing the relationship between the silicon component content of the heat-resistant and antifouling substrate and the heat resistance (c) Alkali of the heat-resistant and antifouling substrate Characteristic diagram showing the relationship between component content and heat resistance (A) Characteristic diagram showing the relationship between the silicon component content of the heat-resistant and antifouling substrate and wear resistance (b) Characteristic diagram showing the relationship between the alkali component content of the heat-resistant and antifouling substrate and wear resistance The characteristic view which shows the relationship between the aluminum component content rate and durability in the heat-resistant antifouling substrate in Embodiment 2 of the present invention The characteristic view which shows the relationship between the zirconium component content rate and durability in the heat-resistant antifouling substrate in Embodiment 3 of the present invention The characteristic view which shows the relationship between the titanium component content rate and durability in the heat-resistant antifouling substrate in Embodiment 4 of the present invention The characteristic view which shows the relationship between ten-point surface roughness and durability in the heat-resistant antifouling substrate in Embodiment 5 of the present invention The block diagram which shows the heating cooking appliance in Embodiment 11-14 and 16 of this invention The block diagram which shows the heating cooking appliance in Embodiment 15 of this invention The block diagram which shows the heating cooking appliance in Embodiment 17 of this invention

DESCRIPTION OF SYMBOLS 1 Heat-resistant antifouling board | substrate 2 Silicic acid system oxide 3 Heat-resistant board | substrate 4 Antifouling thin film 5, 12 Case 6, 11 Parts for cooking heating 7 Baking coating 8 Adhesive 9 Organosilicone film 10 Cooking room 13 Tin thin film

Claims (3)

The heat-resistant and antifouling substrate, a housing disposed under the heat-resistant and antifouling substrate and holding and fixing the heat and antifouling substrate, and an internal space provided between the housing and the heat and antifouling substrate Cooking heating parts,
The heat-resistant and antifouling substrate is
A heat-resistant substrate,
Present on the upper surface of the heat-resistant substrate, 100 to 50 wt% of silicon, an alkali content of 30 wt% or less composed of alkali metal and alkaline earth metal, 1 to 25 wt% of aluminum, 1 to 18 wt% of zirconium, 1 silicate-based oxide having the elemental composition not exceeding a total of 100 wt% and containing any one of ～19Wt% of titanium,
Antifouling thin film of an organic fluorine compound having an upper surface formed in the siloxane bonds of the silicate-based oxide,
Wherein formed on the lower surface of the heat resistant substrate, and baking coating containing platinum, gold, and bismuth oxide and either a refractory metal vanadium,
An organosilicone film formed on the lower surface of the fired coating;
A cooking device provided with a gas phase evaporation film of an organic silicone resin formed between the silicic acid-based oxide and the antifouling thin film . The cooking device according to claim 1, wherein the fired film contains 1 to 30 wt% of bismuth oxide. The cooking device according to claim 1 or 2 , wherein the heat-resistant and antifouling substrate is bonded to the housing using an organic silicone adhesive.

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