WO2011043461A1

WO2011043461A1 - Low-adhesion material, stain-proof material, molding die, and processes for production thereof

Info

Publication number: WO2011043461A1
Application number: PCT/JP2010/067742
Authority: WO
Inventors: 藤原　邦彦; 欣紀野口; 白井　健士郎; 智子岸本; 大助東; 北岡　諭; 川島　直樹
Original assignee: Ｔｏｗａ株式会社; 財団法人ファインセラミックスセンター
Priority date: 2009-10-09
Filing date: 2010-10-08
Publication date: 2011-04-14
Also published as: TW201117939A; JP5561992B2; JP2011079261A

Abstract

In an upper die (1) which is a molding die for use in the molding of a resin, a mold release layer (4) is formed on the surface (8) of a base material (5) comprising a ZrO₂-based ceramic material. The mold release layer (4) comprises a material exhibiting low adhesion to an object composed of a basic substance, a heat-curable resin or a moisture-containing substance. In the mold release layer (4), Zr⁴⁺ (which is a cation of a Group 4A element) and nitrogen are introduced into at least the surface of Y₂O₃. In at least the surface of the material exhibiting low adhesion, the amount of the cation of the Group 4A element is preferably more than 0 mol% and not more than 20 mol%, and the amount of nitrogen is preferably 0.01 to 10 mol% inclusive.

Description

Low adhesion material, antifouling material, mold, and production method thereof

The present invention relates to a material having low adhesion to an object composed of at least one of a basic substance, a thermosetting resin, and a substance containing moisture, and to a soil containing such an object. The present invention relates to a material having antifouling properties, a molding die used when molding a molded article, and a method for producing them.

Conventionally, in various fields, there is a need for materials having low adhesion to an object made of an organic substance, a basic substance, a thermosetting resin, or a substance containing moisture. Those needs have emerged as needs relating to materials having antifouling properties against dirt containing such substances, materials used for molding dies used when molding molded articles, and the like. The term “low adhesion” as used herein refers to “basic materials such as steel materials and cemented carbides that are conventional mold materials and epoxy resins, thermosetting resins, or moisture. It means that the adhesiveness is low when compared with the adhesiveness between the substance and the substance. “Basic” means the property of donating an electron pair or the property of donating a proton (for example, RIKEN Encyclopedia, 4th edition, Iwanami Shoten, 1987, p. 161).

In response to the above-mentioned needs, the applicant of the present application first proposed the following low adhesion material and resin mold. It is a value calculated based on the valence and ionic radius of the metal cation of the rare earth oxide, the surface of the material having low adhesion with respect to the adhesion between the thermosetting resin is constituted by the rare earth oxide. This is a low-adhesive material having a field strength within a predetermined range, and a resin molding die whose mold surface is composed of the above-mentioned low-adhesive material (see Patent Document 1: Japanese Patent No. 3996138).

Secondly, the applicant of the present application has a low adhesion with respect to the adhesion between organic substances, a low adhesion material made of a substance containing at least a rare earth element, and a portion containing at least a part of the mold surface. A resin mold made of a material containing at least a rare earth element has been proposed (see Patent Document 2).

Thirdly, the applicant of the present application has proposed the following low adhesion material and its manufacturing method, mold and its manufacturing method, and antifouling material and its manufacturing method. It is a low adhesion material having low adhesion to a basic substance or a thermosetting resin, comprising a base material containing a rare earth oxide, and a functional layer containing nitrogen provided near the surface of the base material. A low-adhesion material comprising: Also, the molds using the low adhesion material are each provided with the same base material and functional layer. Further, the antifouling material using the low adhesion material also has the same base material and functional layer, respectively (Patent Document 3: Japanese Patent Application Laid-Open No. 2009-226775, Japanese Patent Application No. 2008-075781).

Japanese Patent No. 3996138 (first page, Fig. 2) JP 2006-131429 (2nd page, FIG. 2) JP 2009-226775 A

According to the low adhesion material described above, there is a problem that the adhesion to a basic substance or a thermosetting resin cannot be said to be sufficiently low. In addition, according to the low adhesion material comprising a base material containing a rare earth oxide and a functional layer containing nitrogen provided in the vicinity of the surface of the base material, the types of objects (for example, resins) are different. It has been found that there is a problem in that there is a difference in the degree of low adhesion.

In view of the above-mentioned problems, the present invention has the following objects. The first object is to provide a material having lower and more stable low adhesion to an object consisting of at least one of a basic substance, a thermosetting resin, and a substance containing moisture. It is. A second object is to provide a material that has a higher and more stable antifouling property against dirt containing such objects. A third object is to provide a mold having higher and more stable releasability when using at least one of such objects. The fourth object is to provide a method for producing the above-mentioned low adhesion material, antifouling material, or mold.

In order to solve the above-mentioned problems, the low adhesion material according to the present invention is a low adhesion material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture. And at least the surface thereof is characterized by containing yttrium oxide and nitrogen.

Further, the low adhesion material according to the present invention is a material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and at least the surface thereof is oxidized. It contains yttrium and a cation of a group 4A element.

Further, the low adhesion material according to the present invention is a material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and at least the surface thereof is oxidized. It contains yttrium, nitrogen, and a cation of a group 4A element.

In the above low adhesion material, at least the amount of nitrogen contained on the surface is preferably 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.

In the low adhesion material described above, it is desirable that the amount of the cation of the group 4A element contained at least on the surface thereof exceeds 0 mol% and is 20 mol% or less.

In the low adhesion material described above, the cation of the group 4A element is preferably at least one of Zr ^{4+ and} Hf ⁴⁺ .

The low adhesion material described above has a base material, the base material contains zirconium oxide as a main component, and yttrium oxide and nitrogen are included in a layered portion provided on the surface of the base material. Yttrium oxide and cations of group 4A elements are included in the layered portion provided on the surface of the base material, or yttrium oxide, nitrogen and cations of group 4A elements are on the surface of the base material. It is desirable that it is included in the layered portion provided in.

Further, the antifouling material according to the present invention is a material having antifouling properties against dirt including an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and at least the surface thereof Is characterized in that it contains yttrium oxide and nitrogen.

Further, the antifouling material according to the present invention is a material having antifouling properties against dirt including an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and at least the surface thereof Is characterized in that it contains yttrium oxide and a cation of a group 4A element.

Further, the antifouling material according to the present invention is a material having antifouling properties against dirt including an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and at least the surface thereof Is characterized by containing yttrium oxide, nitrogen, and a cation of a group 4A element.

Further, in the above antifouling material, it is desirable that at least the amount of nitrogen contained on the surface is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.

Further, in the above antifouling material, it is desirable that the amount of the cation of the group 4A element contained at least on the surface thereof exceeds 0 mol% and is 20 mol% or less.

In the antifouling material, the cation of the group 4A element is preferably at least one of Zr ^{4+ and} Hf ⁴⁺ .

Further, the antifouling material described above has a base material, and the base material contains zirconium oxide as a main component, and yttrium oxide and nitrogen are included in a layered portion provided on the surface of the base material. Yttrium oxide and cations of group 4A elements are included in the layered portion provided on the surface of the base material, or yttrium oxide, nitrogen and cations of group 4A elements are on the surface of the base material. It is desirable that it is included in the layered portion provided in.

The molding die according to the present invention is a molding die used when molding a molded product, and is characterized in that at least the surface thereof contains yttrium oxide and nitrogen.

The molding die according to the present invention is a molding die used when molding a molded product, and at least the surface thereof contains yttrium oxide and a cation of a group 4A element. .

The molding die according to the present invention is a molding die used when molding a molded product, and at least the surface thereof contains yttrium oxide, nitrogen, and a cation of a group 4A element. And

In the above-described mold, it is desirable that the amount of nitrogen contained in at least the surface of the mold is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.

In the above-mentioned mold, it is desirable that the amount of the cation of the group 4A element contained at least on the surface thereof exceeds 0 mol% and is 20 mol% or less.

In the above mold, the cation of the group 4A element is preferably at least one of Zr ⁴⁺ or Hf ⁴⁺ .

Further, in the above-described mold, the mold includes a base material, the base material includes zirconium oxide as a main component, and yttrium oxide and nitrogen are included in a layered portion provided on the surface of the base material. Yttrium oxide and 4A group element cations are included in the layered portion provided on the surface of the base material, or yttrium oxide, nitrogen and 4A group element cations are included in the base material. It is desirable that it is contained in a layered portion provided on the surface.

In addition, the manufacturing method of the mold according to the present invention includes a manufacturing method of a material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and an antifouling material. Or a manufacturing method of a mold used when molding a molded product. The manufacturing method is used for manufacturing a material having low adhesion to the above-described object, a method for manufacturing a material having antifouling property against dirt including such an object, or molding a molded product. It is a manufacturing method of a shaping | molding die. The manufacturing method is a method for manufacturing a material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and an antifouling property against dirt containing such an object. It is the manufacturing method of the material which has, or the manufacturing method of the shaping | molding die used when shape | molding a molded article. The manufacturing method includes any one of a step of preparing a first raw material containing yttrium oxide and a group 4A element, a low adhesion material, an antifouling material, and a mold using the first raw material. And a step of bringing at least the surface of the substrate into a state containing yttrium oxide and a cation of a group 4A element.

In addition, the production method of the present invention is a method for producing a material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and against dirt containing such an object. It is the manufacturing method of the material which has antifouling property, or the manufacturing method of the shaping | molding die used when shape | molding a molded article. The above-described manufacturing method includes a step of preparing a base material containing zirconium oxide as a main component, and at least the surface of any of the above-described low adhesion material, antifouling material, and mold is made of yttrium oxide and 4A. In the step of containing a group element cation, it is desirable that the layered portion provided on the surface of the base material contains a yttrium oxide and a group 4A cation.

Further, the production method of the present invention includes a method for producing a low adhesion material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and such an object. It is the manufacturing method of the material which has the antifouling property with respect to the dirt to contain, or the manufacturing method of the shaping | molding die used when shape | molding a molded article. The above-described manufacturing method desirably includes a step of further including nitrogen on at least the surface of any one of the low adhesion material, the antifouling material, and the mold.

In addition, the production method of the present invention is a method for producing a material having low adhesion to an object if it is made of a basic substance, a thermosetting resin, or a substance containing moisture, and against dirt containing such an object. It is the manufacturing method of the material which has antifouling property, or the manufacturing method of the shaping | molding die used when shape | molding a molded article. In the manufacturing method described above, the amount of the cation of the group 4A element included in at least the surface of any one of the low adhesion material, the antifouling material, and the mold is preferably more than 0 mol% and not more than 20 mol%. .

In addition, the production method of the present invention is a method for producing a material having low adhesion to a basic substance, a thermosetting resin, or a substance containing moisture, and has antifouling properties against dirt containing such a target. It is the manufacturing method of a material, or the manufacturing method of the shaping | molding die used when shape | molding a molded article. In the above production method, the cation of the group 4A element is preferably at least one of Zr ⁴⁺ and Hf ⁴⁺ .

In addition, the production method of the present invention is a method for producing a material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and against dirt containing such an object. It is the manufacturing method of the material which has antifouling property, or the manufacturing method of the shaping | molding die used when shape | molding a molded article. The manufacturing method is used for manufacturing a material having low adhesion to such an object, a method for manufacturing a material having antifouling property against dirt including such an object, or molding a molded product. This is a manufacturing method of a mold. The manufacturing method is a method for manufacturing a material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and an antifouling property against dirt containing such an object. A method for producing a material or a method for producing a mold used for molding a molded article, the step of preparing a second raw material containing yttrium oxide as a main component, and the surface of the second raw material It is characterized by comprising a step of containing nitrogen.

In addition, the production method of the present invention is a method for producing a material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, and against dirt containing such an object. It is the manufacturing method of the material which has antifouling property, or the manufacturing method of the shaping | molding die used when shape | molding a molded article. In the production method described above, the amount of nitrogen contained in at least the surface of any one of the low adhesion material, the antifouling material, or the molding die or the surface of the second raw material is 0.01 mol in terms of nitrogen atoms. % Or more and 10 mol% or less is desirable.

According to the present invention, a material in which nitrogen is introduced into the surface of yttrium oxide (hereinafter referred to as “Y ₂ O ₃ ”), a material in which a cation of a group 4A element is introduced into the surface of Y ₂ O ₃ , or Y A material in which nitrogen and a cation of a group 4A element are introduced on the surface of ₂ O ₃ is obtained. These materials have low adhesion to an object made of at least one of a basic substance, a thermosetting resin, and a substance containing moisture. Therefore, these materials can be used as either a low adhesion material for such an object, a material having antifouling properties against dirt containing such an object, or a mold when using such an object. Can be used as

The above and other objects, features, aspects and advantages of the present invention will become apparent from the following detailed description of the present invention which is to be understood in connection with the accompanying drawings.

FIG. 1 shows four types of adhesion strength at 175 ° C. between the bulk material of Y ₂ O ₃ and the epoxy resin X, and nitrogen ions implanted at different ion concentrations into the bulk material of Y ₂ O ₃ . It is explanatory drawing which shows the adhesive strength in 175 degreeC between a material and the epoxy resin X, respectively, taking a nitrogen ion concentration on a horizontal axis. FIG. 2 is an explanatory diagram showing the relationship between the three types of materials and the adhesive strength at 175 ° C. between the respective materials and the epoxy resin Y. FIG. 3 is a partial cross-sectional view showing an outline of the coated mold according to the embodiment. FIG. 4 is a partial cross-sectional view showing an outline of a molding die made of a bulk material, which is the molding die of the embodiment.

Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.

Hereinafter, as Example 1, a first low adhesion material which is a low adhesion material according to the present invention will be described with reference to FIG. FIG. 1 shows adhesion strength at 175 ° C. between the bulk material of Y ₂ O ₃ and the epoxy resin X, and nitrogen ions are implanted into the bulk material of Y ₂ O ₃ at different ion concentrations. It is explanatory drawing which shows the adhesive strength in 175 degreeC between 4 types of other materials and the epoxy resin X, respectively, taking a nitrogen ion concentration on a horizontal axis. Here, the epoxy resin X is not only a thermosetting resin but also a basic substance, and also a substance containing moisture.

Among the materials shown in FIG. 1, four types of materials in which nitrogen ions are implanted into Y ₂ O ₃ bulk materials at different ion concentrations correspond to the first low adhesion material. Here, the term "bulk material Y ₂ O _3" is contains means a "Y ₂ O ₃ material whose main component", Y ₂ stabilizers such as O ₃ is added material It is out. Further, the nitrogen ion concentration shown on the horizontal axis in FIG. 1 is a value measured using a secondary ion-mass spectrometer (SIMS). Further, the nitrogen ion concentration used in the present application document is shown in mol% unit by converting a value measured in atm / cm ³ unit into nitrogen atom.

The four types of materials included in the first low adhesion material are manufactured by implanting nitrogen ions at different ion concentrations into the Y ₂ O ₃ bulk material. Here, the adhesion strength at 175 ° C. between each of the five types of materials including the Y ₂ O ₃ bulk material itself and the epoxy resin X is as follows.

First, the Y ₂ O ₃ bulk material itself indicated by the white triangle (Δ) in FIG. 1 has a nitrogen ion concentration of 1.45 × 10 ⁻² mol%. The bond strength between the Y ₂ O ₃ bulk material and the epoxy resin X is 0.381 hPa on average. Here, the nitrogen ion concentration shown in FIG. 1 is considered to be the concentration of nitrogen ions contained in the Y ₂ O ₃ bulk material itself.

Subsequently, the relationship between the nitrogen ion concentration and the adhesive strength between each material and the epoxy resin X will be described for each of the first low adhesion materials (four types) according to the present invention.

First, of the first low adhesion material, the material indicated by the black circle (●) in FIG. 1 has a nitrogen ion concentration of 4.00 × 10 ⁻² mol%. Moreover, the adhesive strength between this material and the epoxy resin X is 0.162 hPa on average.

Next, of the first low-adhesion material, the material indicated by a white circle (◯) in FIG. 1 has a nitrogen ion concentration of 6.54 × 10 ⁻² mol%. Moreover, the adhesive strength between this material and the epoxy resin X is 0.151 hPa on average.

Next, among the first low adhesion materials, the material indicated by the black square (■) in FIG. 1 has a nitrogen ion concentration of 3.98 × 10 ⁻¹ mol%. Moreover, the adhesive strength between this material and the epoxy resin X is 0.146 hPa on average.

Next, among the first low-adhesion materials, the materials indicated by white squares (□) in FIG. 1 have a nitrogen ion concentration of 6.50 × 10 ⁻¹ mol%. Moreover, the adhesive strength between this material and the epoxy resin X is 0.096 hPa on average. Incidentally, the nitrogen ion concentration for the first low-adhesion material of four types described above is believed to largely dependent on the concentration of implanted nitrogen ions in the bulk material of Y ₂ O _3.

From the results described so far, it can be seen that the higher the concentration of nitrogen ions implanted into the bulk material of Y ₂ O ₃ , the lower the adhesion strength between the material into which nitrogen ions are implanted and the epoxy resin X is reduced. I can say. Therefore, a material produced by injecting nitrogen ions into a Y ₂ O ₃ bulk material is a material having low adhesion to an object made of a basic substance, a thermosetting resin, or a substance containing moisture. Can be used as

Here, the implanted nitrogen ion concentration is preferably 0.01 mol% or more and 10 mol% or less. The reason why the nitrogen ion concentration is preferably 0.01 mol% or more is that when the nitrogen ion concentration is less than 0.01 mol%, the amount of substitution of nitrogen in Y ₂ O ₃ is too small and the effect of lowering the adhesion is obtained. Because it is not allowed. The reason why the nitrogen ion concentration is preferably 10 mol% or less is that when the nitrogen ion concentration exceeds 10 mol%, the crystal structure of Y ₂ O ₃ becomes unstable. This is because it cannot be stably maintained for a long time.

In consideration of the balance between lower adhesion and maintenance of a more stable crystal structure, the concentration of implanted nitrogen ions is more preferably 0.05 mol% or more and 5 mol% or less.

In addition, when the contact angle to water was measured for each of the bulk material of Y ₂ O ₃ and one of the first low adhesion materials, the following results were obtained. First, in the case of Y ₂ O ₃ , the contact angle was 65 °. Next, in the case of the material indicated by the white circle (◯) in FIG. 1 among the first low adhesion materials, the contact angle was 80 °. This result indicates that the first low adhesion material has higher water repellency than Y ₂ O ₃ . Moreover, this result shows that the first low-adhesion material has lower adhesion than Y ₂ O ₃ for substances containing moisture.

So far, it has been explained that the adhesive strength between the first low adhesion material and the epoxy resin X is smaller than the adhesive strength between the Y ₂ O ₃ and the epoxy resin X. The contact angle to water of the first low adhesion material is larger than the contact angle to water of Y ₂ O ₃ has been described. As a result, the first low-adhesion material is used as a low-adhesion material for an object consisting of at least one of a basic substance, a thermosetting resin, and a substance containing moisture. It can be used. "

In addition, the manufacturing method of the 1st low-adhesion material which concerns on a present Example is as follows. _First, the bulk material of Y 2 _{O 3,} i.e. to prepare the material for the _Y 2 _{O 3} as a main component. Next, nitrogen ions are implanted into the surface of the material using well-known methods. In other words, nitrogen is included in the surface of the Y ₂ O ₃ bulk material using known methods. As a result, the first low adhesion material can be manufactured.

Here, the following method can be used as a method of including nitrogen in the surface of the bulk material of Y ₂ O ₃ . Examples of the method include nitrogen atmosphere treatment, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), and sol-gel method. PVD includes vacuum deposition, electron beam deposition, sputtering, plasma spraying, ion implantation, plasma ion implantation, ion plating, and the like.

Further, a layer containing Y ₂ O ₃ as a main component may be provided on a suitable base material, and nitrogen may be included in the surface of the layer. In this case, it is preferable to use a material having excellent mechanical properties, that is, high toughness and wear resistance (for example, ZrO ₂ -based ceramics) as the substrate. Moreover, in the process of including nitrogen on the surface of the layer containing Y ₂ O ₃ as a main component, a suitable method among the various methods described above can be used. In this case, a layer made of the first low adhesion material is formed on the surface of the substrate. Furthermore, “having a layer made of the first low-adhesion material as a low-adhesion material for an object consisting of at least one of a basic substance, a thermosetting resin, and a substance containing moisture The material can be used. "

Hereinafter, as Example 2, a second low adhesion material which is a low adhesion material according to the present invention will be described with reference to FIG. FIG. 2 is an explanatory diagram showing the relationship between the three types of materials and the adhesion strength (Adhesion Strength) at 175 ° C. between the respective materials and the epoxy resin Y. Here, the epoxy resin Y is a thermosetting resin, a basic substance, and a substance containing moisture.

The second low adhesion material has low adhesion to an object composed of at least one of a basic substance, a thermosetting resin, and a substance containing moisture, and has at least a surface. Is characterized by containing yttrium oxide and a cation (cation) of a group 4A element. Examples of the second low adhesion material include a material in which a cation of a group 4A element is introduced into the surface of Y ₂ O ₃ which is a sintered material. In FIG. 2, an example in which Zr ⁴⁺ is introduced into the surface of Y ₂ O ₃ (material A) is shown as material B. In FIG. 2, as a result, 5 mol% of ZrO ₂ exists on the surface of the material B which is the second low adhesion material.

Here, the amount of ZrO ₂ contained in the surface of the second low adhesion material, in other words, the amount of Zr ⁴⁺ is preferably more than 0 mol% and not more than 20 mol%. The same applies to the following examples in that the amount of the cation of the group 4A element contained in the surface of the low adhesion material is preferably more than 0 mol% and 20 mol% or less.

The cation of the group 4A element is preferably at least one of Zr ⁴⁺ (ion radius: 0.83 Å = 83 pm) and Hf ⁴⁺ (ion radius: 0.83 Å = 83 pm). The same applies to the following examples in that the cation of the group 4A element is preferably at least one of Zr ⁴⁺ and Hf ⁴⁺ .

As shown in FIG. 2, the adhesive strength between the rare earth oxide Y ₂ O ₃ (material A) and the epoxy resin Y is 0.54 MPa, while the second low adhesion material ( The bond strength between the material B) and the epoxy resin Y is 0.45 MPa. This is because the cation of the group 4A element is introduced into the surface of Y ₂ O ₃ (material A), whereby the second low-adhesion material (material B), which is the material into which the cation is introduced, and the epoxy resin Y It shows that the adhesive strength between the two decreases.

Furthermore, when the contact angle with respect to water was measured, the contact angle was 65 ° in the case of Y ₂ O ₃ , while the contact angle was 90 ° in the case of the second low adhesion material. This result indicates that the second low adhesion material has higher water repellency than Y ₂ O ₃ . Moreover, this result shows that the second low-adhesion material has lower adhesion than Y ₂ O ₃ for an object made of a substance containing moisture.

As a result, the second low-adhesion material is used as a low-adhesion material for an object composed of at least one of a basic substance, a thermosetting resin, and a substance containing moisture. It can be used. "

Hereinafter, as Example 3, a third low adhesion material which is a low adhesion material according to the present invention will be described with reference to FIG. The third low adhesion material has low adhesion to an object composed of at least one of a basic substance, a thermosetting resin, and a substance containing moisture, and at least the surface thereof Is characterized by containing yttrium oxide, a cation of a group 4A element, and nitrogen.

As shown in FIG. 2, as a third low-adhesion material, Zr ⁴⁺ that is a cation of a group 4A element and nitrogen are introduced on the surface of a rare earth oxide Y ₂ O ₃ (material A). Material (material C). 5 mol% of ZrO ₂ exists on the surface of the material C which is the third low adhesion material.

Further, as shown in FIG. 2, while the adhesive strength between Y ₂ O ₃ (material A) and the epoxy resin Y is 0.54 MPa, the third low adhesion material and the epoxy resin Y The bond strength between the two is 0.32 MPa. This is because the 4A group element cation and nitrogen are introduced into the surface of Y ₂ O ₃ (material A), whereby the third low adhesion material (material). It shows that the adhesive strength between C) and the epoxy resin Y decreases.

Further, when the contact angle with water was measured, the contact angle was 65 ° in the case of Y ₂ O ₃ , while the contact angle was 107 ° in the case of the third low adhesion material. This result shows that the third low adhesion material has higher water repellency (higher water repellency than the second low adhesion material) compared to Y ₂ O ₃ . Further, this result shows that the third low adhesion material has lower adhesion (lower adhesion than the second low adhesion material) to the substance containing moisture compared to Y ₂ O _3. It shows that.

As a result, the third low-adhesion material is used as a low-adhesion material for an object composed of at least one of a basic substance, a thermosetting resin, and a substance containing moisture. It can be used. "

Next, the inventors of the present invention describe the mechanism by which the adhesive strength between the material in which nitrogen is introduced into the surface of Y ₂ O ₃ (first low-adhesion material) and the epoxy resin is reduced. I guess so. The reason why the first low-adhesion material is smaller than the material (third low-adhesion material) in which Zr ⁴⁺ and nitrogen are introduced on the surface of Y ₂ O _{3 is} about the effect of reducing the adhesive strength. Regarding the above, the inventors of the present invention speculate as follows.

When the oxygen in Y ₂ O ₃ is replaced with nitrogen (0 ² → N ³ ), the cause of the decrease in bond strength is that the YN bond is stronger in covalent bonds than the Y—O bond. This is considered to be because the adsorption of organic substances is suppressed due to polarization relaxation. In other words, it can be said that the adsorption activity of organic substances on the surface of Y ₂ O ₃ is reduced. As a result, the first low adhesion material is presumed to have an effect of reducing the adhesive strength, that is, the adhesion.

However, when the oxygen of Y ₂ O ₃ is replaced with nitrogen (0 ^2- > N ^3- ), anion vacancies (anionic vacancies; lattice defects) are maintained in order to maintain the electrical neutrality of the crystal structure. ) Is formed. In the case where anionic vacancies are present, it is considered that an acidic point that promotes organic substance adsorption is newly developed through the vacancies.

Here, in order to further reduce the adhesion strength between the surface of the low adhesion material and the epoxy resin, nitrogen may be introduced into Y ₂ O _{3 and} the formation of anion vacancies may be suppressed. In order to suppress the formation of anion vacancies, the valence is one greater than Y ³⁺ and dissolves in Y ₂ O ₃ in order to counteract N ^3-, which is one valence greater than 0 ^2- cations 4A group element may be added to _Y 2 _{O 3.} As a cation of the group 4A element, one or more of Zr ⁴⁺ (ion radius: 0.83Å = 83 pm) and Hf ⁴⁺ (ion radius: 0.83Å = 83 pm) can be used. From the above description, the first low-adhesion material is presumed to have an effect of lowering the adhesive strength, that is, the adhesion, but the effect is smaller than that of the third low-adhesion material.

The substitution amount of the cation of the group 4A element in Y ₂ O ₃ is preferably more than 0 mol% and 20 mol% or less in terms of MeO ₂ (Me is Zr or Hf). The reason is that when the substitution amount of the cation exceeds 20 mol%, Zr or Hf exceeds the solid solution limit with respect to the yttrium oxide matrix. This is because it is easy to precipitate, and the deterioration of adhesion is suppressed by these. Further, the cation substitution amount is more preferably more than 0 mol% and not more than 10 mol%.

Further, the amount of nitrogen contained in at least the surface of the third low adhesion material is preferably 0.01 mol% or more and 20 mol% or less. The reason for this is that, firstly, when it is less than 0.01 mol%, the substitution amount of oxygen to nitrogen in Y ₂ O ₃ is too small, and the effect of reducing the adhesion is not recognized. Second, when the nitrogen ion concentration exceeds 20 mol%, the crystal structure of Y ₂ O ₃ becomes unstable, so that the structure as a low adhesion material cannot be stably maintained for a long period of time. is there. In order to maintain the electrical neutral condition, the maximum nitrogen amount that can be substituted is equal to the cation amount added to the same material.

In consideration of the balance between low adhesion and the maintenance of a more stable crystal structure, the concentration of implanted nitrogen ions is more preferably 0.01 mol% or more and 10 mol% or less.

Hereinafter, as Example 4, a method for producing a low adhesion material according to the present invention will be described. Here, by forming either the second low adhesion material described in Example 2 or the third low adhesion material described in Example 3 on the surface of the substrate, the entire substrate A method for producing a low-adhesion material comprising the following will be described. In this case, the base material in a state where either the second low adhesion material or the third low adhesion material is formed on the surface constitutes the low adhesion material as the whole base material.

First, prepare an appropriate base material. The substrate is preferably a material having excellent mechanical properties, that is, high toughness and wear resistance. For example, zirconium-based ceramics (ZrO2-based ceramics) can be used as the base material.

Next, the liquid containing the salt containing Y and the salt containing the group 4A element is stirred. Thereby, a coating material containing an organic-inorganic precursor can be produced by complex polymerization. Therefore, this coating material corresponds to at least a part of the raw material of the second low adhesion material.

Next, the ZrO ₂ -based ceramic as the base material is immersed in the coating material. As a result, the coating material is applied to the surface of the substrate (dip coating method). In addition, a coating material can also be apply | coated to the surface of a base material using a spray coat method.

Next, the base material coated with the coating material is heated to perform heat treatment. As a result, a functional layer including Y, O, and Zr, which is composed of a layered portion provided on the surface of the substrate, is formed. As used herein, the term “functional layer” means a layer having a specific function. The specific function is low adhesion to a certain substance, high releasability when used as a mold, and antifouling property to a certain substance. Further, the term “antifouling property” means a property of preventing dirt from adhering to the surface or a property of easily removing (removing) the dirt when the surface adheres to the surface.

Through the steps up to here, the second low adhesion material described in Example 2 is obtained. The second low adhesion material is a low adhesion material containing at least Y ₂ O ₃ and Zr ⁴⁺ which is a cation of a 4A group element on the surface.

Furthermore, the third low adhesion material described in Example 3 is obtained by nitriding the second low adhesion material. The third low adhesion material is a low adhesion material containing at least Y ₂ O ₃ , Zr ⁴⁺ which is a cation of a 4A group element, and nitrogen on the surface.

The following method can be used as the nitriding treatment. These include nitrogen atmosphere treatment, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), and sol-gel method. PVD includes vacuum deposition, electron beam deposition, sputtering, plasma spraying, ion implantation, plasma ion implantation, ion plating, and the like.

As described above, according to the manufacturing method according to this example, Zr, which is a cation of Y ₂ O ₃ and a group 4A element, is formed on the layered portion provided on the surface of the substrate having excellent mechanical properties. ⁴⁺ can be introduced (included). In addition, Y ₂ O ₃ , Zr ⁴⁺ which is a cation of a 4A group element, and nitrogen can be introduced (included) into a layered portion provided on the surface of a substrate having excellent mechanical properties. . According to these manufacturing methods, the amount of Y that is a rare element can be reduced when manufacturing a low adhesion material. Further, the price of the low adhesion material can be suppressed.

Moreover, according to the manufacturing method according to the present embodiment, a diffusion solid solution layer (composition gradient layer) is formed at the interface between the base material and the functional layer. Thereby, the adhesiveness between a base material and a functional layer improves.

In addition, according to the manufacturing method according to the present example, the compressive residual stress is near the surface of the low-adhesive material under normal use temperature because the thermal expansion coefficient of the base material and the thermal expansion coefficient of the functional layer are different. Exists. This increases the fracture toughness value near the surface of the low adhesion material. Therefore, it is possible to produce a low adhesion material having excellent wear resistance and impact resistance.

Heretofore, the following three types of low adhesion materials have been described. First, the first low-adhesion material in which nitrogen ions were implanted into the surface of the Y ₂ O ₃ bulk material was described. Next, a second low-adhesion material was described in which Y ₂ O ₃ and a cation of a 4A group element were contained at least in a layered portion provided on the surface of the substrate. Finally, a third low-adhesion material in which at least a layered portion provided on the surface of the base material contains Y ₂ O ₃ , a cation of a 4A group element and nitrogen is described. Not limited to these, the low adhesion material may be a material (so-called bulk material) containing Y ₂ O ₃ and nitrogen as a whole. Further, the low adhesion material may be a material (so-called bulk material) containing Y ₂ O ₃ and a cation of a group 4A element as a whole. Further, the low adhesion material may be a material (so-called bulk material) containing Y ₂ O ₃ , a cation of a 4A group element, and nitrogen as a whole.

When manufacturing the bulk material of the second low adhesion material, the following steps are performed. First, a liquid containing a salt containing Y and a salt containing a 4A group element is stirred. Thus, a liquid material containing an organic-inorganic precursor is generated by complex polymerization.

Next, the liquid material is dried to be powdered. After that, the bulk material of the second low adhesion material can be manufactured by sintering the powdered material. In addition, as a manufacturing method of the bulk material of the third low adhesion material, a manufacturing method of nitriding the bulk material of the second low adhesion material can be used.

Hereinafter, the antifouling material according to the present invention will be described as Example 5. Example 5 is the first low adhesion material described in Example 1, the second low adhesion material described in Example 2, and the third low adhesion material described in Example 3. Any one of these is used as an antifouling material.

The first to third low-adhesion materials are at least one of a basic substance, a thermosetting resin, and a substance containing moisture, regardless of whether they are layered materials or bulk materials. It has low adhesion to a single object. Therefore, any of the first to third low adhesion materials can be used as a material having a function of preventing the adhesion of dirt including such an object. In addition, when dirt including such an object adheres, any of the first to third low adhesion materials can be used as a material that easily removes (removes) the dirt.

Specifically, any of the first to third low-adhesion materials can be used as a material for building materials, bathtubs, sanitary ware, and similar devices used for the outer walls of buildings. Further, as materials for pipes and tanks that come into contact with an object made of at least one of a basic substance, a thermosetting resin, and a substance containing moisture, the first to third low Any of the adhesive materials can be used. Further, any of the first to third low adhesion materials may be used as a material for coating the surface of the member used for these applications.

Hereinafter, as Example 6, a molding die according to the present invention will be described with reference to FIGS. 3 and 4. FIG. 3 and FIG. 4 are partial sectional views showing the outline of a coated mold and a mold made of a bulk material, respectively, which are molds of this example.

Example 6 is the first low adhesion material described in Example 1, the second low adhesion material described in Example 2, and the third low adhesion material described in Example 3. Any of the materials is used as a mold. As shown in FIG. 3, an upper mold 1 and a lower mold 2 facing the upper mold 1 are provided. A mold release layer 4 made of the second low adhesion material described in Example 2 is formed on the mold surface 3 which is the surface of the upper mold 1. Therefore, the upper die 1 corresponds to the molding die of this embodiment. In addition, the mold release layer 4 is a layer which bears the specific function of high mold release property when used as a mold.

The substrate 5 shown in FIG. 3 is composed of ZrO ₂ based ceramics. The base material 5 is formed with a resin passage 6 which is a space in which a flowable resin (not shown) flows after the mold is completed. Further, the base material 5 is formed with a cavity 7 which is a space filled with the fluid resin after the mold is completed. The resin passage 6 and the cavity 7 are formed by a method such as machining or molding before sintering. Further, the surface 8 of the substrate 5 includes a surface that overlaps the mold surface 3 in the resin passage 6 and the cavity 7 after the molding die is completed. Here, the fluid resin in contact with the mold surface 3 of the resin passage 6 and the cavity 7 is a basic substance such as an epoxy resin that is a thermosetting resin and contains moisture. .

As shown in FIG. 3, by including Y ₂ O ₃ and Zr ⁴⁺ which is a cation of a group 4A element in the vicinity of the mold surface 3 including at least the mold surface 3 in the upper mold 1, a release layer is obtained. 4 is formed. This means that the release layer 4 is composed of the second low adhesion material described in Example 2.

According to the present embodiment, the release layer 4 composed of the second low adhesion material is formed on the substrate surface 8. Thereby, the mold surface 3 of the upper mold 1 which is a mold is constituted by the surface of the release layer 4. Therefore, a mold having high releasability is obtained with respect to releasability between the mold surface 3 and the thermosetting resin.

In addition, it is good also as the mold release layer 4 being comprised with the 1st low-adhesion material demonstrated in Example 1. FIG. Further, the release layer 4 may be constituted by the third low adhesion material described in the third embodiment. In this case, a mold having a higher mold release property can be obtained with respect to the mold release property between the mold surface 3 and the thermosetting resin.

Hereinafter, a mode in which the mold shown in FIG. 3 is used will be described. This mold is used when resin-sealing chip-shaped parts such as semiconductor chips.

As shown in FIG. 3, first, a substrate 9 such as a lead frame, a printed circuit board, or a ceramic substrate is disposed on the lower mold 2. The electrodes of the chip 10 mounted on the substrate 9 and the electrodes of the substrate 9 (both not shown) are electrically connected by wires 11. On the lower mold 2, the substrate 9 is positioned and arranged at a position where the chip 10 and the wire 11 can be accommodated in the cavity 7.

Next, the heated upper mold 1 and lower mold 2 are clamped. Thereafter, a fluid resin (not shown) made of an epoxy resin, which is a thermosetting resin, is filled into the cavity 7 via the resin passage 6.

Next, the fluid resin is subsequently heated. As a result, a cured resin (not shown) is formed in each of the resin passage 6 and the cavity 7.

Next, after the upper mold 1 and the lower mold 2 are opened, a resin sealing body (not shown) in which the chip 10 on the substrate 9 is sealed with resin is taken out. Here, the release layer 4 provided in the vicinity of the mold surface 3 including the mold surface 3 of the upper mold 1 has low adhesion to a basic substance, a thermosetting resin, or a substance containing moisture. . Therefore, the release layer 4 has low adhesion to a cured resin (not shown) made of an epoxy resin that is a basic thermosetting resin and contains moisture. As a result, the cured resin is released from the release layer 4, in other words, from the mold surface 3 of the upper mold 1.

Next, using an appropriate means, an unnecessary resin made of a cured resin (not shown) cured in the resin passage 6 is separated from the resin sealing body. Through the steps so far, a finished product (package) of the electronic component including the substrate 9, the chip 10, and the cured resin is completed.

In addition, as shown in FIG. 4, the entire upper mold 12, which is a mold, may be configured by the bulk material 13. In this case, first, the powdered material may be molded according to the shape of the mold, and then the molded material may be sintered. Moreover, after forming in a rectangular parallelepiped shape, you may sinter and create a bulk material, and you may perform machining, such as cutting, with respect to the bulk material.

When the release layer 4 is formed on the mold surface 3 of the mold (upper mold 1, upper mold 12), a block-like (cuboid) low-adhesion material is applied to the bottom surface or the top surface of the cavity 7. You may use as a cavity block to comprise. In this case, a part of the mold surface 3 with which the fluid resin 13 contacts, for example, the inner bottom surface (upper surface in FIGS. 3 and 4) of the cavity 7 is formed of a low adhesion material.

In this example (Example 6), the molding die (upper die 1 and upper die 12) used when resin-sealing the chip 10 mounted on the substrate 9 using transfer molding is used. Explained with an example. Not limited to this, the structure of the mold of the present invention can be applied to a mold used in general compression molding, injection molding, and the like. In other words, the structure of the mold of the present invention is applied to a mold used when a molded body is produced by curing the fluid resin in a state where the cavity 7 is filled with the fluid resin. Can do.

Further, the mold described in the present embodiment includes a punching die. That is, it is a mold used when a material is punched to produce a molded product, and is in contact with at least one of a basic substance, a thermosetting resin, and a substance containing moisture. The low adhesion material of the present invention can be used for a possible mold.

In the description so far, the amount of the cation of the group 4A element contained on the surface of the low adhesion material or the like is more than 0 mol% and not more than 20 mol%. The reason is that if the amount of the cation of the group 4A element exceeds 20 mol%, the product becomes a composite oxide, and it is expected that it will be difficult to obtain the characteristic of low adhesion in the product. The upper limit ratio of “20 mol%” described above varies depending on the type, combination, addition rate, and the like of the additive. Considering this variation, the amount of the cation of the group 4A element is preferably more than 0 mol% and not more than 15 mol%.

Also, the low adhesion material produced by the method for producing a low adhesion material described in Example 4 can be used as an antifouling material or a mold. Therefore, the method for producing a low adhesion material described in Example 4 can be applied as a method for producing an antifouling material or a method for producing a mold.

Although the invention has been described and shown in detail, it is clearly understood that this is by way of example only and should not be taken as a limitation, the scope of the invention being limited only by the appended claims. It will be.

1,12 Upper mold, 2 Lower mold, 3 Mold face, 4 Release layer, 5 Base material, 6 Resin passage, 7 Cavity, 8 Surface, 9 Substrate, 10 Chip, 11 Wire, 13 Bulk material.

Claims

A low adhesion material (4) having low adhesion to an object comprising a basic substance, a thermosetting resin, or a substance containing moisture,
A low adhesion material containing at least the surface of yttrium oxide and nitrogen.
A low adhesion material (4) according to claim 1, comprising:
The low adhesion material, wherein the amount of nitrogen is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.
A low adhesion material (4) according to claim 1, comprising:
The low adhesion material (4) has a base material,
The base material contains zirconium oxide as a main component,
The low-adhesion material in which the yttrium oxide and the nitrogen are contained in a layered portion provided on the surface of the base material.
A low adhesion material (4) having low adhesion to an object comprising a basic substance, a thermosetting resin, or a substance containing moisture,
A low-adhesion material containing at least a surface thereof containing yttrium oxide and a cation of a group 4A element.
A low adhesion material (4) according to claim 4, comprising:
The low adhesion material, wherein the amount of the cation of the group 4A element is more than 0 mol% and not more than 20 mol%.
A low adhesion material (4) according to claim 4, comprising:
The low adhesion material, wherein the cation of the group 4A element is at least one of Zr 4+ and Hf 4+ .
A low adhesion material (4) according to claim 4, comprising:
The low adhesion material (4) has a base material,
The base material contains zirconium oxide as a main component,
A low-adhesion material in which the yttrium oxide and the cation of the group 4A element are contained in a layered portion provided on the surface of the base material.
A low adhesion material (4) having low adhesion to an object consisting of a basic substance, a thermosetting resin, or a substance containing water,
A low-adhesion material containing at least a surface thereof containing yttrium oxide, nitrogen, and a cation of a group 4A element.
A low adhesion material (4) according to claim 8, comprising:
The low adhesion material, wherein the amount of nitrogen is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.
A low adhesion material (4) according to claim 8, comprising:
The low adhesion material, wherein the amount of the cation of the group 4A element is more than 0 mol% and not more than 20 mol%.
A low adhesion material (4) according to claim 8, comprising:
The low adhesion material, wherein the cation of the group 4A element is at least one of Zr 4+ and Hf 4+ .
A low adhesion material (4) according to claim 8, comprising:
The low adhesion material (4) has a base material,
The base material contains zirconium oxide as a main component,
The low-adhesion material in which the yttrium oxide, the nitrogen, and the cation of the group 4A element are included in a layered portion provided on the surface of the base material.
An antifouling material (4) having an antifouling property against dirt containing an object composed of a substance having basicity, a thermosetting resin, or a substance containing moisture,
An antifouling material containing at least its surface containing yttrium oxide and nitrogen.
An antifouling material according to claim 13, comprising:
The antifouling material, wherein the amount of nitrogen is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.
An antifouling material according to claim 13, comprising:
The antifouling material (4) has a base material,
The base material contains zirconium oxide as a main component,
The antifouling material, wherein the yttrium oxide and the nitrogen are contained in a layered portion provided on the surface of the base material.
An antifouling material (4) having an antifouling property against dirt containing an object composed of a substance having basicity, a thermosetting resin, or a substance containing moisture,
An antifouling material comprising at least a surface thereof containing yttrium oxide and a cation of a group 4A element.
An antifouling material according to claim 16, comprising:
The antifouling material, wherein the amount of the cation of the group 4A element is more than 0 mol% and not more than 20 mol%.
An antifouling material according to claim 16, comprising:
The antifouling material, wherein the cation of the group 4A element is at least one of Zr 4+ and Hf 4+ .
An antifouling material according to claim 16, comprising:
The antifouling material (4) has a base material,
The base material contains zirconium oxide as a main component,
The antifouling material, wherein the yttrium oxide and the cation of the group 4A element are contained in a layered portion provided on the surface of the base material.
An antifouling material (4) having an antifouling property against dirt containing an object composed of a substance having basicity, a thermosetting resin, or a substance containing moisture,
An antifouling material comprising at least a surface thereof containing yttrium oxide, nitrogen, and a cation of a group 4A element.
An antifouling material according to claim 20, comprising:
The antifouling material, wherein the amount of nitrogen is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.
An antifouling material according to claim 20, comprising:
The antifouling material, wherein the amount of the cation of the group 4A element is more than 0 mol% and not more than 20 mol%.
An antifouling material according to claim 20, comprising:
The antifouling material, wherein the cation of the group 4A element is at least one of Zr 4+ and Hf 4+ .
An antifouling material according to claim 20, comprising:
The antifouling material (4) has a base material,
The base material contains zirconium oxide as a main component,
The antifouling material, wherein the yttrium oxide, the nitrogen, and the cation of the group 4A element are contained in a layered portion provided on the surface of the base material.
A mold (1, 12) used when molding a molded article,
Mold with at least its surface containing yttrium oxide and nitrogen.
A mold according to claim 25, wherein
The molding die, wherein the amount of nitrogen is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.
A mold according to claim 25, wherein
The mold (1, 12) has a base material,
The base material contains zirconium oxide as a main component,
The shaping | molding die in which the said yttrium oxide and the said nitrogen are contained in the layered part provided on the surface of the said base material.
A mold (1, 12) used when molding a molded article,
A mold having at least a surface thereof containing yttrium oxide and a cation of a group 4A element.
A mold according to claim 28, wherein
The mold according to claim 4, wherein the amount of the cation of the group 4A element is more than 0 mol% and not more than 20 mol%.
A mold according to claim 28, wherein
The mold according to claim 4, wherein the cation of the group 4A element is at least one of Zr 4+ and Hf 4+ .
A mold according to claim 28, wherein
The mold (1, 12) has a base material,
The base material contains zirconium oxide as a main component,
A molding die in which the yttrium oxide and the cation of the group 4A element are contained in a layered portion provided on the surface of the base material.
A mold (1, 12) used when molding a molded article,
A mold having at least a surface thereof containing yttrium oxide, nitrogen, and a cation of a group 4A element.
A mold according to claim 32, comprising:
The molding die, wherein the amount of nitrogen is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.
A mold according to claim 32, comprising:
The mold according to claim 4, wherein the amount of the cation of the group 4A element is more than 0 mol% and not more than 20 mol%.
A mold according to claim 32, comprising:
The mold according to claim 4, wherein the cation of the group 4A element is at least one of Zr 4+ and Hf 4+ .
A mold according to claim 32, comprising:
The mold (1, 12) has a base material,
The base material contains zirconium oxide as a main component,
The molding die in which the yttrium oxide, the nitrogen, and the cation of the group 4A element are included in a layered portion provided on the surface of the base material.
A method for producing a material having low adhesion to an object made of a substance having basicity, a thermosetting resin, or a substance containing moisture, a method for producing a material having antifouling property against dirt containing the object, or , A method for producing a mold used when molding a molded article,
Providing a first raw material containing yttrium oxide and a group 4A element;
Using the first raw material, at least the surface of any one of the low adhesion material, the antifouling material, and the mold contains the yttrium oxide and the cation of the group 4A element The manufacturing method provided with the process to make.
A manufacturing method as set forth in claim 37,
While preparing a step of preparing a base material containing zirconium oxide as a main component,
In the step of containing the yttrium oxide and the cation of the 4A group element, the layered portion provided on the surface of the base material includes the yttrium oxide and the cation of the 4A group element. A manufacturing method to make a state.
A manufacturing method as set forth in claim 37,
A manufacturing method provided with the process of further including nitrogen in at least the surface of any of the low adhesion material, the antifouling material, and the mold.
A manufacturing method as set forth in claim 39,
The amount of the said nitrogen is a manufacturing method which is 0.01 mol% or more and 10 mol% or less in conversion of a nitrogen atom.
A manufacturing method as set forth in claim 37,
The method according to claim 4, wherein the amount of the cation of the group 4A element is more than 0 mol% and not more than 20 mol%.
A manufacturing method as set forth in claim 37,
The method of producing, wherein the cation of the group 4A element is at least one of Zr 4+ and Hf 4+ .
A method for producing a material having low adhesion to an object made of a substance having basicity, a thermosetting resin, or a substance containing moisture, a method for producing a material having antifouling property against dirt containing the object, or , A method for producing a mold used when molding a molded article,
Preparing a second raw material containing yttrium oxide as a main component;
A manufacturing method comprising a step of including nitrogen in the surface of the second raw material.
A manufacturing method according to claim 43, comprising:
The production method wherein the amount of nitrogen contained in any of the surfaces of the second raw material is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.